Photocatalytic degradation of 4-nitrophenol in aqueous suspension by Using Functionalized Porphyrin-TiO2 Photocatalysis Under Visible Irradiation

Environmentally Friendly Photocatalytic Oxidation of Aromatic Alcohol to Aldehyde in Aqueous Suspension of Brookite TiO(2)

WOS: 000260509000008

Nature of Interactions at the Interface of Two Water-Saturated Commercial TiO2 Polymorphs

Two commercial TiO2 samples, a 100% anatase and a 100% rutile, were used for the fast field cycling NMR experiments. The results showed a different behavior between the different samples. In particular, water molecules were unbonded to the solid surface for the rutile sample, whereas they appeared to chemically interact with the surface through H-bond formation with the anatase sample. The above findings accord with the generally lower activity of rutile with respect to anatase reported in literature for photocatalytic oxidation reactions in water. The difficulty of water to interact with rutile surface, indeed, could hinder the formation of OH radicals, which are the most important oxidant…

Brookite, the Least Known TiO2 Photocatalyst

Brookite is the least studied TiO2 photocatalyst due to the difficulties usually encountered in order to obtain it as a pure phase. In this review, a comprehensive survey of the different methods available for preparing brookite powders and films is reported. Attention has been paid both to the most traditional methods, such as hydrothermal processes at high temperatures and pressures, and to environmentally benign syntheses using water soluble compounds and water as the solvent. Papers reporting the photocatalytic activity of pure and brookite-based samples have been reviewed.

Photocatalytic oxidation of aromatic alcohols to aldehydes in aqueous suspension of home prepared titanium dioxide: 2. Intrinsic and surface features of catalysts

Some intrinsic electronic properties of home prepared (HP) TiO2 catalysts were investigated by diffuse reflectance spectroscopy and quasi-Fermi level measurements. These powders were used for carrying out the photocatalytic oxidation of benzyl alcohol to benzaldehyde and CO2 in water; the selectivity for aldehyde formation was enhanced by the addition of small amounts of ethanol, a typical hole trap. The values of band gap, valence band and conduction band edges are almost identical for all the HP samples in which anatase phase is predominant, whereas appreciable differences can be noticed for an HP sample containing high amount of rutile phase. A comparative ATR-FTIR study of the HP cataly…

Influence of some aromatic and aliphatic compounds on the rate of photodegradation of phenol in aqueous suspensions of TiO2

Abstract The influence of 3-nitrophenol, 4-nitrophenol, pentachlorophenol, ethanol, 2-propanol, ethanoic acid and ethanedioic acid on the photodegradation rate of phenol in an aqueous suspension of TiO2 (anatase) irradiated in the near-UV region was investigated. Binary mixtures of organic compound and phenol in molar ratios of 1:1 and 10:1 were used for the photoreactivity experiments performed in a batch reactor. The mineralization rate of all the mixtures was also monitored by measuring the total organic carbon (TOC) concentration. The reactivity results indicate that the photodegradation rate of phenol is mainly determined by the total amount of aromatic substrates present in the reacti…

TiO2 thin films: preparation, characterisation and their photocatalytic activity

Influence of operational variables on the photodegradation kinetics of Monuron in aqueous titanium dioxide dispersions

The degradation of Monuron [N′—(4-chlorophenyl)—N, N dimethyl urea] in aqueous TiO 2 dispersions irradiated in the near-UV region has been investigated using a Pyrex batch photoreactor. The influence on the degradation kinetics of pH, initial Monuron concentration and catalyst concentration has been studied. The mineralization of the pollutant was also investigated. Measurements of photon absorbed flows allowed to determine the quantum yield values; they were found to increase by increasing the initial pH of the dispersion.

Comparison between catalytic and catalytic photo-assisted propene hydration by using supported heteropolyacid

Abstract Hybrid materials have been prepared by impregnation of the heteropolyacid H 3 PW 12 O 40 on commercial TiO 2 . The polyoxometalates (POM) amount deposited was 15, 30, 50 and 70% with respect to the weight of the TiO 2 support. Moreover two samples containing a POM amount of 15, and 50% with respect to the weight of SiO 2 were also prepared for the sake of comparison. All prepared samples were efficient catalysts for the hydration of propene to 2-propanol in gas–solid regime at atmospheric pressure and at temperatures ranging between 50 and 85 °C. The study carried out on the hybrid TiO 2 based materials evidenced that, as far as the catalytic activity is concerned, exists an optimu…

Junction Effect on the Photocatalytic Activity of Mixed-Phase TiO2 Nanoparticles

Active TiO2 photocatalysts were prepared under mild experimental conditions by thermohydrolysis of TiCl4 in pure water at 100 {degree sign}C. The preparation method is very simple and does not require the use of expensive thermal or hydrothermal treatments. Depending on the TiCl4/H2O ratio, pure rutile, binary mixtures of anatase and rutile or anatase and brookite, or ternary mixtures of anatase, brookite and rutile, can be obtained. 4-nitrophenol photodegradation was used to evaluate the photoactivity of the various powders. The high photocatalytic activity of the mixed samples was explained by the presence of junctions among different polymorphic TiO2 phases that allows an improved charge…

Photocatalytic Selective Oxidation of 5-(Hydroxymethyl)-2-furaldehyde to 2,5-Furandicarbaldehyde in Water by Using Anatase, Rutile, and Brookite TiO2 Nanoparticles

5-(Hydroxymethyl)-2-furaldehyde (HMF) was selectively oxidized to 2,5-furandicarbaldehyde (FDC) in; aqueous medium by using home prepared (HP) anatase, rutile, and brookite TiO2 nanoparticles. HP samples were prepared via a sol-gel method by using TiCl4 as the TiO2 precursor. Commercial TiO2 catalysts were also used for, comparison. All samples were characterized by BET specific surface area, XRD, TGA, and SEM, and the reactivity results showed that HP catalysts are predominantly amorphous and give rise to selectivities toward FDC more than twice that of commercial and well crystallized catalysts.

Introduction by Guest Editors

High activity of brookite TiO2 nanoparticles in the photocatalytic abatement of ammonia in water

Abstract The effects of the TiO 2 crystal structure and its surface modification with Pt nanoparticles on the photocatalytic oxidation of NH 3 in the aqueous phase were studied with home-made TiO 2 photocatalyst powders synthesized by a thermo-hydrolysis approach that allowed a fine control of the crystallographic phase composition. Ammonia conversion and the selectivity toward mildly oxidized N 2 and highly oxidized nitrite and nitrate anions were monitored during the runs. Pure brookite powders modified by Pt nanoparticles, deposited either from a colloidal suspension or by deposition–precipitation, were found to be the most efficient photocatalysts in NH 3 degradation, with a desired goo…

Concerning“An Opinion on the Heterogeneous Photoreduction of N2 with H2O”: Second Letter

Preparation and photoactivity of nanocrystalline TiO2 powders obtained by thermohydrolysis of TiOSO4

Nanocrystalline TiO2 photocatalysts were synthesized in mild conditions by thermohydrolysis of TiOSO4 in water at 100 °C and post-calcination treatment at various temperatures. The TiO2 powders were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, specific surface area determinations, scanning electron microscopy and electron paramagnetic resonance measurements. The photoactivity of the samples was tested employing the photodegradation of 4-nitrophenol in liquid–solid regimen and the photooxidation of gaseous 2-propanol. The best results were obtained with the powder calcined at 600 °C for 10 h. Surprisingly, the not calcined sample was the most active for the abatement…

Oxidation of aromatic alcohols in irradiated aqueous suspensions of commercial and home-prepared rutile TiO(2): a selectivity study.

WOS: 000256241700021

Alcohol-Selective Oxidation in Water under Mild Conditions via a Novel Approach to Hybrid Composite Photocatalysts

Abstract The oxidation of alcohols to carbonyl compounds in a clean fashion (i.e., with water as a solvent or under solvent‐free conditions, and using O2 or H2O2 as the primary oxidant) is the subject of considerable research efforts. A new approach for the selective oxidation of soluble aromatic alcohols in water under mild conditions via a novel composite photocatalyst has been developed. The catalyst is synthesized by grafting 4‐(4‐(4‐hydroxyphenylimino)cyclohexa‐2,5dienylideneamino)phenol and silver nanoparticles onto the surface of moderately crystalline titanium dioxide. The titanium dioxide‐based composite was first extensively characterized and then employed in the catalytic oxidati…

Polymer leaf of expanded material coated with titanium dioxide exhibiting photocatalytic activity, container and package for foodstuffs obtained from said polymer leaf

Photocatalytic activity of titanium dioxide thin films prepared by a sol-gel method

Comparison between catalytic and photocatalytic activity in gas-solid regime of semiconductor oxides and carbon nanotubes supported Keggin heteropolyacid.

Catalytic and photocatalytic 2-propanol dehydration was carried out by using a supported Keggin heteropolyacid H3PW12O40 (PW12). Binary materials were prepared by impregnation and/or solvothermal treatment by using commercial supports: SiO2 (Mallinckrodt), TiO2 (Evonik P25) and multiwall carbon nanotubes (Sunnano) or home solvothermically prepared SiO2 and TiO2. All the materials have been characterized by X-ray diffraction (XRD), scanning electron microscopy observations (SEM) coupled with EDX microanalysis, specific surface area measurements, diffuse reflectance spectroscopy (DRS), FTIR and Raman spectroscopy. (Photo)catalytic 2-propanol dehydration was studied in gas-solid regime by usin…

A structural investigation of titanium dioxide photocatalysts

Abstract A study of the structure and the morphology of a titanium dioxide photocatalyst (Degussa P25) reveals multiphasic material consisting of an amorphous state, together with the crystalline phases anatase and rutile in the approximate proportions 80 20 . Transmission electron microscopy provides evidence that some individual particles are a mixture of the amorphous state with either the anatase phase or with the rutile phase, and that some particles, which are mostly anatase, are covered by a thin overlayer of rutile which manifests its presence by the appearance of Moire fringes. The photocatalytic activity of this form of titanium dioxide is reported as being greater than the activi…

Comparison between preparative methodologies of nanostructured carbon nitride and their use as selective photocatalysts in water suspension

Carbon nitride photocatalysts have been prepared by different methodologies, such as chemical ultrasonic irradiation (sonochemical treatment), hydrothermal and ball milling and thermoexfoliation, and have been used for the selective oxidation of 5-hydroxymethyl-2-furaldehyde (HMF) to form 2,5-furandicarboxyaldehyde (FDC) in water suspension both under UV and natural solar irradiation. The physico-chemical features of the photocatalysts have been studied by X-ray diffraction, infrared spectroscopy, UV–Vis diffuse reflectance spectroscopy, photoluminescence spectroscopy, scanning electron microscopy, and specific surface area measurements. The results indicate that exfoliation of carbon nit…

Adsorption and Photocatalytic Degradation of Acetonitrile on TiO2: FTIR and Kinetic Studies

Coupled Semiconductor Systems for Photocatalysis. Preparation and Characterization of Polycrystalline Mixed WO3/WS2 Powders

Mixed WO3/WS2 powders were prepared by oxidation of WS2. The physical properties of the samples were characterized by X-ray diffraction, diffuse reflectance spectroscopy, and scanning electron microscopy; they were strongly dependent upon the time and temperature of oxidation. The chemical state and the elemental distribution of the sample surface were investigated by X-ray photoelectron spectroscopy. The photocatalytic results have showed that the aqueous suspensions of the mixed WO3/WS2 systems have significantly higher activities than pure WS2 and WO3 for the photodegradation of phenol. The enhanced performance can be related to the presence of heterojunctions WO3/WS2 on the single parti…

Photoactivity of shape-controlled TiO2 in gas-solid regime under solar irradiation

Abstract Differently shape-controlled anatase TiO2 materials were tested as photocatalysts under both simulated and natural solar irradiation. Their photocatalytic activity in 2-propanol and propene partial oxidation and in the complete mineralization of acetaldehyde appears to increase with decreasing the shape control of the TiO2 material. This insight seems to be related to the residual presence of the templating species (fluoride anions) employed during the preparation of the shape-controlled TiO2 materials. In fact, the calcination of the powders, leading to levelling of the fluoride ions content, but also to a remarkable surface area decrease, gave rise to an increase of photocatalyti…

Ossidazione mediante fotocatalisi e ozonizzazione dello ione ossalato in soluzioni acquose contenenti biossido di titanio

Selective heterogeneous photocatalysis: examples of green photosyntheses

Degradation of Drugs in Aqueous Medium: Photocatalytic oxidation of Lincomycin

Photocatalytic selective oxidation of 4-methoxybenzyl alcohol to aldehyde in aqueous suspension of home-prepared TiO2 catalyst

The photocatalytic oxidation of 4-methoxy-benzyl alcohol to p-anisaldehyde (PAA) was performed in water with organic-free suspensions of home-prepared and commercial titanium dioxide (TiO2) catalysts. The nanostructured TiO2 samples were synthesised by boiling aqueous solutions of titanium tetrachloride (TiCl4), under mild conditions, for different times. The crystallinity increased with the boiling time. The 4-methoxybenzyl alcohol oxidation rate followed the same pattern but the highest yield (41.5 % mol) to PAA was found for the least crystalline sample, that showed a quantum efficiency of 0.116 %. A comparison with two commercial TiO2 samples showed that all the home-prepared catalysts …

Special needs and characteristic features of (photo)catalytic reactors with a review of the proposed Solutions

Abstract In the present chapter, the analogies between photocatalytic systems and the systems where the more common thermally activated reactions take place are highlighted. The objective is to propose a unified approach for the analysis and the design, which, however, must take into account how and why photocatalytic reactors differ from reactors with thermal reactions. The necessity of absorbing photons to activate the photocatalytic process adds complexity to the system, but some approaches are presented to simplify the problems and make easier their solution.

Titania Photocatalysts for Selective Oxidations in Water

Heterogeneous photocatalysis by polycrystalline semiconductor oxides is an unconventional technology that has been mainly applied for the degradation of organic and inorganic pollutants in both the vapor and liquid phase. The application of photocatalysis in synthetic routes has also been researched in recent years, demonstrating its viability as an alternative route in organic chemistry. This work illustrates the main findings in the application of heterogeneous photocatalysis to the oxidation of organic compounds dissolved in water, free of any organic co-solvent. Two main aspects of the oxidative process have been studied: the first one is the partial oxidation of various mono-substitute…

Strategy assessment to mediate between purification targets and bromate production during purification of bromide containing water by means of photocatalytic ozonation

TiO2-H3PW12O40 binary solids prepared in different conditions: a comparison of their photocatalytic activity

Photoreactivity of Iron-Doped Titanium Dioxide Powders for Dinitrogen Reduction to Ammonia

The production of NH3 from N2 and H2O on Fe/TiO2 has been studied in a continuous photoreactor under UV radiation. An ESR study of the catalysts shows that Fe3+ ions are better electron traps than Ti4+ ions. This trapping can be irreversible if the corresponding holes originate stable species adsorbed on the catalyst surface. The charge separation, thus favoured by the Fe3+ ions, helps the N2 adsorption by its reaction with surface species activated by holes. The best activity is found when no excess Fe is segregated at the surface; overall turnover for N2 reduction as high as 6 e−/Fe atom can be reached before catalyst deactivation.

Sol-gel derived anatase TiO2: morphology and photoactivity

Abstract High-surface area TiO 2 (anatase) was prepared by the sol-gel method and characterized by various instrumental and analytical methods, including X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, porosimetry, specific surface area measurements, scanning electron microscopy, and titration of surface hydroxyl groups. The specimen was tested for photodegradation of phenol and nitrophenols carried out in aqueous suspension at pH = 3; photoactivity was compared with that of commercially available anatase TiO 2 . Results are discussed in terms of porosity, surface area, and availability and population of surface OH groups, consequent upon the particular method used for…

Synthesis, Characterisation and Photocatalytic Tests of Anatase Titanium Dioxide Powders Prepared Via Sol-Gel with Different Chelating Agents and under Different Gelling Pressure Conditions

Adsorption and photocatalytic degradation of acetonitrile: FT-IR investigation

Abstract The photocatalytic degradation of acetonitrile was carried out in liquid–solid regime in a batch reactor by using two types of commercial TiO 2 powders (Merck and Degussa P25) as photocatalysts. The concentration of acetonitrile and non-purgeable organic carbon (NPOC) were monitored. The initial rate of acetonitrile conversion was found higher on TiO 2 Merck than on TiO 2 P25. FT-IR spectroscopy was used to investigate the molecular features of the adsorption and photo-oxidation of acetonitrile on the two TiO 2 powders in a fully surface hydrated form. Acetonitrile was found adsorbed on Ti 4+ surface ions and hydroxyl groups for both types of TiO 2 . This interaction appeared fully…

Photoelectrocatalytic Selective Synthesis of p-Anisaldehyde in Water by TiO2 Supported on Ti Anodes

Photocatalytic oxidation of toluene on irradiated TiO2: comparison of degradation performance in humidified air, in water and in water containing a zwitterionic surfactant

Photocatalytic degradation of toluene was carried out both in gas–solid and in liquid–solid regime by using polycrystalline samples of TiO2 Merck and TiO2 Degussa P25. For the gas–solid regime two types of continuous photoreactor were used, a fixed bed one of cylindrical shape and a Carberry type photoreactor, both irradiated by near-UV light. The inlet reacting mixture consisted of air containing toluene and water vapours. The influence of the gas flow rate and the presence of water vapour on the photocatalytic process was investigated. CO2 and benzaldehyde were the toluene degradation products detected in the gas phase by using TiO2 Merck. In the presence of water vapour this catalyst exh…

Biological effects and photodegradation by TiO(2) of terpenes present in industrial wastewater.

Abstract The aim of this work was to study the biological effects of four monoterpenes, i.e. α-pinene, β-pinene, 3-carene and d -limonene present in the wastewater of a citrus transformation factory. The study was carried out by exposing V79 Chinese hamster cells to single terpene or to the mixture of four terpenes at concentrations corresponding to those in the wastewater evaluated by head space solid phase micro extraction and gas chromatography (HS-SPME-GC) analyses. Treatments with single or combined terpenes similarly affected cell vitality, but only the combined treatments induced the 6-thioguanine resistant mutants. Moreover the photocatalytic degradation of the four terpenes was suc…

Production of Aldehydes by Oxidation in Aqueous Medium with Selective Recovery of the Product by Means of Pervaporation

Heterogeneous Photocatalysis for Selective Formation of High-Value-Added Molecules: Some Chemical and Engineering Aspects

This review deals with the parameters that influence heterogeneous photocatalysis (PC) for selective synthesis of high-value chemicals by itself or in combination with other technologies. In particular, the parameters related to the photocatalysts, such as crystallinity degree, type of polymorph, surface acid-base properties, exposure of particular crystalline facets, coupling of different semiconductors, position of the valence and conduction band edge, addition of doping agents, and those related to the reaction system, such as setup configuration and reactor geometry, type of solvent, type and amount of photocatalyst, affecting the selectivity toward specific products are described and d…

Photocatalytic degradation of paraquat Combined with a genotoxicity Study of the Intermediate Products

Binary Materials TiO2 or ZnO-Activated Carbon Used as Photomediators in the Photocatalytic Degradation of 2-Propanol in Gas-Solid Regime

Photocatalytic Degradation of 4-Nitrophenol by Using Porphyrin/Fe-Loaded TiO2 Composites Under Heterogeneous Photo Fenton Process

A new class of porphyrin(Pp)/Fe co-loaded TiO2 composites opportunely prepared by impregnation of [5,10,15,20-tetra(4-tert-butylphenyl)] porphyrin (H2Pp) or Cu(II)[5,10,15,20-tetra(4-tert-butylphenyl)] porphyrin (CuPp) onto Fe-loaded TiO2 particles showed high activities toward the degradation of 4-nitrophenol (4-NP) by heterogeneous photo Fenton-like processes.

TiO2-Based Photocatalysis for Organic Synthesis

A major aim of the contemporary chemistry is to replace old environmentally hazardous processes with new, energy efficient routes allowing to reduce or totally avoid the use and production of harmful chemicals and to maximise the quantity of raw material that ends up in the final product. This chapter gives an account of TiO2-based selective photocatalysis as a green synthetic tool for the production of organics. Some case studies of the most common transformations carried out by means of photocatalytic reactions are illustrated in a midway perspective between photochemistry and organic chemistry.

Enhanced Solar Light Photocatalytic Activity of Ag Doped TiO2–Ag3PO4 Composites

Composites comprised of Ag3PO4 and bare TiO2 (TiO2@Ag3PO4) or silver doped TiO2 (Ag@TiO2&ndash

CO2 Reduction in Gas-Solis Regime by Using GaP/TiO2 as Photocatalyst

Tungstophosphoric Acid Supported on TiO2 for the Photodegradation of 4-Nitrophenol in Liquid Phase and of 2-Propanol in gas Phase

Photocatalytic membrane reactors

TiO2 Supported over Hβ and HZSM-5 Photocatalysts for Salmonelle and Escherichia Coli Disinfection

Combination of different advanced oxidation processes and activated carbons for treatment of salt water

Bilgewater is a corrosive polluted effluent from the bilge of ships that mainly originates from seawater infiltration and leakage of engine oil and fuel. Each year, thousands tons of hydrocarbons from bilge are discharged at sea. In order to prevent hydrocarbon discharge at sea from the bilge of ships, the Internation Maritime Organization (IMO) enacted the MARPOL 73/78 convention in which effluents are now limited to those with maximun oil content of 15 ppmv.

Azo-Dyes Photocatalytic Degradation in Aqueous Suspension of TiO2 Under Solar Irradiation

Abstract The photodegradation of two common and very stable azo-dyes, i.e. methyl-orange (C14H14N3SO3Na) and orange II (C16H11N2SO4Na), is reported. The photocatalytic oxidation was carried out in aqueous suspensions of polycrystalline TiO2 irradiated by sunlight. Compound parabolic collectors, installed at the “Plataforma Solar de Almeria” (PSA, Spain) were used as the photoreactors and two identical reacting systems allowed to perform photoreactivity runs for the two dyes at the same time and under the same irradiation conditions. The disappearance of colour and substrates together with the abatement of total organic carbon content was monitored. The main sulfonate-containing intermediate…

Cerium and cerium oxide: A brief introduction

Abstract A short introduction on the history and main properties of cerium and cerium oxide is here provided. The main applications of cerium oxide, reported and discussed in this book, are also briefly summarized, with some final considerations on the future perspectives and the market outlooks of this outstanding oxide.

Pickering Emulsions of Fluorinated TiO2: A New Route for Intensification of Photocatalytic Degradation of Nitrobenzene

International audience; Fluorination of the TiO2 surface has been often reported as a tool to increase the photocatalytic efficiency due to the beneficial effects in terms of production of oxidizing radicals. Moreover, it is shown that the unique amphiphilic properties of the fluorinated TiO2 (TiO2-F) surface allow one to use this material as a stabilizer for the formulation of Pickering emulsions of poorly soluble pollutants such as nitrobenzene (NB) in water. The emulsions have been characterized in terms of size of the droplets, type of emulsion, possibility of phase inversion, contact angle measurements, and optical microscopy. The emulsified system presents micrometer-sized droplets of…

Optical Properties and Quantum Yields Determination in Photocatalytic Suspensions

Environmentally sustainable production of cellulose-based superabsorbent hydrogels

The development of new products and materials, especially those which are non-petrolchemical reserves and based on renewable organic resources, using innovative sustainable processes is nowadays of increasing interest and deserves the attention of both academic and industrial research. Cellulose and its derivatives, as renewable organic resources, have been used to synthesize novel superabsorbent hydrogels. Although the production of cellulose is one of the causes connected to deforestation, the production of suitably engineered cellulose superabsorbent hydrogel materials has been proposed to preserve water in typically arid areas in the world. Paradoxically, divinylsulfone (DVS), a small d…

Sunlight-induced functionalisation reactions of heteroaromatic bases with aldehydes in the presence of TiO2: A hypothesis on the mechanism

In previous studies we reported a new photocatalytic system involving polycrystalline TiO2 for the selective functionalisation of heteroaromatic bases with ethers and amides. In order to extend the applications of this new reaction and to better understand the mechanism involved, we have examined aromatic and aliphatic aldehydes as acyl radical sources for the nucleophilic addition to protonated N-heteroarenes in acetonitrile as the solvent and TiO2/H2O2 as the photocatalytic system. Acyl radicals may undergo decarbonylation to yield the corresponding alkyl radicals. Acyl/alkyl derivative ratios depend on the nature of the aldehydes, and present a different distribution from that obtained i…

The role of different oxides as supports of an heteropolyacid in the catalytic and catalytic photo-assisted propene hydration

Ferulic Acid Oxidation Through Visible Light Induced TiO2 Photocatalysis

Photocatalytic behavior of mixed WO3/WS2 powders

Polycrystalline mixed WO3/WS2 powders have been prepared by different methods. The samples have been characterized by bulk and surface techniques and tested as catalysts for the photodegradation of phenol. The results have indicated that the coupling of WO3 and WS2 leads to an enhanced rate of disappearance of the organic substrate. The effect is explained as the result of the simultaneous electron transfer from WS2 to WO3 and hole transfer from WO3 to WS2. The efficiency of the mixed WO3/WS2 systems strongly depends on the relative amounts of WO3 and WS2 in the various samples. A maximum of photoactivity is obtained when the surface WS2 and WO3 molar fraction is about 0.5.

Kinetics of 4-Methoxybenzyl Alcohol Oxidation in Aqueous Solution in a Fixed Bed Photocatalytic Reactor

WOS: 000280384800004

Evaluation of Biological Effects and Heterogeneous Photodegradation of Terpenes Present in Wastewater From a Citrus Fruit Transformation Factory

Selective Heterogeneous Photocatalysis by TiO2 for Green Innovative Organic Syntheses: Achievements and Challenges

Sol-gel synthesis and photocatalytic activity of ZnO-SnO2 nanocomposites

Abstract ZnO–SnO 2 nanocomposites were synthesized by a facile sol–gel synthesis route and characterized through X-ray diffraction, BET specific surface area analysis, UV–vis diffuse reflectance spectroscopy, photoluminescence spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy. The photocatalytic activity of the samples was tested using the degradation of 4-nitrophenol under UV light as model reaction. The ZnO/SnO 2 molar ratio was varied in order to study its influence on the photoefficiency of the samples. The ZnO–SnO 2 nanocomposites showed higher photoactivity than the pure oxides and in particular the sample with ZnO/SnO 2 mol…

Process for the production of bromine

A process for the preparation of molecular bromine, by means of advanced oxidation processes or their combination is disclosed

Photocatalytic partial oxidation of phenenthrene in green organic solvents

Preparation, Characterisation and Photocatalytic activity of SrTiO3 based Perovskites.

A Solar Photothermocatalytic approach for the CO2 conversion: Investigation of different synergisms on CoO-CuO/Brookite TiO2-CeO2 catalysts

Abstract The photoactive features of the least common polymorph of TiO2, i.e. brookite, were combined with the thermocatalytic redox ones of cerium oxide, focusing on the effects of the addition of small amounts of Co-Cu oxides for the solar CO2 conversion. By considering the characterization data, a surface segregation of the hosted metal oxides on the TiO2-CeO2 composite was evidenced, and their presence increased the amount of oxygen vacancies and improved the charge carriers separation. The bimetallic oxides-based sample was the most performing one in the photocatalytic carbon dioxide reduction at room temperature. The formation of carbon monoxide and methane was 5 and 0.5 μmol g−1h−1, …

Photocatalytic Membrane Reactors in Water Purification

Potable water, industrial water, and wastewater are often polluted by toxic organic species. New methods, such as those involving heterogeneous photocatalytic reactions, allow in many cases a complete degradation of organic pollutants to small and non-noxious species, without using chemicals, avoiding sludge production and its disposal. When combined with membrane separation processes, photocatalytic membrane reactors (PMRs) are obtained. These have some advantages compared to conventional photoreactors. Indeed, confining of the photocatalyst in the reaction environment as a result of the presence of the membrane (separation at molecular level) enables operation with high amounts of catalys…

Heterogeneous photocatalytic aqueous succinic acid formation from maleic acid reduction

This study reports the anaerobic reduction of maleic acid to succinic acid in aqueous dispersion of different TiO2 based photocatalysts. Some home prepared and commercial solids containing different polymorphic phases of TiO2 and loaded with Pt and Ru were compared at different acidic pHs. The aim of the work was to verify the feasibility of the process and to determine the best samples and the optimal experimental conditions of the reaction. The best selectivity towards succinic acid was 23.2 % at 70 % of maleic acid conversion. Fumaric acid was also formed as another high added value compound, and its quantity was related to the experimental conditions and the photocatalyst used.

Turning lipophilic phthalocyanines/TiO2 composites into efficient photocatalysts for the conversion of CO2 into formic acid under UV–vis light irradiation

Metal-free, Cu(II)- or Zn(II) tetrakis [4-(2,4-bis-(1,1-dimethylpropyl)phenoxy)]phthalocyanines loaded over TiO2 (anatase) proved to be active in the photoreduction of CO2 to formic acid (HCO2H) in water under UV-vis light. CuPc/TiO2 is catalyst of choice, allowing to reach a maximum yield of HCO2H, unequalled by any other similar catalytic systems. Because of their low environmental impact, low potential cost, and efficient power conversion, these multipurpose materials show promise in the setup of sustainable methods for CO2 valorization. (C) 2014 Elsevier B.V. All rights reserved.

Polycrystalline TiO2 impregnated with porphyrin derivatives in the photocatalytic degradation of 4-nitrophenol

Characterization of TiO2 thin films for photocatalytic applications

Photocatalytic degradation of organic compounds in aqueous systems by transition metal doped polycrystalline TiO2

Abstract Some probe catalytic photooxidation reactions with aliphatic and aromatic organic compounds having different acid strengths, i.e. methanoic acid, ethanoic acid, benzoic acid and 4-nitrophenol, were carried out in aqueous systems by using polycrystalline TiO2 powders doped with various transition metal ions (Co, Cr, Cu, Fe, Mo, V and W). The Co-doped powder showed to be more photoactive than the bare TiO2 for methanoic acid degradation while the behaviour of TiO2/Cu and TiO2/Fe was similar to that of the support. TiO2/W was the most efficient sample for the photodegradation of benzoic acid and 4-nitrophenol, TiO2 the most active powder for ethanoic acid. A tentative explanation is p…

Heterogeneous photocatalytic materials for sustainable formation of high-value chemicals in green solvents

Abstract The most investigated materials used as heterogeneous photocatalysts for the formation of high-value chemicals under mild experimental conditions are presented in this survey. Only papers reporting reactions carried out in harmless solvents such as water, the green solvent par excellence, are reported. Metal oxides have been used often, but carbon-based materials such as carbon nitride and graphene, metal nanoparticles, sulphides and selenides also have received a great attention mainly due to their good performances both in partial oxidations and reductions. The results presented indicate that an appropriate choice of the photocatalytic material is the main problem to be faced to …

Preparation in mild conditions of photocatalytically active nanostructured TiO2 rutile

Abstract Nano structured TiO 2 rutile samples were prepared in mild conditions by hydrolysis of TiCl 4 in different solutions. The powders revealed a fair photoactivity for the photoeatalytic degradation of 4-nitrophenol. The influence of preparation procedure, pH and presence of Cl − and N 3 − anions on the physicochemical features and photocatalytic activity of the powders was investigated.

Photocatalytic degradation of organic pollutants by using polycrystalline TiO2: case studies for environment remediation

Photocatalytic CO<inf>2</inf> Valorization by Using Ti<inf>O2</inf>, ZrO2 and Graphitic Based Semiconductors

In this century, a broad scientific interest has been devoted to fulfill sustainable industrial processes and climatic change remediation. In this prospective, various green technologies have been studied to valorize CO 2• The aim of this research is the CO 2 reduction in presence of water by using the photocatalytic technology with nanomaterials as the photocatalysts. The present work overviews the main outcomes obtained by using graphitic and oxide based photocatalysts both in gas/solid and liquid/solid batch reactors under simulated solar light. In all gas/solid regime tests the major products detected were methane, carbon monoxide, and acetaldehyde.

A Dialysis Photocatalytic Reactor for the Green Production of Vanillin

In the present work, dialysis was used to recover vanillin while being produced by partial photocatalytic oxidation of ferulic acid in an aqueous solution at ambient temperature. The relatively high value of the permeate flux through a dense polyether-block amide membrane allowed continuously extracting vanillin from the reacting solution, thus avoiding its successive oxidation. The rate of vanillin formation was improved, compared to other reactor configurations, because intermediate compounds permeated from the reacting solution and did not hinder the reaction, while ferulic acid permeated in the opposite direction to partially replenish the reactor with the substrate. The photocatalytic …

Photodegradation of lincomycin in aqueous solutions

The role of H2O in the photocatalytic oxidation of toluene in vapour phase on anatase TiO2 catalyst

Abstract Photocatalytic oxidation of toluene has been carried out in a gas–solid regime by using polycrystalline anatase TiO2 in a fixed-bed continuous reactor. Air containing toluene and water vapours in various molar ratios was fed to the photoreactor irradiated by a medium pressure Hg lamp. Toluene was mainly photo-oxidised to benzaldehyde, and small amount of benzene, benzyl alcohol and traces of benzoic acid and phenol were also detected. In the presence of water, no decrease of photoreactivity was observed at steady-state conditions. By removing water vapour from the feed, the conversion of toluene to benzaldehyde was almost completely inhibited, and an irreversible deactivation of th…

ZrO2 Based materials as photocatalysts for 2-propanol oxidation by using UV and solar light irradiation and tests for CO2 reduction

Abstract Bare ZrO2, Ce doped ZrO2 and Er doped ZrO2 samples have been prepared by a hydrothermal process and have been used as photocatalysts for 2-propanol oxidation reaction in gas solid regime. Moreover, some preliminary tests have been carried out for CO2 reduction. The samples were physico-chemically characterized and both bare and doped ZrO2 based materials resulted active for oxidation and reduction reactions by using UV and solar irradiation. The reactivity results have been correlated with the compositional, structural and morphological features of the photocatalysts.

Photocatalytic oxidation of nitrobenzene and phenylamine: Pathways and kinetics

WOS: 000245150800018

Sunlight-induced reactions of some heterocyclic bases with ethers in the presence of TiO2

The reactions between various heterocyclic bases and ethers induced by sunlight are reported. In several cases the photoreaction occurred with higher yields in liquid–solid heterogeneous system in the presence of polycrystalline TiO2 than in homogeneous system. The derivatives obtained with trioxane may give an easy entry to heterocyclic aldehydes.

Le Potenzialità della Fotocatalisi Eterogenea alle Interfacce Gas-Solido e Liquido-Solido

Surface characterisation of metal ions loaded TiO2 photocatalysts: structure–activity relationship

Abstract Transition metal loaded TiO 2 powders were characterised and tested for the photodegradation of some organic acids. Both Lewis and Bronsted surface acid sites were present in the samples containing large amounts of Mo, V and W. The Bronsted sites are associated to the presence of the transition metals as they do not exist in the unloaded support, and in particular to the presence of these metals in high oxidation states. The trend of the pzc values of the various powders matches rather well both with the surface acidity of the samples experimentally determined by NH 3 adsorption and with a scale of acidity/basicity for bulk binary oxides. XPS investigation indicates that only the p…

Photocatalytic degradation of 4-nitrophenol in a continuous reactor containing titanium dioxide supported on glass beads

WOS: 000258975200009

Photocatalysis in dimethyl carbonate green solvent: degradation and partial oxidation of phenanthrene on supported TiO2

Dimethyl carbonate (DMC) is here proposed – for the first time – as a green organic solvent for photocatalytic synthesis. In this work, the photocatalytic partial oxidation of phenanthrene in dimethyl carbonate (DMC) by using anatase TiO2 as the photocatalyst is described as paradigmatic example of a green synthetic process starting from polycyclic aromatic hydrocarbons (PAHs). For comparison, the same reaction carried out also in ethanol, 1-propanol or 2-propanol is reported. The use of DMC as the solvent allowed us to achieve 19% and 23% selectivity towards 9-fluorenone and 6H-benzo[c]chromen- 6-one, respectively. The proposed approach may represent both a new green synthetic process and …

Sintesi di Piperonale tramite fotocatalisi eterogenea in condizioni green

Surface properties of iron-titania photocatalysts employed for 4-nitrophenol photodegradation in aqueous TiO2 dispersion

Iron(III) doped specimens (0.01–5% atomic Fe ∶ Ti) have been prepared by impregnating polycrystalline “home prepared” TiO2 (mainly anatase) and have been studied for photocatalytic degradation of 4-nitrophenol in aqueous dispersions. Some structural and surface properties have been studied by X-ray diffraction, specific surface area and porosity measurements and FTIR monitoring of pyridine, ammonia and methanoic acid adsorption for surface acidity and basicity. Their surface properties were compared with a corresponding series of photocatalysts prepared by a coprecipitation method. Adsorption of pyridine and ammonia indicates the presence of surface acid Lewis sites, a low concentration of …

TiO2-Anatase powders for photocatalytic applications: sol-gel synthesis and relative thermal characterization

Process intensification in a photocatalytic membrane reactor: Analysis of the techniques to integrate reaction and separation

Abstract Different methods to integrate reaction and separation in a membrane reactor are studied in the present work, with the aim being to highlight the pros and cons of the different alternatives and the effects of the intervening parameters. The coupling of the two processes can take place inside a single apparatus or using separate units. If a single apparatus is utilized, the coupling is more direct, but separate units offer higher degrees of freedom for the design with more opportunities to optimize the system without constraints. However, when using separate units, the integration of the two unit operations depends largely on the parameters intervening in the coupling procedure. The…

Preparation of N-doped TiO2: characterization and photocatalytic performance under UV and visibile light

Nanocrystalline N-doped TiO(2) samples were prepared by using TiCl(4) or TiOSO(4) as precursors. The powders were characterized by X-ray diffraction, BET specific surface area measurements, scanning electron microscopy, diffuse reflectance spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. The photocatalytic activity was tested using the photodegradation of 4-nitrophenol under UV and visible light.Some samples were more active than commercial Degussa P25. A shift of the absorption edge to a lower energy and a stronger absorption in the visible light region were observed in the samples obtained from TiCl(4). Two absorption edges were observed in the samples derived from T…

Keggin heteropolyacid H3PW12O40 supported on different oxides for catalytic and catalytic photo-assisted propene hydration

Catalytic and catalytic photo-assisted hydration of propene to form 2-propanol in gas–solid regime at atmospheric pressure and 85 1C were carried out by using a heteropolyacid (POM) supported on different oxides. Binary materials were prepared by impregnation of H3PW12O40 on different commercial and home prepared supports (TiO2, SiO2, WO3, ZrO2, ZnO, Al2O3). Some of the composites were active both for catalytic and catalytic photo-assisted reactions. The Keggin type POM was completely and partially degraded, when supported on ZnO and Al2O3, respectively, and these binary solids always resulted as inactive for both catalytic and catalytic photo-assisted reactions. The supported Keggin POM sp…

Photocatalytic ozonation: Maximization of the reaction rate and control of undesired by-products

Abstract In the so-called photocatalytic ozonation (PO) synergistic effects between photocatalysis and ozonation enhance the rate of oxidation of organic compounds, therefore this integrated process is very promising for use in water treatment. In the present work, it is demonstrated that the improvement that can be obtained by the integrated process in comparison with the uncoupled processes depends on the relative weight between photocatalysis and ozonation. In this respect, it has been found that a relatively low rate of photocatalysis (0.3 times the rate of ozonation) is sufficient to get the highest synergy and to maximize the performances in the oxidation of formate, the adopted model…

Synthesis and Characterization of TiO2 Based Inorganic-Organic Hybrid Photocatalysts for Enhancing the Selective Formation of 4-Methoxy-benzaldehyde from 4-Methoxybenzyl alcohol

The oxidation of alcohols to carbonyl compounds in a clean fashion (i.e., with water as a solvent or under solvent-free conditions, and using O2 or H2O2 as the primary oxidant) is the subject of considerable research efforts. A new approach for the selective oxidation of soluble aromatic alcohols in water under mild conditions via a novel composite photocatalyst has been developed. The catalyst is synthesized by grafting 4-(4-(4- hydroxyphenylimino)cyclohexa-2,5dienylideneamino)phenol and silver nanoparticles onto the surface of moderately crystalline titanium dioxide. The titanium dioxide-based composite was first extensively characterized and then employed in the catalytic oxidation of 4-…

A study of the interaction between iron(III)oxide and titanium(IV)oxide at elevated temperatures

Abstract The bulk interaction between iron(III) oxide and titanium(IV) oxide occurs at temperatures in excess of 773 K. Initially iron(III) ions dissolve in the titanium(IV) oxide structure to produce a substitutional solid solution. Magnetic evidence suggests that there is a solubility limit of iron(III) ions in the region of ca. 3 atom %. Significantly the phase transition from the anatase phase to the rutile phase is observed to occur approximately 200 K lower in the presence of iron than when it is absent. Further reaction between iron(III) oxide and the saturated solution in the rutile phase occurs at 1073 K with the formation of pseudo-brookite. Under high vacuum conditions the therma…

Selective photocatalytic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxaldehyde by polymeric carbon nitride-hydrogen peroxide adduct

Abstract Polymeric carbon nitride-hydrogen peroxide adduct (PCN-H2O2) has been prepared, thoroughly characterised and its application for selective photocatalytic conversion of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxaldehyde (FDC) in aqueous suspension has been studied. The PCN-H2O2 adduct is stable in aqueous suspension under UV and solar irradiation up to 100 °C. It is also stable up to 200 °C if heated in air, while at temperatures close to 300 °C its decomposition takes place. Based on the obtained characterisation data it has been proposed that H2O2 attaches to the non-polymerised carbon nitride species and to the heptazine nitrogen atoms, thus producing strong hydrogen bond…

Comparison of Different Photocatalytic Systems for Acetonitrile Degradation in Gas-Solid Regime

Role of the support on the activity of H3PW12O40 supported on SiO2 or TiO2 in Catalytic and Photocatalytic propene hydration: An EPR Study

Catalytic and catalytic photo-assisted hydration of propene to 2-propanol in gas-solid regime at atmospheric pressure and 85°C were carried out by using the Keggin heteropolyacid (HPA) H3PW12O40 (PW12) supported on home prepared SiO2, WO3, TiO2 or N-doped TiO2. The HPA played the key role both in catalytic and photocatalytic reactions; however, the support strongly influenced the binary material performance. The contemporary presence of heat and UV light improved the activity of the (photo)catalysts. EPR (Electron Paramagnetic Resonance) has been used to understand the intimate mechanism underlying the photoactivity of the supported heteropolyacid and the role played by the support.

Water Depollution by Advanced Oxidation Technologies

This chapter deals with water treatments by advanced oxidation processes (AOPs) based on chemical and photochemical reactions. The most used processes are described, and for each of them, the main reaction mechanisms, principles, advantages, drawbacks, performances and formation of by-products, coupled with technologies and their applications to waters and wastewater depollution, have been analysed, supporting the main results of studies published in the pertinent literature.

Mineralización fotocatalítica de heterociclos aromáticos y alicíclicos que contienen nitrógeno: relación entre productos de reacción que contienen nitrógeno y estructura del substrato

ChemInform Abstract: Membranes for Photocatalysis in Water and Wastewater Treatment

Abstract: The chapter reports the basic principles of heterogeneous photocatalysis together with a brief presentation of the types of membranes and membrane operations most widely used in this type of application. Coupling the two technologies with the aim of obtaining synergistic effects for conversion in liquid–solid systems is discussed and the relevant papers together with some case studies in pollutants abatement and reaction of synthesis are highlighted.

Selective photocatalytic oxidation of 4-substituted aromatic alcohols in water with rutile TiO2 prepared at room temperature

WOS: 000264978500012

An experimental method for the determination of the photon flow reflected and absorbed by aqueous dispersions containing polycrystalline solids in heterogeneous photocatalysis

An experimental method for the evaluation of the photon flow reflected and absorbed by aqueous dispersions containing polycrystalline solids is proposed. The method is based on actinometric measurements. It is shown that the values obtained are independent of the particle sizes and of the concentration of the solids at least in the experimental conditions and in the range used in the present study (particle size range: 40–500 μm; solids concentration: 0.1–2 g liter−1). The results suggest that the values obtained should be attributed to the interfaces formed between the surface of the solids and the medium. The method is applied to a photocatalytic reaction, namely to the photodegradation o…

La fotocatalisi eterogenea per l’abbattimento di specie inquinanti

Cobalt in strontium titanate based perovskites: preparation, characterization and role in the photocatalytic propene partial oxidation

Strontium titanate perovskite (SrTiO3) and analogous materials in which Y partially substitutes Sr have been prepared as basis to integrate Co in the structure. The Co inserrtion has been performed by wet impregnation or coprecipitation methods. The obtained powders have been physico-chemically characterized and tested as photocatalysts in the propene partial oxidation by using a solar simulating reactor. Correlation between photocatalytic performance and physicochemical characteristics of the different catalysts allows to assess a key role of local nanostructuring of CoOx sites on the selectivity and distribution of products.

Preparation, Characterization of rutile obtained by hydrolisis of TiCl4

Photocatalytic oxidation of gaseous toluene on polycrystalline TiO2: FT-IR investigation of surface reactivity of different types of catalysts

Commercial TiO 2 Merck and TiO 2 Degussa P25 powders were employed as the catalysts for the photo-oxidation of toluene. By using TiO 2 Merck benzaldehyde was found in gas phase as the main product of the toluene partial oxidation. After an initial transient period, this catalyst exhibited a high stability in the presence of water vapour in the gaseous mixture, whereas the photoproduction of benzaldehyde sharply decreases after removal of H 2 O from the feed IR spectra of the used catalyst revealed that in the absence of water vapour benzaldehyde is molecularly held on the catalyst surface. This feature was confirmed by co-adsorbing benzaldehyde and water on the fresh catalyst. By contrast, …

Photocatalytic and Catalytic Reactions in Gas–Solid and in Liquid–Solid Systems

Abstract Heterogeneous photocatalytic and thermal-catalytic reactions are here presented focusing the differences and similarities between the two processes. When possible, the comparison was made for the same chemical reaction in the presence of an inorganic material playing the role of both catalyst or/and photocatalyst. Several examples are presented where a catalytic reaction can occur at milder experimental conditions and, particularly, at lower temperature when the system is also irradiated by UV and/or visible light. The differences in mechanistic aspects, conversions, and selectivities between catalytic and photocatalytic reactions will be also considered because these occurrences a…

Heterogeneous photocatalytic degradation of pharmaceuticals in water by using polycrystalline TiO2 and a nanofiltration membrane reactor

Abstract A study of the photodegradation of different pharmaceuticals [furosemide, ranitidine (hydrochloride), ofloxacine, phenazone, naproxen, carbamazepine and clofibric acid] in aqueous medium at various pHs by using a batch photoreactor and a photocatalytic membrane reactor working in recirculation regime was carried out. Polycrystalline TiO 2 was used as the photocatalyst, and different membranes (NTR 7410, PAN GKSS HV3/T, N 30 F, NF PES 10) were tested. A different adsorption of the substrates onto the catalyst surface was observed owing to the hydrophilic/hydrophobic character of the catalyst, depending on the pH. The photodegradation of the seven molecules in the batch reactor was s…

Synthesis of 9-fluorenone and 6H-benzo[c]chromen-6-one through photocatalytic oxidation of phenanthrene by TiO2 photocatalysis

Photocatalytic membranes based on TiO2 catalysts and fluorinated polymers for CO2 conversion

In this work, prepared TiO2–Nafion™-based membranes were used in a photocatalytic membrane reactor, operated in continuous mode, for converting CO2 to methanol.

Influence of platinum on catalytic activity of polycrystalline WO3 employed for phenol photodegradation in aqueous suspension

Abstract A series of polycrystalline WO3 solids loaded with platinum (0.5; 1.0; 2.0 and 3.0 wt%) were prepared and characterised by X-ray diffraction, diffuse reflectance spectroscopy, scanning electron microscopy, specific surface areas determination, X-ray photoelectron spectroscopy. XPS and X-ray results indicate that the samples loaded with Pt up to 1 wt% contained on the surface mainly Pt(2+) species, while those loaded with higher amounts contained Pt(0). Moreover, the samples were employed for a probe reaction, i.e. phenol photooxidation in aqueous suspension, and their photoactivity was compared with that of two TiO2 commercial samples, mainly in the anatase phase. All the Pt–WO3 sa…

A quantitative method of photoadsorption determination for irradiated catalyst in liquid–solid system

WOS: 000266963000002

Film di TiO2 da idrolisi di TiCl4: preparazione, caratterizzazione e fotoattività

TiO2-H2O Interactions by Fast Field Cycling (FFC) NMR Relaxometry

Analytical control of photocatalytic treatments: degradation of a sulfonated azo dye

The degradation of Methyl Orange (C(14)H(14)N(3)SO(3)Na), chosen as a model sulfonated azo dye, was investigated in aqueous solutions containing suspended polycrystalline TiO(2) particles under irradiation with simulated sunlight. The dye disappearance and the formation of the mineralization end products were monitored; the formation of the main transient intermediates was also examined in detail. Particular attention was devoted to the identification and to the evolution of fragments retaining the chromophoric group. The comparison of data coming from various analytical techniques led to a possible reaction mechanism for the degradation process, giving insight into an aspect of the treatme…

Synthesis of vanillin in water by TiO2 photocatalysis

Abstract The photoproduction of vanillin is studied in aqueous medium starting from trans-ferulic acid, isoeugenol, eugenol or vanillyl alcohol by using both commercial and home prepared TiO2 samples as photocatalysts and batch Pyrex photoreactors. The photo-oxidation at room temperature of these compounds produces vanillin with a selectivity ranging from 1.4 to 21 mol% with respect to the converted substrate. An investigation on the intermediates was performed in the case of trans-ferulic acid; for this substrate the most important intermediates were homovanillic acid, vanillyl mandelic acid, trans-caffeic acid, formic acid, acetic acid, and oxalic acid. The carbon mass balance, including …

Preparazione di TiO2 nanostrutturato a partire da TiCl4.

Coupling heterogeneous photocatalysis with other technologies: a tool for abatement of pollutants in water

Photocatalytic Properties of Nanostructured TiO2 Powders Obtained by Thermohydrolysis of TiOSO4

Photocatalytic ozonation for a sustainable aquaculture: A long-term test in a seawater aquarium

Abstract A long-term test at a laboratory scale with a closed system (a coral reef aquarium) has been carried out to study the potentialities of photocatalytic ozonation and photocatalysis for the removal of noxious organic compounds in recirculating systems (aquaria and recirculating aquaculture systems) working with a minimum make up of new water. Attention has been focused not only on the depuration capabilities but also on possible negative phenomena, some of which could become apparent only at long times. After having tuned the system by setting appropriate operating conditions and procedures, positive results were obtained. In particular, it was observed that the alternation of photoc…

Influence of fluorine on the synthesis of anatase TiO2for photocatalytic partial oxidation: Are exposed facets the main actors?

Anatase TiO2 samples were synthesized in the presence of different amounts of HF acid with the aim of understanding the effect of the presence of fluorine on the photocatalytic activity. It is well known that the presence of fluoride ions influences the photocatalytic performance by adsorption on the surface of TiO2 and that they are capping agents in the control of specific exposed facets. The samples were characterized by X-ray diffraction (XRD), Raman spectroscopy, nitrogen adsorption–desorption measurements, scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-vis spectrophotometry, and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity was eva…

Coupling of membrane and photocatalytic technologies for selective formation of high added value chemicals

Abstract This review presents a survey of some heterogeneous photocatalytic processes for the synthesis of high-value added compounds carried out in photocatalytic membrane reactors (PMRs). The two technologies can be easily integrated due to the similar conditions at which they usually operate. Furthermore, significant advantages derive from the coupling and in some cases also synergistic effects can be observed. These features have been highlighted for the photocatalytic syntheses reviewed along with engineering and design aspects investigated for some industrially relevant high-value added compounds. Notably, photocatalytic syntheses carried out in PMRs are still rare mainly because inte…

H3PW12O40 supportato per l'idratazione di propene in regime gas-solido: attività catalitica e catalitica fotoassistita

Photodegradation of lincomycin in aqueous solution

Aqueous solutions of lincomycin were irradiated with UV light in homogeneous and heterogeneous systems. Lincomycin disappeared in both systems but the presence ofTiO2noticeably accelerated the degradation of the antibiotic in comparison with direct photolysis. The rate of decomposition was dependent on the concentration of lincomycin and followed a pseudo-first-order kinetics. Photolysis involved only the oxidation of lincomycin without mineralization. Differently, the treatment withTiO2and UV light resulted in a complete mineralization of the antibiotic. The degradation pathways involved S- and N-demethylation and propyldealkylation. The mineralization of the molecule led to the formation …

Photocatalytic CO2 reduction in gas-solid regime in the presence of bare or Cu-loaded TiO2 and water

On the Photoisomerization of Caffeic Acid in the Presence of Nanostructured TiO2

Photocatalytic Ozonation: from Science to Aquaculture Applications

Demographic growth and management of water and food resources are probably the most challenging issues of the coming years. In this scenario, intensive aquacultura will be increasingly important in the near future

Preparation, Characterization and Photocatalytic Activity of TiO2 Impregnated with the Heteropolyacid H3PW12O40: Photo-assisted Degradation of 2-propanol in Gas-Solid Regime

Abstract Both commercial and home prepared TiO2 samples impregnated with tungstophosphoric acid (H3PW12O40) were prepared and used for the photo-assisted degradation of 2-propanol in gas–solid regime. The characterization results evidenced a good coverage of the polyoxometalate (POM) onto the surface of both types of TiO2 samples along with a marginal effect of the presence of ethanol or HCl during the POM impregnation step on the specific surface area, porosity, morphology, crystallinity and acidity of the samples. Propene was the main intermediate product found in 2-propanol photocatalytic degradation by using the samples containing POM as the photocatalyst, whereas propanone was mainly o…

Studies on Catalytic and catalytic photo-assisted propene hydration in the presence of H3PW12O40 supported on different oxides

4-Nitrophenol Oxidation in a Continuous Fixed Bed Photoreactor Containing Titanium Dioxide Supported on Glass Beads

Carbon nitride as photocatalyst in organic selective transformations

Abstract Graphitic carbon nitride (g-C3N4) is a metal-free conjugated polymer which has become a new research hotspot in photocatalysis. It can be used for solar energy exploitation like in solar energy organic synthesis, one of the most new and appealing green applications of heterogeneous photocatalysis. This chapter resumes the state-of-the-art and progresses in the application of heterogeneous visible light photocatalysis in organic selective transformations by using C3N4 as photocatalyst.

Selectivity of hydroxyl radical in the partial oxidation of aromatic compounds in heterogeneous photocatalysis

Abstract The photocatalytic oxidation of different benzene derivatives has been investigated in order to understand how the substituent group affects the selectivity to hydroxylated compounds. Experimental runs were performed by using TiO2 (Merck) aqueous suspensions at natural pH irradiated by near-UV light. The organic molecules used as substrate contained an electron withdrawing group (EWG) (nitrobenzene, cyanobenzene, benzoic acid, 1-phenylethanone), an electron donor one (EDG) (phenol, phenylamine, N-phenylacetamide) or both an EWG and an EDG (4-chlorophenol). The results clearly indicated that the primary photocatalytic oxidation of aromatic compounds containing an EDG gives rise main…

Hydroxilation of benzoic acid and phenol in the presence of TiO2 photocatalysts: selectivity and kinetics

Photodegradation of paraquat in aqueous suspension of polycrystalline TiO2 : genotoxicity by using ames test

VOC's abatement: Photocatalytic oxidation of toluene in vapour phase on anatase TiO2 catalyst

Publisher Summary The photocatalytic oxidation of toluene in the presence of water was performed in the gas–solid regime at room temperature by using TiO2. It has been found that the presence of water was beneficial to achieve the almost complete photo-oxidation of toluene to CO2 and H2O, in fact, only very small amounts of benzaldehyde vapor that is the main product of toluene partial oxidation, were detected. Volatile organic compounds, VOC's, are an important class of air pollutants usually found in the atmosphere of all urban and industrial areas. Toluene is one of these compounds, and because of its noxious nature several strategies have been identified to reduce its presence in indoor…

Photocatalytic oxidation of aromatic alcohols to aldehydes in aqueous suspension of home-prepared titanium dioxide

Abstract Oxygenated aqueous suspensions of home-prepared (HP) and commercial TiO2 catalysts were used in a batch photoreactor for carrying out the oxidation of benzyl alcohol (BA) and 4-methoxybenzyl alcohol (MBA) under different operative conditions. HP catalysts were synthesized from TiCl4 and underwent a hydrolysis treatment of different times under mild conditions. The textural characterization of catalysts was carried out with XRD, SEM observations, BET surface area and porosity measurements. For both alcohols the main oxidation products were the corresponding aromatic aldehydes and CO2. The HP catalysts exhibited selectivity values towards the aldehyde production up to 28% (BA convers…

CO2 to Liquid Fuels: Photocatalytic Conversion in a Continuous Membrane Reactor

The photocatalytic reduction of CO, into value-added chemicals using sunlight is a promising approach to promote energy-bearing products, mitigating the adverse effects of anthropogenic CO2 emissions. In this work, exfoliated C3N4 was incorporated into Nafion matrix and used in a continuous photocatalytic reactor for converting CO2 into liquid fuels. Comprehensive structural and morphological diffuse reflectance spectroscopy (DRS), FT-IR, ATR-IR, and SEM measurements were performed for C3N4-loaded Nafion membrane and then compared with those of a Nafion membrane without any catalyst. The synergic effect of C3N4 organic catalyst embedded in a Nafion dense matrix and a continuous operating mo…

Sequential biological and photocatalysis based treatments for shipboard slop purification: A pilot plant investigation

This study investigated the treatment of a shipboard slop containing commercial gasoline in a pilot plant scale consisting of a membrane biological reactor (MBR) and photocatalytic reactor (PCR) acting in series. The MBR contributed for approximately 70% to the overall slop purification. More precisely, the biological process was able to remove approximately 40%, on average, of the organic pollution in the slop. Nevertheless, the membrane was capable to retain a large amount of organic molecules within the system, amounting for a further 30% of the influent total organic content removal. However, this affected the membrane fouling, thus resulting in the increase of the pore blocking mechani…

Characterization of methyl orange and its photocatalytic degradation products by HPLC/UV–VIS diode array and atmospheric pressure ionization quadrupole ion trap mass spectrometry

Abstract HPLC/UV–VIS diode array and HPLC/MS techniques were successfully applied to the analysis of sulfonated molecules present in samples coming from the photocatalytic degradation of the azo dye indicator, methyl orange. The substrate was chosen as a simple model for the study of reactions involving the more complex commercial products used for the dyeing of textile fibers. Unexpected MS fragmentation path was observed, due to the very stable methyl orange molecular structure. The chromatographic information were combined with the obtained MS, MS/MS data and the UV–VIS diode array spectra and allowed to rationalize the molecular structures attributable to the various degradation product…

Perovskiti a base SrTiO3: Preparazione, caratterizzazione ed attività fotocatalitica in regime gas-solido

TiO2-induced photoisomerization of caffeic acid

CO2 conversion in a photocatalytic continuous membrane reactor

The reduction of CO2 with water by using photocatalysts is one of the most promising new methods for achieving CO2 conversion to valuable hydrocarbons such as methanol (MeOH). In this work, prepared TiO2-Nafion (TM)-based membranes were used in a photocatalytic membrane reactor, operated in continuous mode, for converting CO2 to methanol. By using the membrane with the best TiO2 distribution, a MeOH flow rate/TiO2 weight of 45 mu mol (g(catalyst) h)(-1) was measured when operating at 2 bar of feed pressure. This value is higher than those reported in most of the literature data to date. Moreover, methanol production is considered as a relevant advance over the existing literature results wh…

Semiconductor mixed oxides as innovative materials for the photocatalytic removal of organic pollutants

Abstract This work aims to provide a critical survey of the extensive literature concerning the potential applications of nanostructured mixed oxides for environmental remediation. In particular, our attention was focused on the feasibility to employ these materials as photocatalysts for the elimination of toxic organic pollutants contained in water and wastewater. The advantages and perspectives of the various nanocomposites are briefly discussed.

Preparation of Catalysts and Photocatalysts Used for Similar Processes

Abstract This chapter reports the main techniques used to synthesize powders and films of heterogeneous catalysts and photocatalysts, often used for similar processes. Traditional preparation processes of bulky (photo)catalysts including precipitation, sol–gel technique, hydrothermal or solvothermal method, solid-state reactions, and flame syntheses were briefly described. The sonochemical method and microwave irradiation technique were also considered. The syntheses of supported catalysts by different techniques, including deposition–precipitation, impregnation, and wet coating technologies were also described. Moreover, a survey is reported of methods to deposit thin films of catalysts on…

PREPARATION AND CHARACTERIZATION OF BROOKITE TiO2 PHOTOCATALYSTS FOR POLLUTANTS DEGRADATION AND ORGANIC SYNTHESIS

Heteropolyacid-Based Heterogeneous Photocatalysts for Environmental Application

Polyoxometalates (POMs) are a wide class of discrete nanosized transition metal–oxygen clusters. The synthesis of POMs has received great interest not only because they present intriguing architectures but also because they have potential applications in catalysis, medicine, electrochemistry, materials design or models for self-assembling nanoscale systems. Recently, POMs have also been studied as green and cheap photocatalysts. The potentialities of POMs are attributed to their unique structural features; indeed, POMs are photostable and non-toxic, have oxygen-rich surfaces and excellent redox properties and possess photochemical characteristics similar to those of the semiconductor photoc…

Clean by Light Irradiation: Practical applications of supported TiO2

Front Cover: (Photo)electrocatalytic Versus Heterogeneous Photocatalytic Carbon Dioxide Reduction (ChemPhotoChem 9/2021)

Arbeitsmethoden und Versuche: Abschnitte 8.4.2 (Versuche 37 - 43) - 8.6

TRMC, XPS, EPR Characterisations of Polycrystalline TiO2 Porphyrin Impregnated Powders and their Catalytic Activity for 4-Nitrophenol Photodegradation in Aqueous Suspensio

Preparation and Characterization of Tungsten Chalcogenide Photocatalysts

Tungsten chalcogenides powders have been prepared by sulfidation of WO3 with gaseous H2S. Different mixed WS2/WO3 systems have been obtained by varying the amount of initial WO3 powder, the time, o...

ChemInform Abstract: Elemental Bromine Production by TiO2Photocatalysis and/or Ozonation.

Significant production of elemental bromine (Br2 ) was observed for the first time when treating bromide containing solutions at acidic pH, with TiO2 photocatalyst, ozone, or a combination thereof. Br2 selectivities up to approximately 85 % were obtained and the corresponding bromine mass balance values satisfied. The process is general and may be applied at a laboratory scale for green bromination reactions, or industrially as a cheap, safe, and environmentally sustainable alternative to the currently applied bromine production methods.

Reactions in the presence of irradiated semiconductors: Are they simply photocatalytic?

A generally accepted classification distinguishes semiconductor photocatalysis in type A and type B. The first class comprehends reactions where the primary redox products (radical anions and cations) further evolve giving rise to the final reduced and oxidized species. Type B reactions occur when the primary redox products undergo intermolecular bond formation to addition products. Recently, some photocatalytic reactions have been reported wherein the photocatalytically produced compounds are not the final products. In fact, they react in the solution bulk or catalytically on the surface of the semiconductor with other species thus producing the target compounds. These reactions, hereby re…

Degradation of 4-nitrophenol (4-NP) using Fe–TiO2 as a heterogeneous photo-Fenton catalyst

Photocatalytic degradation of 4-nitrophenol was investigated using Fe-doped (1, 3, 5 and 8 wt.% Fe) TiO(2) catalysts under UV light irradiation in aqueous dispersions in the presence of H(2)O(2). Photocatalysts with the lowest Fe content (1%) showed a considerably better behavior with respect to the unloaded TiO(2) and the catalysts with higher Fe contents. Photocatalytic degradation was studied under different conditions such as amounts of 1% Fe-TiO(2) catalyst, H(2)O(2) dose and initial pH of 4-NP solution. The results indicated that about 67.53% total organic carbon of a solution containing 20 mg L(-1) 4-NP was removed at pH 6.17 by using 4.9 mM of H(2)O(2) and 0.4 g L(-1) of the catalys…

New Porphyrin/Fe-Loaded TiO2 Composites as Heterogeneous Photo-Fenton Catalysts for the Efficient Degradation of 4-Nitrophenol

A new class of porphyrin(Pp)/Fe co-loaded TiO2 composites opportunely prepared by impregnation of [5,10,15,20-tetra(4-tert-butylphenyl)] porphyrin (H2Pp) or Cu(II)[5,10,15,20-tetra(4-tert-butylphenyl)] porphyrin (CuPp) onto Fe-loaded TiO2 particles showed high activities by carrying out the degradation of 4-nitrophenol (4-NP) as probe reaction in aqueous suspension under heterogeneous photo-Fenton-like reactions by using UV-visible light. The combination of porphyrin-Fe-TiO2 in the presence of H2O2 showed to be more efficient than the simple bare TiO2 or Fe-TiO2.

Influence of crystallinity and OH surface density on the photocatalytic activity of TiO2 powders

Abstract The aim of the work was to study the influence of crystallinity and OH surface density on the photocatalytic activity of two commercial and two home-prepared TiO 2 powders. The samples were characterized by X-ray diffraction (XRD), thermogravimetric analysis (TG) and electron paramagnetic resonance (EPR) measurements. The photoactivity of the powders was tested employing the photodegradation of 4-nitrophenol (4-NP) and the selective oxidation of 4-methoxybenzyl alcohol (4-MBA) to 4-methoxybenzaldehyde ( p -anisaldehyde) under UV irradiation. An anti-correlation between oxidant power and selectivity of the various samples was found. A higher rate of 4-NP degradation was exhibited by…

Photocatalytic degradation of acid blue 80 in aqueous solutions containing TiO2 suspensions.

The photocatalytic degradation of the anthraquinonic dye Acid Blue 80 in aqueous solutions containing TiO2 dispersions has been investigated. The process has been monitored by following either the disappearance of the dye (via HPLC) and the formation of its end-products (via IC, GC, and TOC analysis). Although a relatively fast decolorization of the solutions has been observed, the mineralization is slower, and the presence of residual organic compounds was evidenced even after long term irradiation, confirming the relevant stability of anthraquinone derivatives. The identification of various unstable intermedi ates formed after low irradiation times was performed by HPLC-MS, allowing us to…

Phthalocyanine/TiO2 and Porphyrin /TiO2 Photocatalysts Used in Processes under Mild Conditions

Composite materials prepared by loading polycrystalline TiO2 powders with lipophilic highly branched Cu(II) and metal-free phthalocyanines or porphyrins, have been used as photocatalysts to promote photo degradative processes as well as the efficient photoreduction of carbon dioxide in aqueous suspension affording significant amounts of formic acid.

TiO2 Nanomaterials Used as Photocatalysts for Selective Heterogeneous Syntheses of Alcohols to Aldehydes in Water

Synthesis, Characterisation and Photocatalytic Degradation of 4-Nitrophenol in Aqueous Phase by Using TiO2 Powders Prepared via Sol-Gel Method under Different Gelling Pressure Conditions

Photocatalytic activity of TiO2/SiO2 systems

Silica-supported TiO(2) powders were synthesized by a wet method under mild conditions. The aim of the work was the preparation of TiO(2)/SiO(2) additives for photocatalytic cements. Three types of commercial SiO(2) were used as supports: Cabot, Axim and Fly Ash. Cabot silica was ultra-pure whereas the other two silica contained different percentages of various oxides. The TiO(2)/SiO(2) samples, denoted TiO(2)/Cabot, TiO(2)/Axim and TiO(2)/Fly Ash, were prepared by boiling suspensions obtained by addition of silica to a solution of TiCl(4) in water (volume ratio 1:10). The photocatalytic activity was evaluated in a gas-solid system both in batch and in continuous reactors using 2-propanol a…

Photocatalytic membrane reactors: configurations, performance and applications in water treatment and chemical production

Abstract: The configurations and performance of photocatalytic membrane reactors (PMRs) assembled with membranes (also photocatalytic type) and/or suspended photocatalyst are described. Examples of the application of PMRs in water/wastewater treatment as well as in photocatalytic synthesis are shown. An outline of the modeling of PMRs is presented with a brief economic analysis; future trends in PMRs are also discussed.

COMPARISON OF THE PHOTOCATALYTIC DEGRADATION OF 2-PROPANOL IN GAS-SOLID AND LIQUID-SOLID SYSTEMS BY USING TiO2 – LnPc2 HYBRID POWDERS

Photocatalytic degradation of 2-propanol was carried out as a probe reaction both in gas–solid and in liquid–solid systems in the presence of TiO2 both bare and impregnated with lanthanide (Sm, Gd, Ho) bis-phthalocyanines (LnPc2) used as sensitizers. Continuous and batch photo-reactors, irradiated with an equal flux of photons, were used in gas–solid and in liquid–solid systems, respectively. Propanone and acetaldehyde were the main intermediates found in both systems during 2-propanol oxidation, whereas carbon dioxide and water were the final oxidation products exclusively in the gas–solid regime. The photocatalysts exhibited significantly higher activity in the liquid–solid system than in…

Highly Active Photocatalytic TiO2 Powders Obtained by Thermohydrolysis of TiCl4 in Water

Highly active photocatalytic TiO2 samples were synthesized by thermohydrolysis of TiCl4 in water at 100 °C. Rutile, binary mixtures of anatase and rutile or anatase and brookite or ternary mixtures of anatase, brookite, and rutile were obtained depending on the TiCl4/H2O ratio. Rietveld refinements were employed to evaluate the crystalline phases and composition of the mixtures. The effect of the aging time on the phase composition was also studied. The band gap values of the samples were obtained by the diffuse reflectance spectra. The position of the flat band potentials of anatase, brookite, and rutile was determined measuring the photovoltage as a function of the suspension pH. From the…

Determination of the crystallinity of TiO2 photocatalysts

Abstract This study reports a new simple method to determine the crystallinity of anatase and rutile TiO2 photocatalysts. The crystallinity degree of various anatase and rutile samples was estimated by XRD analysis from the ratio among the full width at half maximum intensities of the main diffraction peaks of anatase or rutile and the (111) peak of CaF2 as internal standard. The photocatalytic activity of selected powders was tested employing the photodegradation of 4-nitrophenol in aqueous solution as probe reaction. The results showed that the photoactivity of the investigated samples increased with increasing crystallinity and crystallite size.

Photoactivity of Nanostructured TiO2 Catalysts in Aqueous System and their Surface Acid-Base, Bulk and Textural Properties

This work reports on the characterisation and determintion of the photocatalytic activity of some TiO2 catalysts prepared using TiCl4 as precursor. The samples, consisting of suspensions, dispersions or powders of nanonstructured anatase or rutile phases, were obtained in very mild conditions, i.e., by boiling the solution obtained after hydrolysis of TiCl4 at atmospheric pressure: it is worth noting that no calcination was necessary to obtain photoactive phases. The samples were characterised by X-ray diffraction (XRD), determination of the BET specific surface area (SSA), scanning electron microscopy (SEM) observations and diffuse reflectance spectroscopy (DRS). FT-IR spectroscopy was use…

Highly stable defective TiO2-x with tuned exposed facets induced by fluorine: Impact of surface and bulk properties on selective UV/visible alcohol photo-oxidation

Abstract Titanium dioxide samples were prepared in the presence of different amounts of fluorine via hydrothermal method. It has been found that the presence of fluoride influenced the physico-chemical properties of TiO2 in various ways as polymorphic form stability, surface hydroxylation, generation of hydroxyl radicals under irradiation and formation of Ti3+ centers and oxygen vacancies. The generation rate of OH radicals was investigated by the photoluminescence technique in the presence of terephthalic acid. X-ray diffractometry indicated that fluorine stabilized the anatase TiO2. X-Ray photoelectron spectroscopy (XPS) revealed the presence of fluorine on the surface and the shift of th…

Thin-Film Photovoltaics 2014

The interest toward alternative energy sources to fossil fuels (still the most convenient in terms of efficiency and cost) is current. Initiatives that seek to convert wind, geothermal energy, hydropower, marine, solar thermal energy, and photovoltaics or derived from biomass energy into other forms continue to involve several research groups. For example, the transfer from solar energy into electricity, which in turn can be used for water splitting and for the subsequent production of hydrogen, seems a major challenge to provide a sustainable contribution to the “Earth system” together with the realization of devices having high conversion efficiencies, low environmental impact, and low pr…

Preparation of Sm-loaded brookite nanoparticles and thin films

Surface processes in selective photocatalytic oxidation of hydroxybenzyl alcohols by TiO2 P25

Aryl aldehydes and acids are important industrial intermediates, but their synthesis from the corresponding alcohols often requires the use of high temperatures and harmful solvents and oxidant agents. Heterogeneous photocatalysis represents an interesting option for the partial oxidation of alcohols to aldehydes at room temperature using water as solvent. In this work, the partial photocatalytic oxidation of 2-hydroxybenzyl alcohol (salicyl alcohol) and 4-hydroxybenzyl alcohol to the corresponding aldehydes and acids has been compared, under environmental-friendly conditions, employing TiO2 P25 as photocatalyst in water. The selectivity to the corresponding aldehydes and acids, under the s…

A Method for Determining Optical Properties and Quantum Yields of Photocatalytic Suspensions

SrTiO 3 -based perovskites: Preparation, characterization and photocatalytic activity in gas–solid regime under simulated solar irradiation

Strontium titanate-based perovskites have been prepared in the presence of Y and Co with the aim to substitute Sr and Ti, respectively, in the ST crystalline structure. The obtained samples have been characterized by XRD, Raman spectroscopy, FE-SEM, XPS and tested as photocatalysts in two gas-solid regime reactions: (i) 2-propanol complete mineralization and (ii) propene partial oxidation, using a system simulating solar irradiation. All the tested samples resulted active as photocatalysts but with significant differences. The lattice substitution of Sr by Y displays a beneficial effect on the 2-propanol photodegradation. Conversely, the partial presence of cobalt on the ST surface, as Co-o…

H2 and value added chemicals from photocatalytic conversion of glucose

Commercial and home prepared bare and Pt-supported TiO2 samples were used as the photocatalysts for the aqueous aerobic and anaerobic photo-conversion of glucose at ambient pressure and temperature. H2 and valuable chemicals were the obtained products. The home prepared samples resulted more active than the commercial ones

Photocatalytic H2 production over inverse opal TiO2 catalysts

Abstract The influence of BiVO4 and CuO on the chemico-physical properties of TiO2-based systems is reported. The performances of these systems were investigated in the photocatalytic H2 production both under UV and solar light irradiation. The characterization data pointed out that the obtained TiO2 samples have highly porous inverse opal structures with interconnected macropores. Inverse opal TiO2 exhibited higher activity in the H2 production than the commercial TiO2 due to the peculiar porosity that allows photons to enter inside the photocatalyst. A further improvement in terms of photoactivity was verified by addition of increasing amounts of BiVO4. On the contrary a small CuO content…

2-propanol formation by propene hydration: Catalytic and catalytic photo- assisted reaction using H3PW12O40 supported on TiO2 and SiO2.

Photocatalytic oxidatioon of acetonitrile : degradation performance in gas-solid and liquid-solid systems

ChemInform Abstract: Preparation and Characterization of Tungsten Chalcogenide Photocatalysts.

Tungsten chalcogenides powders have been prepared by sulfidation of WO3 with gaseous H2S. Different mixed WS2/WO3 systems have been obtained by varying the amount of initial WO3 powder, the time, o...

Photocatalytic degradation of 4-nitrophenol in aqueous suspension by using polycrystalline TiO2 impregnated with functionalised Cu(II)-porphyrin or Cu(II)-phthalocyanine

The photocatalytic activity of polycrystalline TiO2 samples impregnated with functionalized Cu(II)- or metal-free porphyrins has been investigated. A probe reaction, i.e., 4-nitrophenol (4-NP) photodegradation in aqueous suspension, has been used. The results indicated that the presence of the sensitizers is beneficial for the photoactivity and suggest an important role of Cu(II). A comparison with similar samples impregnated with modified Cu(II)- and metal-free phthalocyanines showed that the presence of porphyrin is more beneficial both for the decomposition rate of 4-nitrophenol and for the disappearance of nonpurgeable organic carbon (NPOC). Experiments were carried out by using cutoff …

Ossidazione fotocatalitica del glucosio in presenza di TiO2

A facile way to synthesize noble metal free TiO2 based catalysts for glycerol photoreforming

In this work anaerobic heterogeneous photocatalytic solar/UV light reforming of glycerol in aqueous media was performed with Pt-photodeposition and noble metal free modified TiO2 photocatalysts prepared through ball milling, a very simple and cheap coupled catalyst preparation method. Different amounts of Cu2O or 3% CuO were loaded on TiO2 using ball milling and during each run glycerol conversion, hydrogen and CO2 formed in the gas phase and 1,3-dihydroxyacetone (DHA) and glyceraldehyde (GA) in the liquid phase were determined. The results were compared with the aim to verify the effectiveness of Cu2O in replacing Pt. Using noble metal free photocatalysts, 33% glycerol conversion, 10.3% an…

Visible-light-induced oxidation of trans-ferulic acid by TiO2 photocatalysis

Abstract The oxidation of trans-ferulic acid (C10H10O4) in aqueous TiO2 dispersion occurs via the formation of a charge-transfer complex on the TiO2 surface that is able to absorb visible light (λ ⩾ 400 nm). The main product is CO2, whereas secondary oxidation products are organic species such as vanillin, caffeic acid, homovanillic acid, and vanillylmandelic acid. Oxidation through the formation of a charge-transfer complex occurs only in the presence of specific TiO2 samples. Experiments in the absence of oxygen, in the presence of bromate ions and by using a phosphate-modified TiO2, have been carried out for investigating the reaction mechanism. In order to study the interaction between …

The Effect of Polycrystalline TiO2 on Sunlight Induced Functionalisation of Some Heterocyclic Bases

A solar photothermo-catalytic combined process for the VOCs combustion and the subsequent CO2 valorization using noble metal-free catalysts

We here investigated a solar photothermo-catalytic combined process where the toluene (as volatile organic compound model) was first oxidized to CO2 which was subsequently converted into solar fuels in a second reactor. For this aim two noble-metal free catalytic systems were used, namely MnOx-ZrO2, which gave the best results for the toluene removal, and brookite TiO2-CeO2 mixed oxides which were the most efficient in the subsequent CO2 conversion. This latter reaction was further improved by the addition of small amounts of copper-based materials on brookite-ceria, acting as co-catalysts. The key point for both the examined reactions was the synergism between the thermocatalytic and the p…

Photocatalytic oxidation of cyanide in aqueous TiO2 suspensions irradiated by sunlight in mild and strong oxidant conditions

Abstract The photocatalytic oxidation of free cyanide ions was carried out in aqueous aerated suspensions containing polycrystalline TiO2 (anatase) irradiated by sunlight. The influence of the presence of an organic compound (phenol) or of a strong oxidant (H2O2) on the photoprocess was also studied. The dependence of cyanide photo-oxidation rate on the following parameters: (1) cyanide concentration; (2) catalyst amount; and (3) phenol concentration was investigated. At the used experimental conditions, the kinetics of cyanide photo-oxidation is independent of the initial cyanide concentration and of the catalyst amount while it is affected by the phenol concentration and by the presence o…

TiO2 based Inorganic-Organic Hybrid Photocatalysts for Highly Selective Alcohol Partial Oxidation

An integrated approach to develop a composite hybrid material made of titanium dioxide functionalized with an organic conjugated phenol (DIOL) and silver NPs suitable for the selective oxidation of water soluble aromatic alcohols to aldehydes in water under UV irradiation and very mild conditions was used. The 86% selectivity observed for the Rutile/DIOL/Ag composite is, to the best of our knowledge, the highest thus far reported for partial oxidation of aromatic alcohols to aldehydes in water suspensions of titanium dioxide. The method is general as it relies on the concomitant easier adsorption of the aromatic alcohol and more facile release of the aldehyde, coupled to fast interfacial el…

A comparison between photocatalytic and catalytic oxidation of 2-Propanol over Au/TiO2-CeO2 catalysts

Abstract Photocatalytic and catalytic oxidation of 2-propanol, representative of volatile organic compounds (VOC’s), were compared over mixed TiO 2 –CeO 2 -based catalysts. The effect of different amounts of CeO 2 and the presence of gold (1 wt%) on TiO 2 was investigated. In the photocatalytic oxidation CeO 2 had a negative effect on the performance towards the alcohol conversion of both TiO 2 –CeO 2 and Au/TiO 2 –CeO 2 catalysts, being Au/TiO 2 the most active system. On the contrary mixed TiO 2 –CeO 2 and Au/TiO 2 –CeO 2 samples showed a higher catalytic oxidation efficiency for 2-propanol conversion compared to the single oxides. In this case Au/CeO 2 catalyst had the best performance. …

Studio di processi fotocatalitici: dalla preparazione del fotocatalizzatore alla comprensione della cinetica e del meccanismo di reazione

New TiO2 based photocatalysts for the degradation of organic pollutants in water

The Combination of Heterogeneous Photocatalysis with Chemical and Physical Operations: a Tool for Improving the Photoprocess Performance

Sintesi di Vanillina tramite Reazione di Ossidazione Fotocatalitica con TiO2 in Fase Acquosa

Photocatalytic Performance of Brookite in Hydrogen Production by Photo-Steam Reforming

Pyrolysis Study of Sol-Gel Derived TiO2 Powders Part IV. TiO2-anatase Prepared by Reacting Titanium(IV) Isopropoxide without Chelating Agents

Photocatalytic Oxidation of Acetonitrile

Photocatalytic Degradation of Paraquat and Genotoxicity of its Intermediate Products

Abstract The photocatalytic degradation of paraquat (1,1-dimethyl-4,4′-bipyridylium dichloride) aqueous solutions in the presence of polycrystalline TiO2 Degussa P25 irradiated by near-UV light was investigated. The substrate and total organic carbon concentrations were monitored by UV spectroscopy and TOC measurements, respectively: the complete photocatalytic mineralization of paraquat (20 ppm) was achieved after ca. 3 h of irradiation by using 0.4 g l−1 of catalyst amount at natural pH (ca 5.8). On the contrary no significant photodegradation of paraquat was observed in the absence of TiO2 under similar experimental conditions. To evaluate the genotoxicity of paraquat and its intermediat…

Comparison of the photocatalytic degradation of 2-propanol in gas–solid and liquid–solid systems by using TiO2–LnPc2 hybrid powders

Photocatalytic degradation of 2-propanol was carried out as a probe reaction both in gas–solid and in liquid–solid systems in the presence of TiO2 both bare and impregnated with lanthanide (Sm, Gd, Ho) bis-phthalocyanines (LnPc2) used as sensitizers. Continuous and batch photo-reactors, irradiated with an equal flux of photons, were used in gas–solid and in liquid–solid systems, respectively. Propanone and acetaldehyde were the main intermediates found in both systems during 2-propanol oxidation, whereas carbon dioxide and water were the final oxidation products exclusively in the gas–solid regime. The photocatalysts exhibited significantly higher activity in the liquid–solid system than in…

Photocatalytic synthesis of piperonal in aqueous TiO2 suspensions

Photocatalytic membrane reactors for water treatment

Abstract Heterogeneous photocatalysis is an advanced oxidation process largely studied in the field of environment recovery by the total degradation of organic and inorganic pollutants and for synthesis. In this chapter, the basic principles of photocatalysis are discussed with the advantages related to its coupling with a membrane separation in photocatalytic membrane reactors (PMRs). The types of membranes most widely used and their criteria of selection are briefly discussed. PMRs’ classification based on their configuration and on the type of membrane operation is also discussed, evidencing as their appropriate choice is a key step in view of large-scale implementation. Finally, some ca…

EDTA excess Zn(II) back-titration in the presence of 4-(2-pyridylazo)-resorcinol indicator and naphthol green beta as inert dye for determining Cr(III) as Cr(III)/EDTA complex: application of the method to a leather industry wastewater.

The colour changes of 4-(2-pyridylazo)-resorcinol and naphthol green beta as new screening metallochromic indicator in back-titration of EDTA excess with Zn(II) to determine Cr(III)/EDTA complex was investigated with the help of tristimulus colorimetry. Specific colour discrimination (SCD) and L*, a*, b* 1976 parameters were successfully applied to evaluate the quality of colour transition at the end-point in non-alkaline media and in the presence of Zn(II) and Ca(II) which resulted in non-interfering species at 1x10(-3) M and 2x10(-3) M, respectively. The above concentrations are comparable with those used for Cr(III). Validation of the fast and accurate reported method was performed by at…

Home-prepared anatase, rutile, and brookite TiO2 for selective photocatalytic oxidation of 4-methoxybenzyl alcohol in water: reactivity and ATR-FTIR study

5th European Meeting on Solar Chemistry and Photocatalysis -- OCT 04-08, 2008 -- Palermo, ITALY

2020 Roadmap on two-dimensional nanomaterials for environmental catalysis

Abstract Environmental catalysis has drawn a great deal of attention due to its clean ways to produce useful chemicals or carry out some chemical processes. Photocatalysis and electrocatalysis play important roles in these fields. They can decompose and remove organic pollutants from the aqueous environment, and prepare some fine chemicals. Moreover, they also can carry out some important reactions, such as O2 reduction reaction (ORR), O2 evolution reaction (OER), H2 evolution reaction (HER), CO2 reduction reaction (CO2RR), and N2 fixation (NRR). For catalytic reactions, it is the key to develop high-performance catalysts to meet the demand for targeted reactions. In recent years, two-dimen…

Heterogeneous photocatalysis from fundamentals to possible applications

This special issue of Catalysis Today Journal, is dedicated to the career of Prof. Vincenzo Augugliaro, University of Palermo, Italy, in the occasion of his retirement in 2015. Prof. Vincenzo Augugliaro was Full Professor of Transport Phenomena at the University of Palermo (Italy) since 1994. He contributed to the fol- lowing research fields: chemical absorption kinetics, biochemical reactor modelling, diffusional kinetics in metallizing alloys and heterogeneous photocatalysis; in this last field he investigated on chemical kinetics of heterogeneous photocatalytic systems, modelling of heterogeneous photoreactors, radiation field in absorbing-reacting media and application of heterogeneous …

TiO2 photocatalysts prepared by thermohydrolysis of TiCl4 in aqueous solutions

Abstract Nanostructured TiO 2 photocatalysts were synthesized by thermohydrolysis of TiCl 4 at 100 °C in various aqueous solutions. Anatase or rutile, binary mixtures of anatase and rutile or anatase and brookite, and ternary mixtures of anatase, brookite and rutile were obtained depending on the hydrolysis solution. The most efficient catalysts consisted of ternary mixtures of the three polymorphic TiO 2 phases.

Oxidación Fotocatalítica de Acetonitrilo en Regimen Gas-Sólido y Líquido-Sólido

Ossidazione del 2-Propanolo Fotocatalizzata da Sistemi Ibridi Bis-Ftalocianina Lantanide-TiO2:Confronto tra Processi Gas-Solido e Liquido-Solido

Oxidation of Azo-Dyes in Water by Means of Heterogeneous Photocatalysis in a Membrane Reactor

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Role of the support and pseudo-liquid phase in the Phosphotungstic Heteropolyacid (photo)catalytic activity

Catalytic and photocatalytic tests for propene hydration to 2-propanol were successfully carried out by using binary materials obtained by supporting a Keggin or Wells-Dawson heteropolyacids via impregnation method to commercial SiO2 or TiO2. (Photo)catalytic hydration was studied in gas-solid regime by using a continuous (photo)reactor working at atmospheric pressure and 80 °C. The alcohol was the main product. The acidity of the cluster accounts for the catalytic role, whereas both the acidity of the cluster and the oxidant ability were responsible for the increase of the reaction rate of the photo-assisted catalytic reaction. Moreover, the presence of a photoactive semiconductor support …

Heterogeneous photocatalysis: guidelines on experimental setup, catalyst characterization, interpretation, and assessment of reactivity

Soon after the publication of the first pioneering works on heterogeneous photocatalysis, the number of papers on this topic continuously increased. This intriguing field of research is very complex as it endows with an interdisciplinary overview that involves different aspects of chemistry, physics, material and environmental sciences. Even if photocatalytic applications in real processes are often difficult to be implemented and scaled-up, investigations at laboratory scale are easy to be performed, and in some cases they may give rise to misconceptions. For this reason, the present work aims to sum up most of the common experimental techniques and procedures generally used in heterogeneo…

Study on a photocatalytic membrane reactor for water purification

Abstract Some results obtained in a photocatalytic membrane reactor, to be used for degradation of toxic organic species dissolved in water, are reported. The catalyst, TiO 2 P25 Degussa, was immobilised by means of a flat sheet polymeric membrane and 4-Nitrophenol (4-NP) was used as a model molecule to evaluate the reactor performance. A preliminary investigation of the stability, under UV irradiation, of some eligible polymeric membranes was carried out by using scanning electron microscopy (SEM), optical microscopy (OM), determinations of water permeation flux (WPF) and total organic carbon (TOC). These tests showed that commercial membranes made of fluoride + PP (FS 50 PP-Dow), polysulp…

Photocatalytic behaviour of metal-loaded TiO2 aqueous dispersions and films

Abstract Titanium dioxide nanoparticles loaded with Ce, Co, Eu, Sm, W and Yb species were prepared by coprecipitation in mild conditions using TiCl 4 as precursor with the aim to enhance the photocatalytic activity, especially under visible light irradiation. The photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), specific surface area (SSA) determination and UV–Vis diffuse reflectance spectroscopy. The photocatalytic activity of the powders of pure and loaded TiO 2 was investigated by employing the photodegradation of 4-nitrophenol as probe reaction in a liquid–solid system. Loading with suitable amounts of W, Co and Sm resulted in a significan…

Photocatalytic Oxidation of Aromatic Alcohols to Aldehydes in Aqueous Suspension of Home Prepared Titanium Dioxide. 1 Selectivity Enhancement by aliphatic alcohols

Oxygenated aqueous suspensions of home-prepared (HP) and commercial TiO2 catalysts were used in a batch photoreactor for carrying out the oxidation of benzyl alcohol (BA) and 4-methoxybenzyl alcohol (MBA) under different operative conditions. HP catalysts were synthesized from TiCl4 and underwent a hydrolysis treatment of different times under mild conditions. The textural characterization of catalysts was carried out with XRD, SEM observations, BET surface area and porosity measurements. For both alcohols the main oxidation products were the corresponding aromatic aldehydes and CO2. The HP catalysts exhibited selectivity values towards the aldehyde production up to 28% (BA conversion: 50%)…

Heterogeneous Photocatalysis and Photoelectrocatalysis: From Unselective Abatement of Noxious Species to Selective Production of High-Value Chemicals

Heterogeneous photocatalysis and photoelectrocatalysis have been considered as oxidation technologies to abate unselectively noxious species. This article focuses instead on the utilization of these methods for selective syntheses of organic molecules. Some promising reactions have been reported in the presence of various TiO2 samples and the important role played by the amorphous phase has been discussed. The low solubility of most of the organic compounds in water limits the utilization of photocatalysis. Dimethyl carbonate has been proposed as an alternative green organic solvent. The recovery of the products by coupling photocatalysis with pervaporation membrane technology seems to be a…

The Existence of Nitrate Radicals in Irradiated TiO 2 Aqueous Suspensions in the Presence of Nitrate Ions

Evidence of the existence of nitrate radical in irradiated aqueous TiO2 suspensions in the presence of nitrate ions are reported for the first time. The joint use of UV/Vis and EPR spectroscopy showed that nitrate radicals are formed by hole induced oxidation of nitrate ions. Photocatalytic degradation of a model alkene compound allowed to highlight the presence of an intermediate organic nitrate deriving from nitrate radical attack to the double bond of the substrate. These results not only allow deeper understanding of photocatalytic processes, but open the route to new green photocatalytic syntheses initiated by nitrate radicals and to new insights in the field of atmospheric chemistry.

Photocatalytic and photothermocatalytic applications of cerium oxide-based materials

Abstract Cerium dioxide (CeO2) presents unique properties as the special electronic and optical properties of the 4f electrons, the capacity to form nonstoichiometric oxygen-deficient CeO2 − x oxides, the high oxygen mobility, and the reversible transformation between Ce4 + and Ce3 + that make it interesting for photocatalytic applications. CeO2 is a wide bandgap semiconductor (3.0–3.4 eV), but different approaches as combination with oxides, deposition of noble metals, doping with metal and nonmetal species, and the formation of surface defects have been adopted to extend its absorption towards the visible region with the aim to improve its photocatalytic performance. Cerium oxide-based ma…

Fundamentals of Heterogeneous Photocatalysis and its Application for Environmental and Synthetic Purposes

Photocatalytic Selective Oxidation of 4-Methoxybenzyl Alcohol to Aldehyde in Aqueous Suspension of Home-Prepared Titanium Dioxide Catalyst

WOS: 000246040000026

One-Pot, Clean Synthesis of Vanillic Acid from Ferulic Acid

Ferulic acid dissolved in water is selectively oxidized to vanillic acid in high yield (≈60 %) under remarkably mild and green conditions, namely at room temperature with air as primary oxidant, over a catalytic amount of nanostructured Bi2WO6. The process is general and opens the route to the selective oxidation of natural substances into derivatives of significant applicative relevance.

Photocatalytic conversion of glucose in aqueous suspensions of heteropolyacid-TiO2 composites.

Photocatalytic conversion of glucose was carried out in aqueous suspensions in the presence of dfifferent commercial and home prepared TiO2 samples functionalized with a commercial heteropolyacid. Different reaction extents and distribution of intermediate oxidation products were observed depending on the photocatalyst.

Preparation of Photocatalytic Nanostructured TiO<sub>2</sub> Thin Films

Photoactive films consisting of pure anatase, brookite or rutile were deposited on glass slides by a dip coating process from water dispersions or solutions obtained by using TiCl4 as the precursor. The films were characterized by X-ray diffraction, scanning electron microscopy and atomic force microscopy. The photocatalytic activity of the various samples was evaluated by using the photooxidation of 2-propanol in gas solid regime as probe reaction. Brookite and anatase films showed a good photoactivity degrading the substrate and the propanone produced during the reaction.

Synthesis of zeolite/geopolymer composite for enhanced sequestration of phosphate (PO43−) and ammonium (NH4+) ions; equilibrium properties and realistic study

Abstract Zeolite impeded geopolymer (Z/G) was synthesized from natural kaolinite and diatomite. The structure (Z/G) was characterized as an enhanced adsorbent for PO43− and NH4+ ions from aqueous solutions, groundwater, and sewage water. The synthetic Z/G structure exhibits sequestration capacities of 206 mg/g and 140 mg/g for PO43− and NH4+, respectively which are higher values than the recognized results for the geopolymer and other adsorbents in literature. The sequestration reactions of PO43− and NH4+ by Z/G are of Pseudo-Second order kinetic behavior considering both the Chi-squared (χ2) and correlation coefficient (R2) values. The sequestration reactions occur in homogenous and monola…

Photocatalytic degradation of toluene in aqueous suspensions of polycrystalline TiO2 in the presence of the surfactant tetradecyldimethylamino-oxide

The heterogeneous photocatalytic method has been used for carrying out the toluene oxidation in synthetic aqueous solutions containing also a zwitterionic surfactant, i.e. tetradecyldimethylamino-oxide (C 14 DMAO). A batch photoreactor with immersed lamp and two kinds of polycrystalline TiO 2 catalysts were used. The results indicate a substantial increase of the toluene degradation rate in the presence of the surfactant; the complete photo- oxidation of toluene was achieved in a few hours of irradiation at the used experimental conditions; at higher irradiation times also C 14 DMAO was completely degraded. The main intermediates of toluene degradation were p-cresol (4-methyiphenol) and ben…

Efficient Degradation of 4-Nitrophenol by Using Functionalized Porphyrin TiO2 Photocatalysts Under Visible Irradiation

Abstract The novel porphyrins 5,10,15,20-tetra-[4-(3-phenoxy)-propoxy]phenyl porphyrin, H2Pp(a) and 5,10,15,20-tetra-[2-(3-phenoxy)-propoxy]phenyl porphyrin, H2Pp(b) and their corresponding copper(II) complexes CuPp(a), CuPp(b) were synthesized and characterized by using various spectroscopic techniques. The photocatalytic activity of polycrystalline TiO2 samples impregnated with H2Pp(a), H2Pp(b), CuPp(a) and CuPp(b) as sensitizers have been investigated by carrying out the photo-degradation of 4-nitrophenol (4-NP) as a probe reaction in aqueous suspension and under visible light. The maximum photocatalytic activity was obtained using TiO2 loaded with a monolayer of the copper porphyrin CuP…

Kinetics of photocatalytic degradation of pharmaceuticals in aqueous TiO2 suspension

Sintesi e caratterizzazione di polveri e film di TiO2

Studio della Fotodegradazione di Antibiotici in Ambiente Acquoso

Photocatalytic degradation of 4-nitrophenol in aqueous suspension by using polycrystalline TiO2 impregnated with lanthanide double-decker phthalocyanine complexes

The photocatalytic activity of polycrystalline TiO2 samples impregnated with rare-earth-metal diphthalocyanines was investigated. The 4-nitrophenol (4-NP) photocatalytic degradation in aqueous suspension was used as a probe reaction. Commercial anatase TiO2 was impregnated with home-prepared double-decker phthalocyanine complexes of the lanthanide metals, such as Ce, Pr, Nd, Sm, Ho, and Gd. In particular, the impregnation with Ho, Sm, and Nd complexes, acting as sensitizers, proved beneficial for the photoactivity of the studied systems. Significant improvements of the TiO2-based catalytic system appeared possible in terms of lower impregnation loading, enhanced photoreactivity under solar …

Photocatalytic Oxidation of Cyanides in Aqueous Titanium Dioxide Suspensions

The photocatalytic oxidation of free cyanides in aqueous suspensions containing polycrystalline TiO2(anatase) powders irradiated in the near-UV region has been investigated. The rate of cyanide photooxidation has been studied by varying the following operative parameters: (i) initial cyanide concentration; (ii) catalyst concentration; (iii) initial pH; (iv) power of irradiation; and (v) chloride ion concentration in the reacting mixture. Under the used experimental conditions the photoreaction proceeded at a measurable rate until the complete disappearance of cyanides. The kinetics of cyanide photooxidation is affected by the catalyst concentration, the chloride ion concentration, and the p…

ChemInform Abstract: Inorganic Materials Acting as Heterogeneous Photocatalysts and Catalysts in the Same Reactions

General considerations on the differences and similarities between heterogeneous photocatalysis and thermal catalysis are presented. Some research papers are reviewed where a reaction has been carried out in the presence of an inorganic material used both as catalyst and photocatalyst. The existing literature often compares catalytic reactions undertaken with the contemporaneous presence of radiation, showing only that photocatalytic reactions can occur under milder experimental conditions and at much lower temperatures. Nevertheless, differences in mechanistic aspects, conversions and selectivities between catalytic and photocatalytic reactions should also be highlighted. These are due to …

Nanocrystalline TiO2 Photocatalysts Obtained by Thermohydrolysis of TiCl4 in Aqueous Solutions

A Study on the Influence of the Presence of Activated Carbon in TiO2 and ZnO Photo-Assisted Degradation of 2-Propanol

Preparation and photoactivity of nanostructured TiO2 particles obtained by hydrolysis of TiCl4

This work reports the preparation of nanostructured polycrystalline TiO2 photocatalysts obtained by hydrolysis of TiCl4 in very mild conditions. Several samples were prepared as suspensions or colloidal dispersions by using TiCl4/H2O volume ratios ranging between 1:1 and 1:100. The samples were characterised by X-ray diffraction analysis, specific surface area determination, diffuse reflectance spectroscopy and scanning electron microscopy. 4-Nitrophenol photodegradation was used as probe reaction to test the photoactivity of the catalysts. Some samples revealed a photoactivity higher than that of Degussa P25 in similar experimental conditions and the most photoactive one was that prepared …

Zn,Al hydrotalcites calcined at different temperatures: Preparation, characterization and photocatalytic activity in gas–solid regime

Abstract Layered double hydroxides (LDH) containing zinc and aluminium within the brucite-like layers and carbonate as the interlayer anion have been used as precursors for the preparation of mixed metal oxides by calcination. Zinc oxide and the ZnAl 2 O 4 spinel were formed with different degree of crystallinity depending of two parameters, i.e., the Zn 2+ /Al 3+ molar ratio and the calcination temperature (500–800 °C) of the LDH precursor. A pure spinel phase was obtained to remove ZnO upon a basic post-treatment in NaOH solution of the samples calcined at 800 °C. All the samples were tested for the photodegradation of 2-propanol in gas–solid regime. All the samples resulted active as het…

Photocatalytic thin films of TiO2 formed by a sol-gel process using titanium tetraisopropoxide as the precursor

Abstract Thin TiO 2 films were prepared with the dip-coating technique by using sols deriving from titanium tetraisopropoxide. TiO 2 films were formed on glass substrates previously covered by a SiO 2 layer obtained from a tetraethylortosilicate sol. The films, after a thermal treatment at 673 K, mainly consisted of TiO 2 anatase. The samples were characterised by X-ray diffraction, UV–Vis spectroscopy, scanning electron microscopy and atomic force microscopy. The photoactivity of the various films was tested by using as probe reaction the photo-oxidation of 2-propanol in gas-solid regime. The photoreactivity results indicated that the TiO 2 films were efficient for degrading 2-propanol und…

Photocatalytic oxidation mechanism of benzonitrile in aqueous suspensions of titanium dioxide

Abstract The photocatalytic oxidation of benzonitrile was carried out in aqueous suspensions (pH 11) of commercial polycrystalline TiO 2 (Merck and Degussa P25) irradiated by ultraviolet light. The rate of decomposition was dependent on the concentration of benzonitrile and followed a pseudo-first order kinetics. The complete mineralization of a 0.70 mM benzonitrile solution was achieved in ca. 8 h by using TiO 2 Degussa P25, whereas the substrate was only partially mineralized even after 14 h of irradiation in the presence of TiO 2 Merck. The final oxidation products were carbonate and nitrate. The appearance and the evolution of organic and inorganic intermediate species were also investi…

Photocatalytic oxidation of 4-methoxybenzyl alcohol to p-anisaldehyde in a fixed bed continuous reactor,

Photocatalytic Solar Light H 2 Production by Aqueous Glucose Reforming

Formation of high added value chemicals by photocatalytic treatment of biomass

The depletion of fossil fuel requires the search for alternative renewable feedstock and environmentally friendly methods for the production of high value-added compounds and fuels. In this context, the efficient use of biomass has emerged as a significant research field as it represents an alternative green and renewable carbon source. Various technologies have been explored for this purpose and heterogeneous photocatalysis represents a valid alternative to the catalytic methods since it can be carried out under mild experimental conditions without the addition of harmful oxidizing agents. Different biomass components have been used as the starting materials, and many valuable chemicals h…

Preparation in mild conditions of photocatalitically active nanostructured TiO2 rutile

Photocatalytic mineralization of N-containing alicyclic and aromatic heterocycles: Relationship between products containing nitrogen and structure of the substrate

Green Organic Reactions by TiO2 Photocatalysis

This contribution gives an account of TiO2-based selective photocatalysis as a green synthetic tool for the production of organics. Some case studies of the most common transformations carried out by means of photocatalytic reactions are illustrated.

Preparazione e fotoattività di rutilo e brookite ottenuti per termoidrolisi di TiCl4

Synthetic Green Chemistry through Heterogeneous Photocatalysis

This contribution deals with a short review of some application of TiO2 to green organic synthesis. In particular to selective oxidation of aromatic alcohols under mild conditions.

Photocatalytic Nanofiltration Reactors

Catalytic applications of TiO2

Abstract The use of TiO2 as heterogeneous catalyst and/or active support for metals or other oxides is here reported. Many reactions of industrial relevance involve, in fact, titania-based catalysts, among them, NOx abatement, Fischer–Tropsch and water–gas shift, Deacon and Claus processes, hydrodesulfurizations and hydrogenations, selective reductions and selective oxidations. This chapter aims to discuss the main applications of TiO2, in its different forms, as effective support or catalyst for thermocatalytic and photo-thermocatalytic reactions, focusing on the role of its structural and physicochemical properties on the catalytic performance (activity, selectivity, stability).

Selective Photocatalytic Production of Aldehydes

Effects of the TiO2 Phase in the Photocatalytic Oxidation of Aqueous NH3

Polycrystalline TiO2 Powders Impregnated with Porphyrins Used for the Photocatalytic Degradation of 4-Nitrophenol

Relative proportions of rutile and pseudo-brookite phases in the Fe(III)-TiO2 system at elevated temperature

Abstract The Fe(III)-TiO2 system has been studied at T ≥ 1023 K in the range of concentration 2–10 at.% of iron by powder X-ray diffraction, transmission and scanning electron microscopy, and optical microscopy. The relationship between the relative proportions of the TiO2 rutile phase and the pseudo-brookite phase Fe2TiO5, has been investigated in powder samples. Single crystals of pure rutile and rutile doped with 0.5 at.% of iron have been examined to elucidate the microstructures found in the powders. The results suggest that a low degree of solid solubility exists and that doped crystals contain planar faults on 101 planes.

Overview on oxidation mechanisms of organic compounds by TiO2 in heterogeneous photocatalysis

This review provides the reader with a general overview on heterogeneous photocatalytic oxidation mechanisms in the presence of TiO2, with a special address to conversion of aliphatic and aromatic organic species. The aim was to clarify the steps of the photo-oxidation of the various classes of compounds and to relate them with the properties of the catalysts and the experimental conditions used. Reactions carried out to perform complete degradation and photocatalytic partial oxidations have been deeply discussed. Recent isotopic studies highlighted new reaction pathways concerning partial oxidation of alcohols to aldehyde and oxidation of benzene while EPR investigations confirmed that not…

Preparation and characterization of Al2O3 supported TiO2 catalysts employed for 4-nitrophenol photodegradation in aqueous medium

Abstract In this paper the preparation and some bulk and surface characterizations of set of Al2O3 supported TiO2 photocatalysts are reported. The powders were home prepared by a wet impregnation method using titanium (IV) isopropylate. The impregnation was followed by thermal treatments and this procedure was repeated several times in order to obtain samples with different amounts of TiO2. The solids were characterized by X-ray diffraction, specific surface area determination, scanning electron microscopy coupled with an electron microprobe used in an energy-dispersive mode and diffuse reflectance spectroscopy. Moreover, all of them were tested as photocatalysts by using different kinds of…

The combination of heterogeneous photocatalysis with chemical and physical operations: a tool for improving the photoprocess performance

Heterogeneous photocatalysis is a process of great potential for pollutant abatement and waste treatment. In order to improve the overall performance of the photoprocess, heterogeneous photocatalysis is being combined with physical or chemical operations, which affect the chemical kinetics and/or the overall efficiency. This review addresses the various possibilities to couple heterogeneous photocatalysis with other technologies to photodegrade organic and inorganic pollutants dissolved in actual or synthetic aqueous effluents. These combinations increase the photoprocess efficiency by decreasing the reaction time in respect to the separated operations or they decrease the cost in respect o…

Photocatalytic CO2 reduction in gas–solid regime in the presence of H2O by using GaP/TiO2 composite as photocatalyst under simulated solar light

GaP/TiO2 composites exhibited a remarkable photocatalytic activity for CO2 reduction in the presence of water vapor producing methane. By decreasing the GaP:TiO2 mass ratio an increase in the photocatalytic activity of the composite was observed for up to a 1:10 mass ratio. The photocatalytic activity of the composite can be attributed to the band structures of the solids as well as to the efficient charge transfer between GaP and TiO2 heterojunction.

Enhanced (photo)catalytic activity of Wells-Dawson (H6P2W18O62) in comparison to Keggin (H3PW12O40) heteropolyacids for 2-propanol dehydration in gas-solid regime

Abstract Catalytic and photocatalytic 2-propanol dehydration to propene at atmospheric pressure and a temperature range of 60–120 °C were carried out in gas-solid regime by using bare and supported Keggin H 3 PW 12 O 40 (PW 12 ) and Wells-Dawson H 6 P 2 W 18 O 62 (P 2 W 18 ) heteropolyacids (HPAs). Binary materials were prepared by impregnation of the HPAs on commercial SiO 2 and TiO 2 . The Wells-Dawson was in any case more active than the Keggin heteropolyacid and the differences were enhanced when the supported samples were used. In particular, Wells-Dawson HPA supported on TiO 2 and under irradiation showed the highest activity. The HPA species played the key role both in the catalytic …

Preparation and characterisation of TiO2 (anatase) supported on TiO2 (rutile) catalysts employed for 4-nitrophenol photodegradation in aqueous medium and comparison with TiO2 (anatase) supported on Al2O3

Abstract In this paper the preparation of two sets of polycrystalline photocatalysts prepared by supporting TiO2 (anatase) on TiO2 (rutile) or Al2O3 is reported. The powders were prepared by a wet impregnation method using titanium(IV) isopropylate. The impregnation was followed by thermal treatment and this procedure was repeated several times in order to obtain samples with progressively increasing amounts of TiO2 (anatase). The photocatalytic activity of all of the specimens was tested by carrying out the 4-nitrophenol photodegradation, used as a “probe” reaction, in aqueous medium and in different kinds of batch photoreactors. The solids were characterised by X-ray diffraction (XRD), sp…

Enhancing Selectivity In Photocatalytic Formation Of P-Anisaldehyde In Aqueous Suspension Under Solar Light Irradiation Via Tio2 N-Doping

The photocatalytic partial oxidation of 4-methoxybenzyl alcohol to the corresponding aldehyde (p-anisaldehyde) was performed under simulated solar irradiation by using home prepared N-doped TiO2 catalysts. The photocatalysts were prepared by a sol–gel method, using TiCl4 as TiO2 precursor and NH4Cl, urea or NH4OH as N-doping sources. A commercial TiO2 (Degussa P25) was also used for comparison aims. The prepared catalysts were characterized by BET specific surface area, XRD, ESEM and UV-vis spectroscopy. The reactivity results show that (i) the doped catalysts are predominantly amorphous, and they show selectivity values far higher than those of the corresponding undoped ones and of well cr…

Pyrolysis study of sol-gel derived TiO2powders

An amorphous TiO2 gel was obtained by hydrolysing titanium(IV) isopropoxide with a stoichiometric amount of water using SnCl2 as catalyst. In these operative conditions, a TiO2 gel matrix containing a lower fraction of organic residual was obtained with respect to samples prepared by previously modifying the titanium alkoxide precursor with chelating ligands. Dried gel powders were characterized by N2 adsorption analyses, FT-IR and XRD measurements. Thermogravimetric (TG) and differential thermal analysis (DTA) coupled with mass spectrometric (MS) and gas chromatographic (GC) measurements were performed in order to identify the organic products released from TiO2 gel pyrolysis. The Tg-MS se…

"Caratterizzazione ottica di sospensioni acquose di fotocatalizzatori utilizzati in processi di abbattimento di inquinanti organici

Influence of Adsorbed Water on the Activation Energy of Model Photocatalytic Reactions

Two commercial (Merck and Sigma-Aldrich) and two home prepared (HP05 and HP05C) powdered TiO2 photocatalysts were investigated by fast field cycling nuclear magnetic resonance experiments in order to explore the nature of the interactions between water and the solid surfaces. The results were related to the activation energies determined at temperatures ranging from 303 to 353 K for the photocatalytic oxidation in water of three model molecules presenting different interactions with the solid surface (catechol, phenol, and metylbenzoate). The photoactivity results at different temperatures were comparable to each other because the runs were carried out while keeping constant the concentrati…

Preparation and photoactivity of nanostructured anatase, rutile and brookite TiO2 thin films

Photoactive films consisting of pure anatase, brookite or rutile TiO2 were prepared by dip coating from water dispersions obtained by using TiCl4 as the precursor under similar mild experimental conditions

Heterogeneous photocatalytic degradation of nitrophenols

The photocatalytic degradation of 2-, 3- and 4-nitrophenol has been investigated in oxygenated aqueous suspensions containing TiO2. The organic reaction intermediates have been determined by high performance liquid chromatography. The results indicate the complete mineralisation of the substrates and the formation of both nitrate and ammonium ions. The degradation pathways involve a rapid opening of the aromatic ring followed by a slower oxidation of the aliphatic compounds. The hydroxyl radicals are responsible for the primary attack of the nitrophenols with formation of dihydroxynitrobenzenes. The ring hydroxylation occurs in the positions activated by the contemporaneous presence of phen…

Inorganic gels as precursors of TiO2 photocatalysts prepared by low temperature microwave or thermal treatment

Abstract A simple procedure for preparing active TiO2 photocatalysts is presented. The starting materials were unusual TiO2 gels formed from TiCl4. The use of microwaves for a very short time enhanced the TiO2 crystallinity preventing an increase of particle size and minimizing the decrease of specific surface area. This result makes this preparation very attractive. The formation of the gels was monitored through measurements of viscosity. All the samples were characterized by means of X-ray diffraction, diffuse reflectance spectroscopy and BET specific surface area measurements. The photoactivity of the samples was evaluated using the photodegradation of 4-nitrophenol in liquid–solid regi…

Photoactivity under visible light of metal loaded TiO2 catalysts prepared by low frequency ultrasound treatment

Abstract Visible-light responsive bare and metal loaded (Pt, Ag, Rh, Pd) TiO 2 photocatalysts were prepared by using a simple ultrasound treatment. This method induced bulk oxygen deficiency resulting in a narrowing bandgap (from 3.18 to 3.04 eV) and in visible light absorption. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), BET specific surface area (SSA) and pore size distribution (PSD), UV–vis diffuse reflectance spectroscopy (DRS), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity of the samples was evaluated by using the 4-nitrophenol oxidation reaction and the photocatalytic oxidation of glucose w…

Photodegradation kinetics of aniline, 4-ethylaniline, and 4-chloroaniline in aqueous suspension of polycrystalline titanium dioxide

The photodegradation process of aniline, 4-ethylaniline, and 4-chloroaniline in aqueous suspension of irradiated TiO2 (anatase) powder has been investigated. A batch photoreactor with immersed lamp irradiating in the near-UV region has been used for carrying out the reactivity experiments. For each substrate the influence of the initial concentration of organic compound and of pH on the degradation rate has been investigated. The main intermediates and the end products have been identified and determined, the total mass balance being satisfied. The kinetic modelling of the series of reactions occurring in the system has been satisfactorily carried out with a Langmuir-Hinshelwood rate law. T…

A reaction engineering approach to kinetic analysis of photocatalytic reactions in slurry systems

Abstract The knowledge of the rate equation is fundamental for the assessment of the activity of the photocatalytic material and for the study, design and optimization of photocatalytic reactors. In the case of photocatalytic reactions, the local volumetric rate of photon absorption (LVRPA) affects the reaction rate and its inherently uneven distribution within a “slurry” reactor makes complex a correct kinetic analysis. In the present work it is shown which are the critical aspects of the kinetic analysis in slurry reactors and how to carry out photocatalytic experiments to minimize the misinterpretations of the experimental results. In particular, the influence of the type of illumination…

Selective oxidation of aromatic alcohols in the presence of C3N4 photocatalysts derived from the polycondensation of melamine, cyanuric and barbituric acids

AbstractA set of C3N4 samples has been prepared by using melamine, cyanuric acid and barbituric acid as the precursors. The materials were subjected both to physical and chemical characterization and were used as photocatalysts for the selective oxidation of aromatic alcohols in water suspension under UV and visible irradiation. The photoactivity of the materials versus the partial oxidation of four substituted benzyl alcohols was investigated. The type and position of the substituents in the aromatic molecule influenced conversion and selectivity to the corresponding aldehyde. The presence of barbituric and cyanuric acids in the preparation method has changed the graphitic-C3N4 structure, …

Mechanistic aspects of oxalic acid oxidation by photocatalysis and ozonation

Photoadsorption determination for irradiated catalyst in liquid-solid system

Photocatalytic Degradation of 4-Nitrophenol in Aqueous Suspension by Using Polycrystalline TiO2 Impregnated with Lanthanide Double-Decker Phthalocyanine Complexes

The photocatalytic activity of polycrystalline TiO2 samples impregnated with rare-earth-metal diphthalocyanines was investigated. The 4-nitrophenol (4-NP) photocatalytic degradation in aqueous suspension was used as a probe reaction. Commercial anatase TiO2 was impregnated with home-prepared double-decker phthalocyanine complexes of the lanthanide metals, such as Ce, Pr, Nd, Sm, Ho, and Gd. In particular, the impregnation with Ho, Sm, and Nd complexes, acting as sensitizers, proved beneficial for the photoactivity of the studied systems. Significant improvements of the TiO2-based catalytic system appeared possible in terms of lower impregnation loading, enhanced photoreactivity under solar …

Preparazione, Caratterizzazione e Fotoattività di Film di TiO2

Preparation and characterization of photocatalytic TiO2 films

Performance of a Continuousfixed Bed Photocatalytic Reactor for Selective Oxidation of 4-Methoxybenzyl Alcohol to Aldehyde in Organic-free Water

Process Intensification through Coupled Photocatalysis-Ozonation of Contaminated Bromide Containing Waters

Properties of titanium dioxide

"Properties of titanium dioxide" presents a survey of the main physicochemical properties of TiO2 upon which rely all of the applications of this material. Structures and morphologies of titanium dioxide have been taken into account, also in correlation with thermodynamic properties. Bulk and surface defectivity has been described in detail, because of its relevant consequences in terms of catalytic activity. The basic mechanisms of interaction between photons and TiO2 have been discussed on the basis of the optoelectronic features of the semiconductor. Finally, electrical, mechanical, and rheological properties of TiO2 have been presented.

Electron and Energy Transfer Mechanisms: The Double Nature of TiO2 Heterogeneous Photocatalysis

Photocatalytic chemical transformations in the presence of irradiated TiO2 are generally considered in terms of interfacial electron transfer. However, more elusive energy-transfer-driven reactions have been also hypothesized to occur, mainly on the basis of the indirect evidence of detected reaction products whose existence could not be justified simply by electron transfer. Unlike in homogeneous and colloidal systems, where energy transfer mechanisms have been investigated deeply for several organic syntheses, understanding of similar processes in heterogeneous systems is at only a nascent level. However, this gap of knowledge can be filled by considering the important achievements of syn…

SrTiO3 Based Perovskites: Preparation, Characterization and Photocatalytic Activity in Gas-Solid Regime

Degradazione Fotocatalitica Eterogenea di Acetonitrile e Toluene in Regime Gas-Solido e Liquido-Solido

Elementi di Chimica

Photocatalytic oxidation of aromatic alcohols to aldehydes in aqueous suspension of home prepared titanium dioxide

In this paper some intrinsic electronic properties of home prepared (HP) TiO2 catalysts were investigated by diffuse reflectance spectroscopy and quasi-Fermi level measurements. These powders were used for carrying out the photocatalytic oxidation of benzyl alcohol to benzaldehyde and CO2 in water; the selectivity for aldehyde formation was enhanced by the addition of small amounts of ethanol, a typical hole trap. The values of band gap, valence band and conduction band edges are almost identical for all the HP samples in which anatase phase is predominant, whereas appreciable differences can be noticed for an HP sample containing high amount of rutile phase. A comparative ATR-FTIR study of…

Preparation of photocatalytic brookite thin films

Pure brookite films were deposited from a brookite dispersion obtained by peptizing a mixture brookite–rutile prepared by thermolysis of TiCl4 in a HCl solution. The films were characterised by X-ray diffraction and Raman spectroscopy. The photoactivity of the samples was tested by using the photo-oxidation of 2-propanol in gas–solid regime as a probe reaction. The brookite films efficiently degraded 2-propanol under UV illumination.

Photocatalytic Membrane Reactors in the Conversion or Degradation of Organic Compounds

Photocatalytic activity in gas–solid regime of ZnO-ZnAl2O4 composites

Preparazione e caratterizzazione di fotocatalizzatori a base di TiO2

Degradación fotocatalítica de 2-Propanol en régimen gas-sólido utilizando como fotocatalizadores materiales binarios TiO2-carbón activo y ZnO-carbón activo

Photocatalytic degradation of phenol in aqueous titanium dioxide dispersions

The results of a study of photocatalytic degradation of phenol using aqueous oxygenated TiO2 (anatase) suspensions in a batch Pyrex photoreactor are reported. The influence on the photodegradation rate of various parameters as pH, phenol and TiO2 content, oxygen partial pressure, anions present in the dispersions was investigated. A complete oxidation of phenol was observed. Intermediate compounds, catechol and quinone, were detected. It was observed that the photodegradation also proceeded with sunlight radiation. A mechanistic and kinetic model, which accounts for the results obtained, is given. Likely reasons for inactivity of the rutile modification for this reaction are also given.

Determination of Photoadsorption Capacity of Polychrystalline TiO2 Catalyst in Irradiated Slurry

WOS: 000322711800002

ChemInform Abstract: Advances in Selective Conversions by Heterogeneous Photocatalysis

Selective photocatalytic conversions are offering an alternative green route for replacing environmentally hazardous processes with safe and energy efficient routes. This paper reports the most recent advances in the application of heterogeneous photocatalysis to synthesize valuable compounds by selective oxidation and reduction.

Study on TiO2 Photocatalytic Membrane Reactors for Purification of Aqueous Media

Decontamination of wastewater effluents by heterogeneous photocatalysis couplet with other technologies

Structural Changes of Titanium Oxide Induced by Chromium Addition as Determined by an X-Ray Diffraction Study

Abstract An X-ray diffraction study has been carried out on a series of polycrystalline TiO 2 (anatase) catalysts containing Cr(III) at different atomic concentrations (0.2-5.0 at. %), prepared by a co-precipitation method. Analysis of the variation of the unit cell parameters of chromium-doped anatase with respect to pure anatase has allowed us to estimate the solubility limit for the system at around 1.4 at. %. There is no evidence for the existence of a separate crystalline chromium oxide phase. Temperature effects on the cell parameter and on the anatase-rutile transformation rate were also analyzed. An increase in temperature produced release of the chromium from the solid solution. At…

Photocatalytic oxidation in green organic solvent: the case study of water-insoluble phenanthrene

Photocatalytic Partial Oxidation of 5-hydroxymethyl-2-furfural Under UV and Natural Solar Irradiation in Aqueous Suspension of K Containing C3N4

Background: The influence of the potassium metal cation on the graphitic carbon nitride (g-C3N4) photocatalyst has been studied in the partial oxidation of 5-hydroxymethyl-2-furfural (HMF) to 2,5-furandicarboxaldehyde (FDC). Objective: The aim of this study was to understand if the presence of K in C3N4 could increase the oxidative conversion of HMF to high added value species. Methods: Two sets of photocatalysts were prepared by following two different methodologies. In both series of the materials, the precursor of C3N4 was melamine with different types of the K containing species including KCl and KOH in one case and KNO3 alone in the other case. However, for both series of photocatalys…

Photocatalytic activity of TiO2 thin films prepared in the presence of organic and inorganic additives

In search of layered antimony(III) materials: synthesis and characterization of oxo-antimony(III) catecholate and further studies on antimony(III) phosphate

Abstract A new layered oxo-antimony(III) catecholate, [Sb(C6H4O2)]2O, can be obtained by reacting senarmontite with aqueous catechol. The same reaction performed with valentinite, the other allotropic form of Sb2O3, shows an intermediate hydrate that loses water at about 100°C. Both compounds can be obtained from SbPO4 under appropriate experimental conditions. [Sb(C6H4O2)]2O and the hydrated form, which appear to be layered materials, have been characterized by X-ray diffraction, thermogravimetric/differential thermal analyses, and infrared techniques. Preliminary evidence of a reversible intercalation of pyridine into [Sb(C6H4O2)]2O was collected. Taking into consideration the possible us…

Influence of pH on the degradation kinetics of nitrophenol isomers in a heterogeneous photocatalytic system

Abstract The kinetics of photocatalytic degradation of 2-, 3- and 4-nitrophenol in aqueousdispersions containing TiO2 (anatase) has been investigated at different initial values of pH and concentrations of substrate. A pseudo-first order kinetics with respect to the nitrophenol concentration was found to hold; an increase of the substrate concentration and the initial pH was detrimental on the degradation rate.

Preparation and Photoactivity of Rutile Obtained by Hydrolysis of TiCl4

DINAMICA DELL’ACQUA SULLA SUPERFICIE DI UN BIOSSIDO DI TITANIO NANOSTRUTTURATO SINTETIZZATO IN LABORATORIO

Un campione biossido di titanio sintetizzato in laboratorio è stato ottenuto mediante idrolisi di TiCl4 in acqua deionizzata (rapporto in volume 1:10) a temperatura ambiente. Dopo 12 h di agitazione la soluzione trasparente è stata portata all’ebollizione per 0.5 h per ottenere la sospensione finale. La sospensione è stata quindi seccata alla temperatura di 50°C per ottenere il catalizzatore in polvere. Successivamente, la polvere così ottenuta è stata lavata e centrifugata diverse volte allo scopo di ridurre fino a valori trascurabili la concentrazione di ioni cloruro nell’acqua di lavaggio. Il catalizzatore così ottenuto è stato denominato HP0.5 (Home Prepared bollito per 0.5 h) [1]. Un g…

Photocatalytic process intensification by coupling with pervaporation

The integration of photocatalysis with a membrane separation process, in particular pervaporation, permits the recovery of valuable intermediate compounds (aromatic aldehydes) while they are produced avoiding their further degradation in the reactive ambient. In this way the yield and the conversion are enhanced. The coupling of the two processes is straightforward and the integration is complete even maintaining pervaporation and photocatalysis in two separate apparatuses provided that the process stream is continuously recycled at a sufficiently high flow rate. Additional advantages are: higher degree of purification of the aldehyde in the powder-free product stream, semicontinuous produc…

Preparation characterization and photocatalytic activity of polycrystalline ZnO/TiO2 systems. 1. Surface and bulk characterization

Polycrystalline ZnO/TiO2 solids have been prepared with four different methods using home prepared TiO2 (anatase) or TiO2 (rutile) as supports and Zn(NO3)2·6H2O or Zn(CH3COO)2·2H2O as precursors for ZnO. The bulk and surface properties of the samples were investigated by means of TG-DTA, XRD, TEM, SEM-EDAX, XPS, BET surface area determination, and porosity measurements. XRD and TEM results indicate that no significant defect structures exist in any of the samples. The ZnO crystallinity and its enrichment on the surface of TiO2 particles were dependent on the preparation method. The surface areas generally decrease by increasing the amount of ZnO except when ZnO from Zn(CH3COO)2·2H2O was sup…

Process Intensification by Using Ozonation Coupled with TiO2 Photocatalysis for Treating Bromide and/or Bromate Ions Containing Water: The Role of Co-present Model Organic Compounds

ChemInform Abstract: Green Oxidation of Alcohols to Carbonyl Compounds by Heterogeneous Photocatalysis

PHOTOCATALYTIC ACTIVITY OF TIO2 IN ITS POLYMORPHIC FORMS ANATASE, BROOKITE AND RUTILE

Photocatalysis for Green Synthesis

ChemInform Abstract: Heteropolyacid-Based Materials as Heterogeneous Photocatalysts

Invited for the cover of this issue is the group of Giuseppe Marci and Leonardo Palmisano at the Universita degli Studi di Palermo, Italy. The cover image shows one aspect of the photocatalytic use of heteropolyacids: dye bleaching by irradiation with sunlight.

Preparation of Sm-loaded brookite TiO2 photocatalysts

Abstract Pure and Sm-loaded brookite nanoparticles and thin films were prepared using TiCl4 as precursor of TiO2. The samples were characterized by X-ray diffraction (XRD), specific surface area (SSA) determination, diffuse reflectance spectroscopy (DRS) and photoluminescence (PL) measurements. The photocatalytic activity of the powders was investigated by employing the photodegradation of 4-nitrophenol in a liquid–solid system whilst the photoreactivity of the films was tested by evaluating the rate of degradation of 2-propanol in a gas–solid system. Loading with Sm resulted in a significant improvement of the photoreactivity of brookite and the beneficial effect was attributed to an incre…

Polycrystalline TiO2 impregnated with cardanol-based porphyrins for the photocatalytic degradation of 4-nitrophenol

Hydrogenated cardanol (3-n-pentadecylphenol), a renewable organic resource obtained by vacuum distillation of roasted “cashew nut shell liquid” (CNSL), a by-product of the cashew industry, has been used to synthesize novel lipophilic porphyrins. Polycrystalline TiO2 impregnated with these novel “cardanol-based” porphyrins as sensitizers has been investigated in the photodegradation of 4-nitrophenol (4-NP) in aqueous suspension. The results indicated that the presence of the sensitizer enhances the photoactivity of polycrystalline bare TiO2 in the process. The activating effect was higher in the case of the Cu-complex.

(Photo)electrocatalytic Versus Heterogeneous Photocatalytic Carbon Dioxide Reduction

The present review summarizes some of the main results achieved in electrochemical, photocatalytic, and (photo)-electrocatalytic systems for the reduction of carbon dioxide. After a preliminary survey of the electrocatalytic and photocatalytic systems in terms of materials used, efficiencies, operating conditions, and product distribution, it is shown how the combination of the two approaches affords often higher efficiency than the single technologies and allows better control of the product distribution. In fact, the peculiar energetic distribution at the interface of irradiated semiconductors under opportune electrical bias enables enhancement of the spatial separation of the photogenera…

Effect of the addition of different doping agents on visible light activity of porous TiO2 photocatalysts

Abstract The influence of the addition of different doping agents (N, W and Hf) on the macroporous TiO2 photoactivity toward the Rhodamine B degradation and ethanol photo-oxidation was evaluated. The samples were characterized by XRD, XPS, SEM, TEM, N2 adsorption-desorption, UV–vis Diffuse Reflectance and Photoluminescence spectroscopies to study also the changes in the physico-chemical properties due to the presence of dopants. The photonic effect and the high ordered porous structure of the macroporous TiO2 that lead to increase the path length of the light, were the key factors that allow to enhance the catalytic activity towards the dye and VOC degradation under visible and solar light …

Photocatalytic partial oxidation of limonene to 1,2 limonene oxide

The silylation of crystalline TiO2 P25, commonly used for photocatalytic degradation of pollutants, results in an exceptionally selective catalyst for the aerobic limonene epoxidation to 1,2-limonene oxide under solar light irradiation. The hypothesized mechanism involves the singlet oxygen generated through energy transfer from the excited TiO2 to adsorbed O2 molecules. The reaction product is the valued precursor of bio-based poly(limonene carbonate), a thermoplastic polymer of superior thermal and optical properties whose industrial production is in need of an efficient green synthesis of limonene oxide.

Characterisation and photoactivity of nanostructured TiO2 obtained by hydrolysis of TiCl4

TiO2 in Organic Photosynthesis: Sunlight Induced Functionalization of Heterocyclic Bases in the Presence of TiO2

N-TiO2 Photocatalysts highly active under visible irradiation for NOX abatement and 2-propanol oxidation

N-doped TiO2 powders were prepared by two different sol-gel methods. Samples were characterised by X-ray diffraction (XRD), BET specific surface area measurements (SSA), scanning electron microscopy (SEM), diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS) and Electron Paramagnetic Resonance (EPR). XPS measurements revealed a signal at 400 eV assignable to nitrogen in the form of Ti-N-O. EPR signals are attributed to molecular NO trapped with cavities/defects possibly interacting with oxygen vacancies. The photocatalytic activity under UV and visible light was determined following the abatement of NOx and the photodegradation of 2-propanol in gas-solid systems. N…

Structural and surface characterization of the polycrystalline system CrxOy · TiO2 employed for photoreduction of dinitrogen and photodegradation of phenol

The polycrystalline system CrxOy-TiO2, used as a catalyst for photoreactions, was studied by X-ray diffractometric method, visible-ultraviolet diffuse reflectance and infrared spectroscopic methods, surface area determination, and porosimetry to characterize its structural and surface features. Two series of catalysts were prepared by two different methods, namely by coprecipitation and by impregnation. The first series was tested as photocatalysts for the dinitrogen photoreduction in a gas-solid regime and for the phenol photodegradation in a liquid-solid regime. The results indicate that the interaction of chromium ions with OH groups modifies the surface properties of the supports and co…

Synthesis and characterization of titanium dioxide and titanium dioxide–based materials

Abstract The aim of the chapter is to describe some different preparation methods and characterization techniques for bare, supported, and coupled TiO2 samples used in different fields. Particular attention has been paid both to the fundamental aspects of the different TiO2 preparation and characterization methods and the practical applications that the results obtained can have. Various examples have been reported from the literature to demonstrate the usefulness that students and scientists working with TiO2-based materials in different research areas can derive from various characterizations.

Photodegradation of Lincomycin in aqueous TiO2 suspension by using artificial or solar light

Photocatalytic formation of H2 and value-added chemicals in aqueous glucose (Pt)-TiO2 suspension

Abstract Commercial and home prepared bare and Pt-supported TiO2 samples were used as the photocatalysts for the aqueous photo-conversion of glucose at ambient pressure and temperature. Aerobic and anaerobic conditions were used to study the products of glucose degradation both in the liquid (arabinose, erythrose, gluconic acid, glucaric acid, fructose and formic acid) and gaseous (H2 and CO2) phases. The distribution of these molecules was different in the presence of the various powders, depending on the structural and physico-chemical properties of the materials, and Pt resulted essential for the anaerobic production of H2. The home prepared samples resulted more active than the commerci…

A survey of photocatalytic materials for environmental remediation

Abstract Heterogeneous photocatalysis is an advanced oxidation process which has been the subject of a huge amount of studies related to air cleaning and water purification. All these processes have been carried out mainly by using TiO 2 -based materials as the photocatalysts and ca. 75% of the articles published in the last 3 years is related to them. This review illustrates the efforts in the search of alternative photocatalysts that are not based on TiO 2 , with some exceptions concerning particularly innovative modifications as nanoassembled TiO 2 or TiO 2 composites with active carbon, graphite and fullerene. Papers reporting preparation, characterization and testing of binary, ternary…

Degradation of Lincomycin in Aqueous Medium: Coupling of Solar Photocatalysis and Membrane Separation

Heteropolyacid‐Based Materials as Heterogeneous Photocatalysts (Eur. J. Inorg. Chem. 1/2014)

Photocatalytic degradation enhancement in pickering emulsions stabilized by solid particles of bare TiO 2

Pickering emulsions provide a new way to enhance the efficiency of photocatalytic degradation of water-insoluble pollutants. Indeed, the semiconductor solid particles dually act as the photocatalyst and stabilizer of the emulsion droplets whose size dramatically affects the photocatalytic reaction. The present work aims at the validation of this concept by using bare TiO 2 without any surface modification. Nanostructured TiO 2 has been prepared by a simple sol-gel process and characterized by X-ray diffraction, specific surface area analysis, scanning electron microscopy, and diffuse reflectance spectroscopy. The emulsions were prepared by using 1-methylnaphthalene (1-MN) as a model organic…

Preparation, thermal analysis and photoactivity of TiO2 samples

Photon absorption by aqueous TiO2 dispersion contained in a stirred photoreactor

We present a simple experimental method which allows the evaluation of the absorbed photon flow. The method is based on measurements of transmitted photon rates (by means of standard actinometer solutions) for different reactor thicknesses and/or catalyst concentrations. The method was applied to phenol degradation reaction carried out in a stirred batch phtotoreactor containing aqueous TiO 2 (anatase) dispersion, directly irradied by a 1,500 W Xe lamp

Porphyrin cardanol based impregnated polycriystalline TiO2 samples in the photocatalytic degradation of 4-nitrophenol

TIO2 brookite: Properties, synthesis and applications

Brookite is one of the less studied polymorphic phases of titanium dioxide. Indeed, synthetic procedures affording brookite as a pure phase were not straightforward and have been only recently optimized. For this reason, brookite has received particular attention in the last years, especially as a promising photocatalytic material for environmental remediation and for the synthesis of valuable organic products. The present chapter will review the main synthetic methods reported in literature to produce brookite as a pure phase or mixed with rutile and/or anatase. Morphological, structural and electronic properties both of pure or variously modified brookite will be presented. The particular…

TiO2 Heterogeneous Photocatalysis as a Selective Tool for Organic Green Syhtneses

Photo-assisted degradation of 2-propanol in gas–solid regime by using TiO2 impregnated with heteropolyacid H3PW12O40

Abstract Commercial and home prepared TiO2 samples impregnated with tungstophosphoric acid (H3PW12O40) were used for the photo-assisted degradation of 2-propanol in gas–solid regime. The characterization results evidenced a good coverage of the polyoxometalate (POM) onto the surface of TiO2 along with a marginal effect of the presence of the POM on the specific surface area, morphology and cristallinity of the samples. Propene was the main intermediate product revealed in 2-propanol photocatalytic degradation by using as photocatalysts the samples containing the POM, whereas propanone was mainly obtained when the photocatalysts was bare TiO2, both commercial or home prepared. Acetaldehyde w…

Elemental Bromine Production by TiO2 Photocatalysis and/or Ozonation

Significant production of elemental bromine (Br2 ) was observed for the first time when treating bromide containing solutions at acidic pH, with TiO2 photocatalyst, ozone, or a combination thereof. Br2 selectivities up to approximately 85 % were obtained and the corresponding bromine mass balance values satisfied. The process is general and may be applied at a laboratory scale for green bromination reactions, or industrially as a cheap, safe, and environmentally sustainable alternative to the currently applied bromine production methods.

Keggin heteropolyacid supported on TiO2 used in gas-solid (photo)catalytic propene hydration and in liquid-solid photocatalytic glycerol dehydration

Abstract (Photo)catalytic propene hydration to 2-propanol and glycerol dehydration to acrolein were carried out by using Keggin heteropolyacids (HPAs) supported on TiO 2 . Binary materials have been prepared by impregnation of H 3 PW 12 O 40 , H 3 PMo 12 O 40 and H 4 SiW 12 O 40 , on TiO 2 Evonik P25. Moreover, a binary material consisting of H 4 SiW 12 O 40 and TiO 2 was prepared via a hydrothermal treatment and tested for the same reactions. All the materials were characterized by X-ray diffraction (XRD), scanning electron microscopy observations (SEM) coupled with energy dispersive X-ray (EDX) measurements, diffuse reflectance spectroscopy (DRS), Raman spectroscopy and Fourier transform …

Green Oxidation of Alcohols to Carbonyl Compounds by Heterogeneous Photocatalysis

Influence of the Substituent on Selective Photocatalytic Oxidation of Aromatic Compounds in Aqueous TiO2 Suspensions.

Experimental results are reported showing that the photocatalytic oxidation of aromatic compounds containing an electron-donor group (EDG) gives rise mainly to ortho- and para-monohydroxy derivatives while in the presence of an electron-withdrawing group (EWG) all the monohydroxy derivatives are obtained.

TiO2 nanocrystalline powders by W/O microemulsion synthesis

Photocatalytic Isomerization of Caffeic Acid and its Cyclization to Esculetin

tThe photoisomerization of trans-caffeic acid to cis-caffeic acid has been studied in the presence of N2in homogeneous aqueous solutions and in suspensions of various TiO2catalysts. The results supportedthe hypothesis of an energy transfer process from TiO2 to the substrate due to the recombination of the photogenerated electron–hole pairs.

A comparative study of the photocatalytic activities of iron-titanium (IV) oxide photocatalysts prepared by various methods; spray pyrolysis, impregnation and co-precipitation

Abstract A series of iron/titanium oxide photocatalysts of varying Fe 3+ content have beenprepared by a number of different methods and subjected to controlled thermal treatment. Specimens have been characterised in terms of their crystalline structure and morphology, and indicate solid solutions containing both the anatase and rutile phases of TiO 2 , together with the formation of pseudo-brookite in some specimens. Intrinsic photo-activity measurements have been performed using a standard liquid-phase photocatalytic reaction. Results indicate that the photocatalytic activity of the specimens differs according to the method of preparation, and that all solids containing iron (III) species …

Exploring the photothermo-catalytic performance of brookite tio2-ceo2 composites

The thermocatalytic, photocatalytic and photothermo-catalytic oxidation of some volatile organic compounds (VOCs), 2-propanol, ethanol and toluene, was investigated over brookite TiO2-CeO2 composites. The multi-catalytic approach based on the synergistic effect between solar photocatalysis and thermocatalysis led to the considerable decrease in the conversion temperatures of the organic compounds. In particular, in the photothermo-catalytic runs, for the most active samples (TiO2-3 wt% CeO2 and TiO2-5 wt% CeO2), the temperature at which 90% of VOC conversion occurred was about 60 &deg

Heteropolyacid‐Based Materials as Heterogeneous Photocatalysts

Heteropolyacids (HPAs) that are often used as heteropolyanions are cheap and stable compounds that have been extensively used as acid and oxidation catalysts as a result of their strong Brønsted acidity and ability to undergo multielectron-transfer reactions. HPAs, which are very soluble in water and polar solvents, have been also used as homogeneous photocatalysts for the oxidation of organic substrates in the presence of oxygen, but their use in heterogeneous systems is by far desirable. Dispersing HPAs onto solid supports with high surface area is useful to increase their specific surface area and hence (photo)catalytic activity. Moreover, owing to the high energy gap between the HOMO an…

Photocatalytic activity of binary and ternary SnO2–ZnO–ZnWO4 nanocomposites

Binary and ternary SnO2-ZnO-ZnWO4 nanocomposites were prepared by a sol-gel route. The photocatalytic activity of the samples was evaluated through the decomposition of 4-nitrophenol and partial oxidation of 4-methoxybenzyl alcohol to p-anisaldehyde. All the mixed catalysts revealed higher photoactivity than bare ZnO, SnO2 or ZnWO4 and the best performances were exhibited by the binary nanocomposites. The high photocatalytic activity was explained by the presence of heterojunctions among different semiconductors that enhance the separation of the photogenerated electron-hole pairs, hindering their recombination. As a general consideration, an essential role was played by the electronic feat…

Photocatalytic properties of TiO2 doped with metal and non metal species

Partial photocatalytic oxidation of glycerol in TiO2 water suspensions

2nd European Conference on Environmental Applications of Advanced Oxidation Processes -- SEP 09-11, 2009 -- Nicosia, CYPRUS

Preface

Preface of the book "Heterogeneous Photocatalysis Relationships with Heterogeneous Catalysis and Perspectives"

Photocatalytic abatement of organic compounds using home prepared TiO2 as photocatalysts

Sunlight induced functionalisation of heterocyclic bases in the presence of TiO2

The influence of Al doping on the photocatalytic activity of nanostructured ZnO: The role of adsorbed water

Abstract Al doped ZnO nanoparticles (labeled as x% A-ZnO, x = 0.0, 0.5, 1.0, and 1.5) were synthesized by a simple sol-gel method, characterized and tested as photocatalysts for the degradation of a model compound under UV-light irradiation. Diffuse reflectance spectroscopy (DRS) and photoelectrochemical analysis have been performed to evidence their optical and electronic behavior. The structural features of the powders were highlighted by means of specific surface area (SSA) analysis, X-ray diffraction (XRD), Fourier-transform infrared (FTIR) and Raman spectroscopy. Al doping results in enhanced photocatalytic activity of the modified powders with respect to pure ZnO. In particular, the h…

Pervaporation membrane reactors (Chapter 3)

Photocatalytic oxidation of gaseous toluene on anatase TiO2 catalyst: Mechanistic aspects and FT-IR investigation

Abstract Photo-oxidation of toluene has been carried out in gas–solid regime by using polycrystalline anatase TiO2 as the catalyst. The reacting gaseous mixture was toluene, air and water in various molar ratios. A pyrex fixed-bed continuous photoreactor irradiated by a medium pressure Hg lamp was used for performing the photoreactivity experiments. The main oxidation product was benzaldehyde but benzene, benzyl alcohol and traces of benzoic acid, phenol and unidentified compounds were also detected. The molar conversion to benzaldehyde with respect to the initial amount of toluene was ca. 20% in the best experimental conditions. Benzene was produced only as a transient product during the f…

TiO2 Impregnated with Polyoxometallate as Photomediator in 2-Propanol Gas-Solid Regime Photocatalytic Degradation

Efficient H2 production by photocatalytic water splitting under UV or solar light over variously modified TiO2-based catalysts

Abstract This paper focused for the first time on the comparison between three different approach to modify the chemico-physical properties of TiO2-based photocatalysts and their effect in the H2 production by photocatalytic water splitting both under UV and solar light irradiation, under the same experimental conditions. The application of pulsed laser irradiation to aqueous TiO2 suspensions (first approach) induced structural transformations both on the bulk and on the surface of TiO2, boosting the H2 production, under UV light irradiation, of almost three times (20.9 mmol/gcat·h) compared to bare TiO2 (7.7 mmol/gcat·h). The second strategy was based on a templating method to obtain TiO2 …

Green synthesis of bromine by TiO2 heterogeneous photocatalysis and/or ozone: A kinetic study

Abstract Elemental bromine is an industrially relevant compound traditionally produced from bromide ions by using chlorine as the oxidizing agent. Problems related to transportation and handling of the corrosive, expensive and toxic chlorine make green synthetic alternatives highly desirable. In this paper the green synthesis of bromine from bromide in aqueous solutions under mild conditions by means of TiO2 photocatalysis and/or ozonation has been investigated from a kinetic point of view. The ozonation in the absence of the photocatalyst follows a first order kinetic with respect to both ozone and bromide. The kinetics of the reactions in the presence of the photocatalyst has been describ…

CO2 reduction by C3N4-TiO2 Nafion photocatalytic membrane reactor as a promising environmental pathway to solar fuels

Abstract We investigated CO2 photocatalytic reduction coupling, for the first time in literature, the assets offered by the continuous operating mode using C3N4-TiO2 photo-catalyst embedded in a dense Nafion matrix. The reactor performance was analyzed under UV–vis light in terms of productivity, selectivity and converted carbon. Reaction pressure was specifically investigated for its effect as a “driver” in determining reactor performance, modulating products removal from the reaction volume. In addition, the membrane reactor performance was explored as a function of H2O/CO2 feed molar ratio and contact time. The higher feed pressure (5 bar) led to a lesser MeOH production and a greater am…

Photodegradation of Pharmaceuticals in Water Catalyzed by Polycrystalline TiO2 Powder in a Nanofiltration Membrane Reactor

Confronto tra attività catalitica e fotocatalitica dell’eteropoliacido di Keggin H3PW12O40 supportato su ossidi o su nanotubi di carbonio

Catalytic and catalytic photo-assisted dehydration of 2-propanol to form propene in gas-solid regime at atmospheric pressure and 80°C was carried out by using a Keggin heteropolyacid H3PW12O40 (PW12) supported on different oxides. Binary materials have been prepared by impregnation of PW12 on different commercial and home prepared supports (TiO2, SiO2 or carbon nanotubes). The supported Keggin PW12 species played a key role both for the catalytic and the photo-assisted catalytic reactions, due to their strong acidity and ability to form strong oxidant species under UV irradiation, respectively. The contemporary presence of heat and UV light improved the activity of almost all POM supported …

Photocatalytic oxidation of trans-ferulic acid to vanillin on TiO2 and WO3-loaded TiO2 catalysts

Abstract The photocatalytic oxidation of trans-ferulic acid to vanillin in water has been studied by using various TiO2 and WO3-loaded TiO2 samples as catalysts. Different values of selectivity were obtained depending on the physico-chemical properties of the single samples and a vanillin selectivity of 10% was reached in the presence of the commercial TiO2 Merck. Higher selectivity values were obtained by impregnation of TiO2 with H2WO4 followed by calcination. The increased production of vanillin exhibited by the obtained WO3-loaded TiO2 powders was attributed to a reduced further oxidation of the aldehyde caused by the presence of the practically inactive tungsten trioxide hydrate on the…

Fine chemistry by TiO2 heterogeneous photocatalysis

Abstract Heterogeneous TiO2 photocatalysis is a promising technology based on the capability of the semiconducting material to generate charges upon irradiation of suitable energy. The photogenerated electrons and holes, in turn, induce redox reactions involving species adsorbed on the surface of the photocatalyst, giving rise to chemical transformations. The presence of highly oxidizing radicals, thus generated, has long led to consider TiO2 photocatalysis only a nonselective oxidation process. In fact, so far it is possible to find in the literature many examples of its use in the field of environmental remediation aimed at the degradation of harmful molecules, although the studies are al…

Mechanistic aspects of oxalic acid oxidation by photocatalysis and ozonation

Oxalic acid has been oxidised in acidic aqueous solutions (pH 3) using photocatalysis and ozonation alone or coupled. The simultaneous presence of ozone, titanium dioxide and near UV irradiation increases the oxidation rate of oxalic acid to values greater than those deriving from the single contributions of photocatalysis and ozonation. In particular in the present paper ozonation alone, heterogeneous photocatalysis and also combined ozonation with heterogeneous photocatalysis have been used for the oxidation of oxalic acid at acidic pH in the presence of TiO2 Degussa P25. A likely mechanism, able to explain both the homogeneous and heterogeneous processes, is discussed.

Improvement of membrane performances to enhance the yield of vanillin in a pervaporation reactor.

In membrane reactors, the interaction of reaction and membrane separation can be exploited to achieve a “process intensification”, a key objective of sustainable development. In the present work, the properties that the membrane must have to obtain this result in a pervaporation reactor are analyzed and discussed. Then, the methods to enhance these properties are investigated for the photocatalytic synthesis of vanillin, which represents a case where the recovery from the reactor of vanillin by means of pervaporation while it is produced allows a substantial improvement of the yield, since its further oxidation is thus prevented. To this end, the phenomena that control the permeation of bot…

Phthalocyanines-TiO2: A New Efficient and Tunable Catalyst for CO2 Reduction in Water

Fundamentals of photocatalysis: The role of the photocatalysts in heterogeneous photo-assisted reactions

Abstract This chapter provides some general definitions of heterogeneous photocatalysis and evaluates its performance, which is influenced by the parameters most closely related to the properties of the solid material that acts as a photocatalyst. It also discusses aspects of heterogeneous photocatalytic reactions and explains the properties that influence photoactivity. Finally, the chapter examines thermodynamic and kinetic features, including mechanistic details and parameters to define the reaction rate and correlates them to the effects of the interaction of light with the photocatalyst surface and adsorption-desorption of species involved in heterogeneous photo-assisted reactions.

Surface and Electronic Features of Fluorinated TiO 2 and Their Influence on the Photocatalytic Degradation of 1-Methylnaphthalene

International audience; Surface fluorination improves the photocatalytic activity of TiO2, and the influences of various features of fluorinated TiO2 (TiO2–F) have often been discussed in the literature. The present paper addresses the changes induced by surface fluorination on the morphological, structural, surface, and electronic features of TiO2. In particular, X-ray diffraction, specific surface area analysis, and transmission and scanning electron microscopy give evidence that surface fluorination does not affect the structural properties and the morphology of TiO2 nanoparticles. In contrast, fluorination induces changes of surface and electronic properties. Chemical and thermogravimet…

Oxidacíon fotocatalítica de alcoholes aromáticos. Influencia de la adicíon de atrapadores de huecos en la selectividad a aldehídos

Highly active photocatalytic TiO2 powdwers obtained by thermohydrolysis of TiCl4 in water

Highly active photocatalytic TiO2 samples were synthesized by thermohydrolysis of TiCl4 in water at 100 °C. Rutile, binary mixtures of anatase and rutile or anatase and brookite, or ternary mixtures of anatase, brookite and rutile were obtained depending on the TiCl4/H2O ratio. Rietveld refinements were employed to evaluate the crystalline phases and composition of the mixtures. The effect of the aging time on the phase composition was also studied. The band gap values of the samples were obtained by the diffuse reflectance spectra. The position of the flat band potentials of anatase, brookite and rutile was determined measuring the photovoltage as a function of the suspension pH. From thes…

Influence of Surface-Related Phenomena on Mechanism, Selectivity, and Conversion of TiO2 -Induced Photocatalytic Reactions

Heterogeneous photocatalysis is the result of an inextricable connection of several factors differently contributing to the overall process. Photon absorption is the “sine qua non” condition for the reaction to occur. In fact, photons can be considered as immaterial reactants, and all of the phenomena related to the interaction of light–matter play a prominent role. However, other factors contribute in a concerted way to address the reaction, so that the relative contribution of each of them is often difficult to evaluate. In this framework, the present paper highlights some aspects of the interaction of TiO 2 surface-adsorbate species that could be underestimated and their influence on the…

Photocatalytic ozonation:Maximization of the reaction rate and control of undesired by-products

In theso-calledphotocatalyticozonation(PO)synergisticeffectsbetweenphotocatalysisandozonation enhance therateofoxidationoforganiccompounds,thereforethisintegratedprocessisverypromising for useinwatertreatment.Inthepresentwork,itisdemonstratedthattheimprovementthatcanbe obtained bytheintegratedprocessincomparisonwiththeuncoupledprocessesdependsontherelative weight between photocatalysis and ozonation. In this respect, it has been found that a relatively low rate of photocatalysis (0.3 times the rate of ozonation)issufficienttogetthehighestsynergyandtomaximize the performancesintheoxidationofformate,theadoptedmodelorganiccompound.Thebenefitsof the couplingofphotocatalysistoozonationarenotlimi…

Surface characterization of metal ions loaded TiO2 photocatalysts: structure-activity relationship

Transition metal loaded TiO2 powders were characterised and tested for the photodegradation of some organic acids. Both Lewis and Brønsted surface acid sites were present in the samples containing large amounts of Mo, V and W. The Brønsted sites are associated to the presence of the transition metals as they do not exist in the unloaded support, and in particular to the presence of these metals in high oxidation states. The trend of the pzc values of the various powders matches rather well both with the surface acidity of the samples experimentally determined by NH3 adsorption and with a scale of acidity/basicity for bulk binary oxides. XPS investigation indicates that only the presence of …

Photocatalytic degradation of nitrophenols in aqueous titanium dioxide dispersion

Abstract The results are reported of an investigation into the photodegradation of nitrophenol isomers carried out in aqueous titania (anatase) dispersions under various experimental conditions. We investigated the influence of various parameters on the photodegradation rate, such as the concentrations of the catalyst, dissolved oxygen and organic compound, and the presence of various anions in the dispersion. A plausible explanation is proposed for the influence of these parameters, both mechanistic and kinetic factors being accounted for. Gas chromatography and mass spectrometry were used as analytical methods in order to determine intermediate products. Spectroscopic methods (UV-vis and …

Selective Heterogeneous Photocatalysis: Achievements and Challenges

Determination of Cr(III) as Cr(III)/EDTA Complex by EDTA Excess Back-Titration with Zn(II) in Presence of 4-(2-Pyridylazo)-Resorcinol Indicator and Naphthol Green β as Inert Dye

Determination of Cr(III) as Cr(III)/EDTA Complex by EDTA Excess Back-Titration with Zn(II) in Presence of 4-(2-Pyridylazo)-Resorcinol Indicator and Naphthol Green β as Inert Dye.

The electrochemistry of carbon monoxide reductive cyclotetramerization to squarate anion

Abstract The electrochemical reduction, of carbon monoxide to C4O2−4 squarate anion is investigated. Particular attention is devoted to the influence that solvents, electrolytes, electrodes and carbon monoxide pressure have on the yields. The main feature appears to be that strictly controlled conditions are not necessary for cyclotetramerization. In dmf — Bu4NBr the following yields vs reacted CO and circulated charge were obtained with different cathodes: Pt(49%, 34%); Au(48%, 29%); Al(47%, 38%); stainless steel (36%, 33%); graphite (39%, 31%). A distinct influence of the supporting electrolyte (inorganic and tetraalkylammonium halides) was however observed.

Removal of drugs in aqueous systens by photoassisted degradation

Aqueous solutions of tetracycline, lincomycin and ranitidine were irradiated with UV light in homogeneous and heterogeneous systems. Two commercial polycrystalline TiO2 powders (Degussa P25 and Merck) were used as photocatalysts. After 5A h, an appreciable photolytic degradation of tetracycline and ranitidine was observed while the degradation of lincomycin was noticeably lower. As far as the mineralization is concerned, a small decrease of the TOC values was measured in the case of tetracycline whereas negligible variations were found for lincomycin or ranitidine. The presence of the photocatalysts greatly enhanced the degradation rates of the drugs with respect to those observed during th…

Pervaporation membrane reactors

Pervaporation is a peculiar membrane separation process which is now considered for the integration with some types of reactions in new promising and interesting applications. Indeed, pervaporation membrane reactors are suitable to some specific utilizations also in sustainable chemistry, which is an area currently characterized by a growing interest. The fundamentals of this type of membrane reactors are presented and the advantages and the difficulties in many applications are discussed and reviewed with particular attention to the opportunities for future developments.

Local structure of the supported Keggin and Wells-Dawson heteropolyacids and its consequence on their (photo)catalytic activity

Photo-oxidation of Azo-dyes in Water Catalyzed by TiO2 in a Membrane Reactor

An Investigation into the Stability of Graphitic C 3 N 4 as a Photocatalyst for CO 2 Reduction

The increasing CO 2 concentration in the atmosphere exerts a significant influence on global warming and climate change. The capture and utilization of CO 2 by conversion to useful products is an area of active research. In this work, the photodriven reduction of CO 2 was investigated using graphitic carbon nitride (g-C 3 N 4 ) as a potential photocatalyst. The photocatalytic reduction of CO 2 was investigated with g-C 3 N 4 powder immobilized on a glass support in a batch gas-phase photoreactor. The experiments were carried out under UV-vis irradiation at 70 °C and an initial pressure of 2.5 bar. The only gas-phase product detected during the irradiation of the g-C 3 N 4 in the presence of…

Preparation, characterisation and photoactivity of nanostructured TiO2 catalysts

Comparison between catalytic and catalytic photo-assisted propene hydration by using supported polyoxometalate.

Optical characterization of TiO2 suspensions: influence of some operational parameter on mean particle size

Photoassisted Mineralization of N-Heterocycles in TiO2 Aqueous Suspensions: Fate of the N-Heteroatoms

ChemInform Abstract: Rate of Photon Absorption and Turnover Number: Two Parameters for the Comparison of Heterogeneous Photocatalytic Systems in a Quantitative Way

Abstract In order to correctly compare the performance of different photocatalytic systems using polycrystalline semiconductor oxides, two parameters are proposed: the rate of photon absorption (rpa) and the turnover number (tn). From these quantities the quantum yield (qy), which indicates the efficiency of the absorbed photons for promoting a reaction event, can be determined. The phenol photodegradation reaction, carried out in aqueous dispersions of polycrystalline TiO2 (anatase) of different preparation methods and sources, has been used as “test reaction” in order to determine the tn, rpa and qy values.

Photodegradation of pharmaceutical drugs in aqueous TiO2 suspensions: mechanism and kinetics

WOS: 000251165800003

Photocatalytic oxidation of acetonitrile in aqueous suspension of titanium dioxide irradiated by sunlight

The photocatalytic oxidation of acetonitrile (CH3CN) was carried out in aqueous suspensions of polycrystalline TiO2 P25 Degussa irradiated by sunlight. A plug flow photoreactor in a total recycle loop was used for carrying out reactivity experiments in which the concentrations of acetonitrile, of its intermediate oxidation products and of not-purgeable organic carbon (NPOC) were monitored. The influence of the presence of strong oxidant species (H2O2, S2O82−, ClO−) on the process rate was studied. The dependence of acetonitrile photo-oxidation rate on the substrate concentration and on the catalyst amount was also investigated. The photodegradation rate of substrate and NPOC followed first …

Catalytic and photothermo-catalytic applications of TiO2-CoOx composites

Objective: The necessity to have green and sustainable industrial processes has promoted new technologies for air and water purification together with the research of new energy sources. In this contest, the TiO2-based photocatalysis can be considered a promising route for both environmental applications aIn this work, we have investigated the photocatalytic performance of TiO2-CoOx composites on both photooxidation and photoreduction reactions. Specifically, we have compared the performance of the composites in the thermo-catalytic, photo-catalytic and photothermal-catalytic oxidation of ethanol chosen as model volatile organic compound (VOC) and in the photocatalytic hydrogen production …

A study on the catalytic perfomances of H3PW12O40 supported on TiO2 and SiO2 for propene hydration in the presence and in the absence of UV light

Rate of photon absorption and turnover number: two parameters for the comparison of heterogeneous photocatalytic systems in a quantitative way

Abstract In order to correctly compare the performance of different photocatalytic systems using polycrystalline semiconductor oxides, two parameters are proposed: the rate of photon absorption (rpa) and the turnover number (tn). From these quantities the quantum yield (qy), which indicates the efficiency of the absorbed photons for promoting a reaction event, can be determined. The phenol photodegradation reaction, carried out in aqueous dispersions of polycrystalline TiO2 (anatase) of different preparation methods and sources, has been used as “test reaction” in order to determine the tn, rpa and qy values.

ChemInform Abstract: Coupled Semiconductor Systems for Photocatalysis. Preparation and Characterization of Polycrystalline Mixed WO3/WS2 Powders.

Mixed WO3/WS2 powders were prepared by oxidation of WS2. The physical properties of the samples were characterized by X-ray diffraction, diffuse reflectance spectroscopy, and scanning electron microscopy; they were strongly dependent upon the time and temperature of oxidation. The chemical state and the elemental distribution of the sample surface were investigated by X-ray photoelectron spectroscopy. The photocatalytic results have showed that the aqueous suspensions of the mixed WO3/WS2 systems have significantly higher activities than pure WS2 and WO3 for the photodegradation of phenol. The enhanced performance can be related to the presence of heterojunctions WO3/WS2 on the single parti…

Photocatalytic green synthesis of piperonal in aqueous TiO2 suspension

Abstract Piperonal (heliotropine or 3,4-methylenedioxybenzaldehyde) has been synthesized by oxidizing piperonyl alcohol in aqueous UV-irradiated TiO2 suspensions. This compound was identified by GC–MS chromatography, 1H NMR and melting point determination. The other products of the photoprocess were 1,3-bis(3,4-(methylenedioxy)benzyl) ether (found in traces) and CO2, derived from the parallel pathway of photo-mineralization. Commercial and home-prepared TiO2 samples have been tested and the best selectivity (ca. 35%) was obtained by using the home-prepared ones. The reported green process allows to obtain an added value product (piperonal), upon partial oxidation of a cheap reagent.

Effect of Substituents on Partial Photocatalytic Oxidation of Aromatic Alcohols Assisted by Polymeric C3N4

In the present work we scrutinize the effect of substituents in the phenyl ring of the benzyl alcohol on its photo-oxidation to the corresponding benzaldehyde driven by polymeric carbon nitride photocatalyst in aqueous medium. It has been established that electron donating (ED) substituents in para- and ortho-position with respect to the CH2OH-group promote the reactivity of the substrate without compromising the selectivity towards benzaldehyde formation, maintaining it in the range of 84–98 %, if compared to the unsubstituted molecule. The same observation is true for meta-substituted benzyl alcohol with an electron withdrawing (EW) group. On the other hand, the presence of ED-group in me…

Photocatalytic Oxidation of Drugs by Using Artificial and Solar Irradiation

Studio dell’Influenza del Carbonio Attivo sulla Degradazione Fotocatalitica del 2-Propanolo Condotta in Presenza di Biossido di Titanio o di Ossido di Zinco

Visible light photocatalytic activity of macro-mesoporous TiO2-CeO2inverse opals

Macro-mesoporous TiO2 inverse opal materials were synthesized and they were tested as photocatalysts under visible light irradiation. The influence of cerium oxide addition towards the Rhodamine B (RhB) photodegradation activity was evaluated. Structural, textural, spectral and surface properties of the TiO2-CeO2 inverse opal nanocomposites were studied by XRD, XPS, SEM, TEM, N2 adsorption-desorption, Diffuse Reflectance UV–vis and Photoluminescence spectroscopies. Compared to commercial TiO2 anatase, the macro-mesoporous TiO2 inverse opal exhibited six times higher kinetic rate constant in the RhB degradation under visible light irradiation. The good photocatalytic activity was related to …

Reduced grey brookite for noble metal free photocatalytic H2evolution

Herein we introduce for the first time a reduced “grey” brookite TiO2 photocatalyst, produced by thermal hydrogenation of brookite nanoparticles, that shows a remarkable noble metal free photocatalytic H2 evolution. Its activity is substantially higher than that of other TiO2 polymorphs, i.e. anatase or rutile, comparably sized and activated by hydrogenation under optimized conditions. Along with brookite powders, an oriented brookite single crystal was investigated as a defined surface to confirm the effects of the hydrogenation treatment. By a combination of electron paramagnetic resonance (EPR), electron and X-ray characterization techniques applied to the powders and single crystal, we …

Photo-assisted Degradation of 2-Propanol in Gas-Solid Regime by Using TiO2 Impregnated with Heteropolyacids H3PW12O40

Commercial and home prepared TiO2 samples impregnated with tungstophosphoric acid (H3PW12O40) were used for the photo-assisted degradation of 2-propanol in gas–solid regime. The characterization results evidenced a good coverage of the polyoxometalate (POM) onto the surface of TiO2 along with a marginal effect of the presence of the POM on the specific surface area, morphology and cristallinity of the samples. Propene was the main intermediate product revealed in 2-propanol photocatalytic degradation by using as photocatalysts the samples containing the POM, whereas propanone wasmainly obtained when the photocatalysts was bare TiO2, both commercial or home prepared. Acetaldehyde was also fo…

Ossidazione fotocatalitica di benzonitrile in sospensioni acquose di biossido di titanio

Photocatalytic CO2 Reduction in Gas-Solid Regime in the Presence of Bare, SiO2 Supported or Cu-Loaded TiO2 Samples

Both commercial and home prepared (HP) TiO2 samples have been tested for the photocatalytic reduction of CO2. (HP) TiO2 powders were prepared by using TiCl4 or Ti(OC4H9)4 as the precursors to obtain HP1 and HP2 samples, respectively. Also HP Cu-loaded and SiO2 supported TiO2 powders were prepared. The HP samples were more active than the commercial ones for the photoreduction of CO2 with and without water vapour. HP1 produced mainly formaldehyde, HP2 principally methane. Acetaldehyde was found to be the primary product obtained when HP1 was supported on SiO2. The addition of Cu increased the photocatalytic reactivity either of bulk and SiO2-supported HP1. In particular, 1 wt % of Cu improve…

Influence of activated carbon in the TiO2 mediated photo-assisted degradation of 2-propanol in gas-solid regime

Preface

Attività catalitica e fotocatalitica di eteropoliacidi Wells-Dawson e Keggin per la disidratazione del 2-propanolo in regime gas-solido

Tra i più studiati poliossometallati (nanoagglomerati di ossigeno con metalli transizionali), figurano gli eteropoliacidi (EPA) che sono degli acidi inorganici forti con ben defin ite strutture molecolari. In funzione della loro geometria, essi vengono classificati come Keggin e Wells-Dawson. Gli (EPA) sono usati in catalisi omogenea ed eterogenea e funzionano anche come fotocatalizzatori, essenzialmente in sistemi omogenei. Questi materiali sono, inoltre, economici e non tossici.

Genotoxicity of Terpenes Present in Wastewater of a Citrus Transformation Factory in Bacterial and Mammalian Cells and Effectiveness of Photocatalytic Degradation

The aim of this work was to compare the genotoxic responses of mixtures of terpenes present in wastewaters of a citrus transformation factory with the genotoxicity of the individual compounds. Samplings of wastewater collected before (untreated sample) and past water purification by biological method (treated sample) were analyzed using Solid Phase Micro-extraction (SPME) followed by GC analyses. The chromatograms showed in all effluents the presence of four terpenes: pinene, -pinene, 3-carene, D-limonene. The concentrations of terpenes in the untreated sample were 1–3 orders of magnitude higher than in the treated sample. Genotoxicity was evaluated in the Salmonella reversion assay (Ames t…

Photoreduction of carbon dioxide to formic acid in aqueous suspension: a comparison between phthalocyanine/TiO2 and porphyrin/TiO2 catalysed processes

Composite materials prepared by loading polycrystalline TiO2 powders with lipophilic highly branched Cu(II)- and metal-free phthalocyanines or porphyrins, which have been used in the past as photocatalysts for photodegradative processes, have been successfully tested for the efficient photoreduction of carbon dioxide in aqueous suspension affording significant amounts of formic acid. The results indicated that the presence of the sensitizers is beneficial for the photoactivity, confirming the important role of Cu(II) co-ordinated in the middle of the macrocycles. A comparison between Cu(II) phthalocyanines and Cu(II) porphyrins indicated that the Cu(II)- phthalocyanine sensitizer was more e…

Inorganic materials acting as heterogeneous photocatalysts and catalysts in the same reactions

General considerations on the differences and similarities between heterogeneous photocatalysis and thermal catalysis are presented. Some research papers are reviewed where a reaction has been carried out in the presence of an inorganic material used both as catalyst and photocatalyst. The existing literature often compares catalytic reactions undertaken with the contemporaneous presence of radiation, showing only that photocatalytic reactions can occur under milder experimental conditions and at much lower temperatures. Nevertheless, differences in mechanistic aspects, conversions and selectivities between catalytic and photocatalytic reactions should also be highlighted. These are due to …

Brookite, the least known TiO2 photocatalyst, Catalysts

Brookite is the least studied TiO2 photocatalyst due to the difficulties usually encountered in order to obtain it as a pure phase. In this review, a comprehensive survey of the different methods available for preparing brookite powders and films is reported. Attention has been paid both to the most traditional methods, such as hydrothermal processes at high temperatures and pressures, and to environmentally benign syntheses using water soluble compounds and water as the solvent. Papers reporting the photocatalytic activity of pure and brookite-based samples have been reviewed.

Zn,Al hydrotalcites calcined at different temperature: Characterisation and photocatalytic activity for the degradation of 2-propanol in gas-solid regime

Renewable Organic Resources for Fine Chemicals and Photo-sensitizers in TiO2 Based Photocatalytic Processes

Selective Photocatalytic Oxidation of 4-Methoxybenzyl Alcohol to p-Anisaldehyde in Organic-Free Water in a Continuous Annular Fixed Bed Reactor

Photocatalytic oxidation of 4-methoxybenzyl alcohol to p-anisaldehyde was performed in water organic-free solutions by using a fixed bed continuous photoreactor containing Pyrex beads on which a TiO2 home prepared photocatalyst was supported. The influence of liquid flow rate, inlet alcohol concentration and catalyst amount on the photoprocess was studied. The highest selectivity to p-anisaldehyde was about 47% being CO2, the other main oxidation product; traces of 4-methoxybenzoic acid were also detected. The radiation field inside the photoreactor has been modelled by applying the Monte Carlo method thus allowing the determination of the local volumetric rate of photon absorption (LVRPA).…

GaP/TiO2 Composite Photocatalyst for CO2 Reduction in Gas-Solid Regime under Simulated Solar Light Irradiation

Ossidazione selettiva di alcoli aromatici ad aldeidi in sospensioni acquose di TiO2 anatasio e rutilo

Preparation, Characterisation and Photocatalytic Activity of Zn,Al Oxides Derived from Zn,Al LDHs

Selective (photo)catalytic formation of 2-propanol from propene by using an heteropolyacid supported on different oxides

Influenza del Sostituente sulla Ossidazione Fotocatalitica Selettiva di Composti Aromatici

Selective aqueous oxidation of aromatic alcohols under solar light in the presence of TiO2 modified with different metal species

AbstractA set of metals modified TiO2 photocatalysts were prepared starting from titanium tetraisopropoxyde and different metal precursors to study the influence of the addition of the various foreign agents on the physico-chemical and photocatalytic properties of the catalysts. The powders were characterized by X-ray diffraction, Raman spectroscopy, specific surface area measurements, scanning electron microscopy, energy dispersive X-ray spectroscopy, UV–Vis diffuse reflectance spectroscopy, photoluminescence, temperature programmed desorption after CO2 adsorption. The photocatalytic activity was evaluated using as probe reactions the partial oxidation of three aromatic alcohols: benzyl al…

Photocatalytic membrane reactors: fundamentals, membrane materials and operational issues

Abstract: This chapter reports the properties of semiconductor materials used in heterogeneous photocatalysis together with a comparison of heterogeneous photocatalytic systems and a brief description of the types of membranes that can be used. Some aspects of membrane operations, such as fouling, separation of a photocatalyst and effectiveness of photodegradation on permeate quality are discussed.

Photoelectrochemical and EPR features of polymeric C 3 N 4 and O-modified C 3 N 4 employed for selective photocatalytic oxidation of alcohols to aldehydes

Four different C 3 N 4 specimens have been prepared, a bulk one (MCN), a thermally etched (MCN-TE), a solid prepared by hydrothermally treating MCN with H 2 O 2 (MCN-H 2 O 2 ) and a polymeric carbon nitride-hydrogen peroxide adduct (MCN-TE-H 2 O 2 ). The principal aim of this work was to correlate the capability of the prepared material to generate reactive oxygen species (ROS), under irradiation, with their photocatalytic activities in terms of conversion and selectivity for partial oxidation reactions. Photoelectrochemical studies revealed that MCN-TE represented the best material in terms of photoconductivity, whereas MCN-H 2 O 2 was defective and evidenced a poor mobility of carriers. E…

Photochemical and photocatalytic isomerization of trans -caffeic acid and cyclization of cis -caffeic acid to esculetin

Abstract The photoisomerization of trans-caffeic acid to cis-caffeic acid has been studied in the presence of N2 in homogeneous aqueous solutions and in suspensions of various TiO2 catalysts. The results supported the hypothesis of an energy transfer process from TiO2 to the substrate due to the recombination of the photogenerated electron–hole pairs. The differences among the measured photostationary [cis]/[trans] ratios have been attributed to the different physico-chemical properties of the catalysts. In particular, the lowest ratio measured in the presence of Merck TiO2 was ascribed to the very low adsorption of trans-caffeic acid onto the surface of this sample. In the presence of O2 a…

Enhancing Selectivity of Photocatalytic Synthesis of p-Anisaldehyde in Water under Solar Irradiation by N- Doped TiO2

Determinazione Volumetrica di Cr(III) con EDTA in Presenza di Verde Naftolo come Agente Schermante

Comparison of activity in the 2-propanol dehydration of supported heteropolyacid (photo)catalysts at the gas-solid interface

Catalytic and photocatalytic tests for 2-propanol dehydration to propene were successfully carried out by using binary materials obtained by supporting a Keggin heteropolyacid H3PW12O40 (PW12) via impregnation method and/or solvothermal treatment. The supports used were commercial SiO2 (Mallinckrodt), TiO2 (Evonik P25) and multiwall carbon nanotubes (Sunnano) or home solvothermically prepared SiO2 and TiO2. (Photo)catalytic 2-propanol dehydration was studied in gas-solid regime by using a continuous (photo)reactor working at atmospheric pressure and 80 °C. the reaction was also studied by performing FTIR spectra of the gas-phase over the HPA-support composites, where the 2-propanol had been…

Photoassisted Mineralization of Aromatic and Aliphatic N Heterocycles in Aqueous Titanium Dioxide Suspensions and the Fate of the Nitrogen Heteroatoms

Abstract The photoassisted degradation of aromatic heterocycles (pyrrole, imidazole, pyrazole, isoxazole, oxazole and thiazole) and N-containing alicycles (aliphatic heterocycles: pyrrolidine, 4-butanelactam and 5-pentanelactam) was examined in liquid–solid dispersions. Complete mineralization (TOC) of the aromatic heterocycles was attained within ca. 1 h of UV irradiation of the TiO 2 /heterocycle system in acidic (pH 3), near-neutral (pH 6.0–7.6) and alkaline (pH 11) media. Mineralization kinetics were, in general, not appreciably influenced by the presence of acid but tended to be somewhat slower in alkaline media. N-alicycles were photomineralized more slowly than were the aromatics. Th…

Thermal Evolution of Titania Nanostructured Powders Obtained from Reverse Micelle Method

A PERVAPORATION PHOTOCATALYTIC REACTOR FOR THE GREEN SYNTHESIS OF VANILLIN

Abstract Pervaporation is the ideal membrane separation process to be coupled with photocatalysis for the green synthesis of vanillin from ferulic acid. In fact the operative conditions of the two processes are absolutely congruent and the integration is straightforward even operating with separate equipments. The utilization of a highly selective membrane allows the continuous recovery of vanillin by pervaporation from the reacting solution, so that its oxidative degradation is largely avoided and the yield is substantially enhanced. The effects of the main parameters are analyzed resorting to a mathematical model, which is validated by a comparison with the experimental data. In particula…

Visible Light Induced Oxidation of Ferulic Acid by TiO2 Photocatalysis

Oxidation of ferulic acid (C10H10O4) in aqueous medium occurs by using both commercial and home prepared TiO2 samples under visible light irradiation. Among the oxidation products vanillin was found with a selectivity ranging from 1 to 2% with respect to the converted substrate. By considering that TiO2 is unable to absorb visible light and ferulic acid does not react in the absence of TiO2, the observed photoactivity may be explained by the formation of a charge-transfer complex between ferulic acid and TiO2, being the complex able to absorb visible light. Among all the tested semiconductor oxides, only Merck anatase TiO2 does not perform the oxidation of ferulic acid under visible light i…

Thin-Film Photovoltaics 2013

Photodecomposition of adsorbed ethanoic acid over silica gel catalyst in a flow system

Abstract The photodecomposition of ethanoic acid adsorbed on silica gels from various sources was studied at wavelengths greater than 300 nm. The experiments were carried out in a flow apparatus. A few photoreactivity tests using acetone or ethanol were also performed. The photodecomposition of ethanoic acid and acetone produced mainly carbon dioxide and methane, in the ratio 2:1, and traces of ethane and methanol. Adsorbed ethanol was not affected at all by the radiation. Infrared and UV-vis reflectance spectra of ethanoic acid adsorbed on silica gels as well as UV-vis reflectance spectra of acetone and ethanol adsorbed on silica gels were recorded. The spectra show the presence of a varie…

Thin-Film Photovoltaics 2011 (Editorial)

Thin-Film Photovoltaics

Heterogeneous photocatalysis: optical characterisation of polycrystalline photocatalysts for pollutant degradation in aqueous medium

Preparazione di fotocatalizzatori a base di TiO2 brookite drogati con samario

Photocatalytic Membrane Reactors: Case Studies and Perspectives

Photocatalysis by polycrystalline semiconductor oxides is being successfully applied to the abatement of organic and inorganic pollutants both in gas and in liquid phase. In order to increase the efficiency of this method, the coupling of this technology with the membrane separation process has been the object of sound investigation. In this combination, the membrane may act in different ways: to confine the photocatalytic powder in the reacting suspension, to selectively separate the photoreaction products, or to be the support of photocatalyst. This article reports recent studies in which different types of membranes (such as distillation, dialysis, nanofiltration, pervaporation and osmos…

TiO2 photocatalysts prepared by thermohydrolysis of TiCl4 solutions

Nanomateriali a base di TiO2 come fotocatalizzatori per sintesi selettive di alcoli ad aldeidi in fase acquosa

Photocatalytic oxidation of benzonitrile in aqueous suspensions of titanium dioxide

TiO2-based photocatalysts impregnated with metallo-porphyrins employed for degradation of 4-nitrophenol in aqueous solutions: role of metal and macrocycle

Photodegradation of organic compounds in water solutions by means of economically advantageous and environment-friendly processes is a topic of growing interest. In recent years a great attention has been devoted to TiO2-based photocatalysts for the oxidative degradation of various organic pollutants. In this context, we have prepared new photo-catalytic polycrystalline TiO2 systems impregnated with sensitizers, i.e., copper, iron or manganese porphyrins, and investigated their photoactivity for 4-nitrophenol oxidation compared with that of bare TiO2. A significant improvement of the photoreactivity was observed in the case of TiO2 impregnated with copper porphyrin, while only a slight bene…

Preparation and photoactivity of samarium loaded anatase, brookite and rutile catalysts

Abstract Pure and samarium loaded anatase, brookite and rutile nanopowders were synthesized by thermohydrolysis of TiCl 4 . The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), specific surface area (SSA) determination, UV–vis diffuse reflectance spectroscopy (DRS), atomic force microscopy (AFM), contact angle (CA) measurements and photoluminescence (PL) spectroscopy. The photocatalytic activity of pure and Sm-loaded TiO 2 polymorphs was investigated by employing the photodegradation of 4-nitrophenol as probe reaction in a liquid-solid system. Loading with Sm resulted in an improvement of the photoreactivity of the three TiO 2 polymorphs. The benefi…

Green Production of Aldehydes from Alcohols by Heterogeneous Photocatalysis

Advances in selective conversions by heterogeneous photocatalysis

Selective photocatalytic conversions are offering an alternative green route for replacing environmentally hazardous processes with safe and energy efficient routes. This paper reports the most recent advances in the application of heterogeneous photocatalysis to synthesize valuable compounds by selective oxidation and reduction.

Preparation and photocatalytic activity of ZnO-SnO2, ZnO-ZnWO4 and SnO2-ZnO-ZnWO4 nanocomposites

Synthesis and Characterization of TiO2 Deposited on Silica

Autocatalytic Photo-Oxidation of 2-Methoxybenzyl Alcohol and O2 Quenching therein

Characterization and photoactivity of coupled ZnO-ZnWO4 catalysts prepared by a sol-gel method

Abstract ZnO–ZnWO4 nanocomposites were synthesized by a novel sol–gel method and characterized through X-ray diffraction, BET specific surface area analysis, UV–Vis diffuse reflectance spectroscopy, scanning electron microscopy and transmission electron microscopy. The photocatalytic activity of the samples was evaluated using the degradation of 4-nitrophenol under UV light as probe reaction. The ZnO/ZnWO4 molar ratio was varied in order to study its influence on the photoefficiency of the mixed samples. The ZnO–ZnWO4 nanocomposites showed higher photoactivity than ZnO and ZnWO4. The high efficiency of the mixed samples was explained by the coupling and the intimate contact of two different…

Photocatalytic membrane reactors for degradation of organic pollutants in water

Abstract Different flowsheets (batch and continuous) of photocatalytic membrane reactors, to be used for degradation of organic pollutants present in water, together to some experimental results, are reported. 4-Nitrophenol (4NP) was used as a probe polluting agent and titanium dioxide in suspension was the catalyst. The photodegradation tests in the batch system were carried out without membrane changing the characteristic variables of the process (light intensity, TiO 2 concentration, 4NP concentration, O 2 concentration, pH) to find their optimum values. The batch system consisted of a water jacket thermostatted and stirred beaker irradiated from above with a UV–Vis lamp (light intensity…

PMRs Utilizing Non–Pressure-Driven Membrane Techniques

In the present chapter it is shown how photocatalytic membrane reactors utilizing membrane processes, which are not pressure driven, can exploit various mechanisms to obtain a substantial improvement of the process. The fundamentals of this particular type of membrane reactors are reviewed including the effects of the most important parameters and the methods and rules of coupling photocatalysis and membrane separation. The survey of the studies on photocatalytic membrane reactors (PMRs) utilizing pervaporation, dialysis, membrane contactors and membrane distillation offers the opportunity of discussing the advantages with respect to PMRs adopting pressure driven membrane processes. Indeed,…

REWAQUA: an advanced technology for water purification in sustainable aquaculture based on photocatalytic ozonation

The present study has been undertaken in order to test the real potential of photocatalytic ozonation in a bench-scale recirculating aquaculture system working on a 180 L reef coral aquarium. Notably, this choice may be considered representative. In fact, (i) the system is virtually closed so that fresh water turnover is practically negligible, (ii) the presence of living organisms is highly diversified (corals, fishes, molluscs, echinoderms and crustaceans) and some of them are particularly sensitive to water quality, (iii) high salinity strongly puts a strain on the purification system. The hereby presented purification method has been named REWAQUA, which stands for REcycling Water for A…

Preparation, characterization and photocatalytic activity of TiO2 rutile

Nanosponge-C3N4 composites as photocatalysts for selective partial alcohol oxidation in aqueous suspension

A set of four composite materials was prepared, consisting of a nanosponge matrix based on beta-cyclodextrin in which carbon nitride was dispersed. The materials were characterized by the presence of diverse cross-linker units joining the cyclodextrin moieties, in order to vary the absorption/release abilities of the matrix. The composites were characterized and used as photocatalysts in aqueous medium under UV, visible and natural solar irradiation for the photodegradation of 4-nitrophenol, and for the selective partial oxidation of 5-hydroxymethylfurfural and veratryl alcohol to the corresponding aldehydes. The nanosponge-C3N4 composites showed higher activity than the pristine semiconduc…

Room Temperature Home Prepared TiO2 Rutile Used for Selective Photocatalytic Oxidation of Aromatic Alcohols to Aldehydes in Aqueous Medium

Production of dibutyl carbonate by insertion of CO2 in titanium(IV) tetrabutoxide

The species resulting from insertion of 12CO2 and 13CO2 into titanium(IV) butoxide is for the first time fully characterized by means of infrared and nuclear magnetic resonance spectroscopy. Results show formation of Ti-monobutylcarbonate, that easily undergoes nucleophilic attack by an aliphatic amine. The hydrolysis of the resulting species produces butylcarbamate and dibutylcarbonate as the only main products. Characterization results of the carbonate-like adduct, along with its reactivity with amine molecules open the route to new ways of CO2 utilization as building block for valuable organic compounds.

Photocatalytic Oxidation of Acetonitrile in Aqueous Suspension of Titanium Dioxide Irradiated by Sunlight

Pyrolysis Study of Sol-Gel Derived TiO2 Powders Part III. TiO2-anatase Prepared by Reacting Titanium(IV) Isopropoxide with Acetic Acid

Oxidación Fotocatalítica del Acetonitrilo en Régimen Gas-Sólido y Líquido-Sólido

Nanostructured rutile TiO2 for selective photocatalytic oxidation of aromatic alcohols to aldehydes in water

WOS: 000253100100022

Glossary of terms used in photocatalysis and radiation catalysis (IUPAC Recommendations 2011)

This glossary of terms covers phenomena considered under the very wide terms photocatalysis and radiation catalysis. A clear distinction is made between phenomena related to either photochemistry and photocatalysis or radiation chemistry and radiation catalysis. The term “radiation” is used here as embracing electromagnetic radiation of all wavelengths, but in general excluding fast-moving particles. Consistent definitions are given of terms in the areas mentioned above, as well as definitions of the most important parameters used for the quantitative description of the phenomena. Terms related to the up-scaling of photocatalytic processes for industrial applications have been included. Thi…

Photoelectrocatalytic oxidation of 3-pyridinemethanol to 3-pyridinemethanal and vitamin B3 by TiO2 nanotubes

In this paper, the first photoelectrocatalytic (PEC) 3-pyridinemethanol oxidation to 3-pyridinemethanal and vitamin B-3 was investigated. To meet this aim, efficient nanotube structured TiO2 on a Ti plate as a photoanode was prepared by an anodic oxidation method in ethylene glycol and characterized by XRD, SEM, and photocurrent techniques. The effect of nanotube morphology, applied potential, Na2SO4 concentration, stirring speed of solution, and pH on the reaction activity and product selectivities were investigated. The TiO2 phase of all of the anodes was mainly the anatase one. The PEC activity, the intensity of the XRD peak and the photocurrent increased by increasing the nanotube lengt…

Selective photocatalytic oxidation of 5-hydroxymethyl-2-furfural in aqueous suspension of polymeric carbon nitride and its adduct with H2O2 in a solar pilot plant

Abstract This work reports a study on the reactivity of polymeric carbon nitride (PCN) and PCN-H2O2 adduct samples for sunlight photocatalytic selective oxidation reactions. The characterization of these materials was reported in a previous paper where the reactivity towards the partial oxidation of 5-hydroxymethylfurfural (HMF) was studied by using two different laboratory scale photoreactors; one irradiated by UV lamps and the other one by natural sunlight. In the present study it has been confirmed the effectiveness of these C3N4 based materials for the selective partial oxidation of HMF to FDC (2,5-furandicarboxaldehyde) in aqueous medium in a pilot plant photoreactor irradiated by natu…

Selective photocatalytic oxidation of 5-hydroxymethyl-2-furfural to 2,5-furandicarboxyaldehyde in aqueous suspension of g-C3N4

Graphitic carbon nitride assisted partial photocatalytic oxidation of 5-hydroxymethyl-2-furfural (HMF) in aqueous medium was investigated. Different carbon nitride precursors were considered, being melamine the one yielding the most efficient photocatalyst. The obtained 30% selectivity of HMF oxidation to 2,5-furandicarboxaldehyde (FDC) is higher than those reported up to now. A further thermal exfoliation of the g-C3N4 samples showed under artificial light irradiation both an enhanced photocatalytic activity in conversion of HMF, and selectivity (ca. 42–45%) to FDC. The performance of the catalysts increased when the experiments were carried out under real outdoor illumination, reaching 50…

Hybrid processes coupling photocatalysis and membranes for degradation of organic pollutants in water

Abstract Tests of degradation in a photocatalytic membrane system with the lamp immersed in the suspension inside the photoreactor have been carried out by using polycrystalline TiO2 (Degussa P25) as catalyst and humic acids, organic dyes, 4-nitrophenol as pollutants. The influence of the type of nanofiltration membrane, initial concentration of pollutant and pH on the photodegradation rate was investigated in discontinuous and continuous configurations. Two membranes were tested, i.e. NF-PES-010 (Celgard, Germany) of polyethersulphone and NTR-7410 (Nitto-Denko, Japan) of sulphonated polyethersulphone. The last one was chosen for all of the photoreactivity experiments because permeability a…

Insight into the role of the zeolitization process in enhancing the adsorption performance of kaolinite/diatomite geopolymer for effective retention of Sr (II) ions; batch and column studies.

Abstract Diatomite/kaolinite-based geopolymer (GP) was synthesized and incorporated in zeolitization process (Z/GP) to investigate the role of the zeolite phases in inducing its retention capacity of the dissolved Sr (II) ions in water. The retention of Sr (II) ions using Z/GP in comparison with GP was evaluated based on both batch and fixed-bed column studies. In the batch study, the zeolitized geopolymer (Z/GP) shows enhancement in the Sr (II) retention capacity (193.7 mg/g) as compared to the normal geopolymer (102 mg/g). Moreover, the recyclability studies demonstrate higher stability for Z/GP than GP with a retention percentage higher than 90% for five reusing runs. The kinetic and the…

Oxidation of oxalate ion in aqueous suspensions of TiO2 by photocatalysis and ozonation

Abstract Oxalate anion has been oxidized in aqueous alkaline solution by using ozonation and photocatalysis in the presence of TiO 2 . A batch annular reactor has been used for carrying out reactivity runs in the presence of air/ozone, air/ozone/near UV irradiation, air/ozone/TiO 2 , air/near UV-irradiated TiO 2 and air/ozone/near UV-irradiated TiO 2 . The Langmuir–Hinshelwood kinetic model adequately describes the photocatalytic results obtained at different reaction conditions and allows determining the values of the kinetic and equilibrium adsorption constants. The contemporary presence of photocatalysis and ozonation shows a significant improvement of the process performance as the oxid…

Optical Characterisation of Semiconductors Used as Photocatalysts for the Degradation of Organic Pollutans in Acqueous Medium

Design of new porphyrin/Fe-loaded TiO2 composites for the efficient degradation of 4-nitrophenol by heterogeneous photo Fenton process

Concerning “An Opinion on the Heterogeneous Photoreduction of N2 with H2O”

Formation of dibutyl carbonate and butylcarbamate via CO2 insertion in titanium(IV) butoxide and reaction with n-butylamine

Abstract The species resulting from insertion of 12CO2 and 13CO2 into titanium(IV) butoxide is for the first time fully characterized by means of infrared and nuclear magnetic resonance spectroscopy. Results show formation of Ti-monobutylcarbonate, that easily undergoes nucleophilic attack by an aliphatic amine. The hydrolysis of the resulting species produces butylcarbamate and dibutylcarbonate as the only main products. Characterization results of the carbonate-like adduct, along with its reactivity with amine molecules open the route to new ways of CO2 utilization as building block for valuable organic compounds.

Preparazione di Fotocatalizzatori Nanostrutturati a Base di TiO2

ZrO2SiO2 mixed oxides: surface aspects, photophysical properties and photoreactivity for 4-nitrophenol oxidation in aqueous phase

Abstract Mixed oxides of ZrO2 and SiO2 were synthesized by a sol-gel technique by using zirconyl chloride and commercial silica gel as starting materials. The paper reports some surface features of the powders and the photoreactivity results obtained in the oxidation of 4-nitrophenol in aqueous suspensions of powdered photocatalyst. The optical characterization of the suspension was also performed by measuring the photon flows reflected and absorbed by the reacting system. The photoactivity exhibited by the ZrO2SiO2 samples is very scarce especially if compared with that shown by a TiO2 sample tested at equal experimental conditions. The low photoreactivity can be justified on the basis of…

Photolysis of Adsorbed Phases: Ethanoic Acid-Insulators and Semiconductors Systems. Influence of Acid-Base Properties.

The paper reports the results of experiments in which the photodecomposition of adsorbed ethanoic acid (and in few cases of adsorbed acetone and ethanol) was carried out by using several silica gel samples, whose properties were modified by adding oxidic dopants as γ-Al2O3, which is acidic in character, and MgO, which is mainly basic. Also the related system MgO-Al2O3 was investigated. Few IR spectra on selected pure specimens and on specimens containing adsorbed ethanoic acid were recorded with the aim of following the variation of the surfaces-adsorbate interaction with the variation of the acid-base properties. It was also of interest to compare the photoreactivity of insulators and semi…

Photocatalytic activity of transition-metal-loaded titanium(IV) oxide powders suspended in aqueous solutions: Correlation with electron–hole recombination kinetics

Photocatalytic reactions by transition-metal (V, Cr, Fe, Co, Cu, Mo, or W) loaded TiO2 (M-TiO2) powders suspended in aqueous solutions of methanol, (S)-lysine (Lys), or acetic acid were investigated. The photoactivities of various samples were compared with the rate constant (kr) of recombination of photoexcited electrons and positive holes determined by femtosecond pump–probe diffuse reflection spectroscopy (PP-DRS). As a general trend, increased loading decreased the rate of formation of the main products (H2 , pipecolinic acid (PCA), and CO2) under UV (>300 nm) irradiation, and the effect became more intense on increasing the loading. In PP-DRS, these M-TiO2 gave similar decays of absorp…

Guidelines for the assessment of the rate law of slurry photocatalytic reactions

Abstract The assessment of the rate law of slurry photocatalytic reactions appears to be a hard task, mainly because in this type of reactions the average rate of reaction, which is experimentally observed in a real reactor, could be very different from the “true” (intrinsic) rate of reaction, which cannot be measured directly. In the present work, it is shown how a proper mathematical model allows the utilization of the differential and/or the integral methods of kinetic analysis. The mathematical model must take into account not only the momentum and the mass balances, but also the radiative transfer equation. However, the discrimination among different proposed kinetic laws remains diffi…

Optical properties and quantum yield determination in photocatalytic suspensions

Knowledge of the optical properties of photocatalytic suspensions is vital for a correct comparison of their energetic efficiency. In this work, the determination of both absorption and scattering coefficients of aqueous suspensions of commercial TiO2 powders irradiated by monochromatic light was carried out by measuring only one quantity—the transmitted photon flow—as a function of the catalyst mass and by applying an asymptotic form of the Kubelka–Munk solution of the radiative transfer equation. Applying a nonlinear fitting procedure the evaluation of the actual values of absorption and scattering coefficients was carried out. The limit for optically thick media of the Kubelka–Munk equat…

Photocatalysis: Applications

Heterogeneous photocatalysis is a sustainable technology mainly employed for water and air cleaning purposes. However, in the last two decades a lot of attention has been given to photocatalysis as an alternative route to be used in place of traditional industrial processes. The sustainability of photocatalysis mainly comes from the exploitation of renewable sources, such as solar light, and the possibility to avoid unsafe reagents/solvents and severe temperatures and pressures. In this chapter we give a critical presentation of some case studies concerning the use of heterogeneous photocatalysts, such as modified and bare TiO2, ZnO, ZnS, WO3, titanium silicalite, V2O5, polyoxometalates, Cd…

Applicazioni della Fotocatalisi

Role of Hydroxyl, Superoxide, and Nitrate Radicals on the Fate of Bromide Ions in Photocatalytic TiO2 Suspensions

The influence of bromide ions on systems containing highly reactive radical species is of great interest for environmental remediation, atmospheric chemistry, and the synthesis of high-added-value ...

Selective Gree-Syntheses of Flavour-Molecules through TiO2 Photocatalysis in Aqueous Suspension

High Activity of Brookite TiO2 Nanopowders in the Photocatalytic Abatement of Ammonia in Water

The Preparation and the Characterisation of some Ternary Titanium Oxide Pkotocatalysts.

TiO 2 catalysts, of moderate surface areas and minimal porosities, containing various nominal quantities of iron have been prepared. E.s.r spectra indicate that Fe 3+ is well dispersed in coprecipitated samples, and in impregnated Tioxide samples, when the iron concentration is

Photocatalytic Active Polymer Expanded Materials Coated with TiO2 Used as Package for Foodstuffs

Photocatalytic Ozonation of Bromide Containing Waste Water: Related Problems and Kinetics Based Strategy Evaluation

In the so-called photocatalytic ozonation (PO) synergistic effects between photocatalysis and ozonation enhance the rate of oxidation of organic compounds, therefore this integrated process is very promising for use in water treatment. In the present work, it is demonstrated that the improvement that can be obtained by the integrated process in comparison with the uncoupled processes depends on the relative weight between photocatalysis and ozonation. In this respect, it has been found that a relatively low rate of photocatalysis (0.3 times the rate of ozonation) is sufficient to get the highest synergy and to maximize the performances in the oxidation of formate, the adopted model organic …

Preparation of Photoactive Polycrystalline Titanium Dioxide

Reduction of Dinitrogen to Ammonia in Irradiated Heterogeneous Systems

The recent developments of the research in the field of dinitrogen reduction to ammonia at mild conditions of pressure and temperature are reported. After a brief historical recapitulation of the traditional thermal process, the new routes for NH3 synthesis (biological photosynthesis, direct electrochemical reduction, and photocatalytic reduction) are presented and critically discussed. A particular attention is devoted to heterogeneous photocatalytic reduction performed by irradiating pure, mixed, and doped semiconducting catalysts in gas-solid and liquid-solid systems. The fixation of dinitrogen in aqueous solutions containing complexes and photoactive particulate systems is also reported…

Keggin heteropolyacid supported on BN and C3N4: Comparison between catalytic and photocatalytic alcohol dehydration

The Keggin heteropolyacid (HPA), H3PW12O40 (PW12) has been supported on commercial boron nitride (BN) and two types of home prepared carbon nitride (C3N4). The supported PW12 was used in the gas-solid (photo)catalytic 2-propanol dehydration reaction to give propene at atmospheric pressure and temperatures in the range 70–120 °C and resulted more active than the pristine PW12. Reaction rate increased by increasing the temperature. Noticeably, the propene formation rate was higher by irradiating the catalytic system. The PW12/BN material resulted more active than PW12/C3N4. The acidity of the HPA cluster accounts for the catalytic role, whereas both the acidity and the redox properties of the…

P46: ADSORPTION AND PHOTOCATALYTIC DEGRADATION OF ACETONITRILE ON TiO2: FT-IR AND KINETIC STUDIES

Proprietà ottiche e determinazione della resa quantica per sospensioni fotocatalitiche

Heterogeneous Photocatalysis: a Promising Tool for Green Organic Syntheses

The present work deals with a short review of some applications of photocatalysis to green organic synthesis of valuable products in mild experimental conditions and in the presence of water as solvent.

Combination of advanced oxidation processes and active carbons adsorption for the treatment of simulated saline wastewater

Abstract In the present work, an integrated process combining three different technologies, i.e. heterogeneous photocatalysis, homogeneous ozonation and adsorption on granular activated carbon (GAC) was used for the treatment of a synthetic solution simulating saline wastewater. The synergistic effects between the different methods enhance the oxidation rate of the organic compounds in the integrated process, so that its use may result sustainable. It has been found that a relatively low oxidation rate is sufficient to obtain the highest synergy between the three technologies and to maximize the performances. In particular, coupling ozonation and photocatalysis resulted in 20% enhancement i…

Preparazione e caratterizzazione di film fotocatalitici

Lanthanide Diphthalocyanine – Photosensitizers in TiO2 Hybrid Catalytic Systems: Green Chance for The Nature

Solar Eneergy Conversion to Chemical Photocatalytic Selective Oxidation of 5-(Hydroxymethyl)-2-furaldehyde to 2,5-furandicarbaldehyde in Water by Using TiO2 Nanoparticles

Improved (photo)catalytic propene hydration in a gas/solid system by using heteropolyacid/oxide composites: Electron paramagnetic resonance, acidity, and role of water

Binary materials composed of the oxides SiO2, TiO2 and N-doped TiO2 and the Keggin heteropolyacid (PW12) were prepared and physicochemically characterized. They were used as catalysts and photocatalysts for the hydration of propene to 2-propanol. The characterization of the samples, particularly the electron paramagnetic resonance (EPR) spectroscopy results and the acidity properties, were useful to explain the key role played by the PW12 in the composite materials in the thermal and photoassisted catalytic processes. The simultaneous pres-ence of heat and UV light improved the activity of PW12 in the thermal process, and the binary materials showed better (photo)catalytic activities than t…

Photocatalysis: a promising route for 21st century organic chemistry

One of the main goals of 21st century chemistry is to replace environmentally hazardous processes with energy efficient routes allowing to totally avoid the use and production of harmful chemicals and to maximise the quantity of raw material that ends up in the final product. Selective photocatalytic conversions will play a major role in this evolution and this account shows how photocatalysis is offering an alternative green route for the production of organics.

The role of water in the photocatalytic degradation of acetonitrile and toluene in gas-solid and liquid-solid regimes

Photocatalytic degradation of acetonitrile and toluene was carried out both in gas-solid and in liquid-solid regimes by using commercialTiO2samples (Merck and Degussa P25). The investigation was mainly aimed to study the influence of water present in the reaction environment on the mechanism and degradation rate of two probe molecules. In gas-solid regime, the reacting mixture consisted of toluene or acetonitrile, oxygen, nitrogen, and water vapour. The main degradation product of toluene wasCO2with small amounts of benzaldehyde. In the presence of water vapour, the activity ofTiO2Merck remained stable but greatly decreased if water was absent.TiO2Degussa P25 continuously deactivated, even …

Heterogeneous Photocatalysis Coupled with other Technologies for the Purification of Aqueous Effluents

Combination of Photocatalysis and Ozonation for the treatment of Contaminated Water Containing Bromide Ions

The influence of the catalyst on the photacatalytic synthesis of vanillin

Keggin and Wells-Dawson supported heteropolyacids as heterogeneous (photo)catalysts for gas-solid 2-propanol dehydration

Catalytic and photocatalytic tests for 2-propanol dehydration to propene were successfully carried out by using binary materials obtained by supporting a Keggin or Wells-Dawson heteropolyacids via impregnation method to commercial SiO2 or TiO2. (Photo)catalytic 2-propanol dehydration was studied in gas-solid regime by using a continuous (photo)reactor working at atmospheric pressure and 80 °C. Propene and diisopropyl ether were the main reaction products. For the continuous photo-assisted runs the reactor was also illuminated with UV light. The heteropolyacid species played a key role both for the catalytic and the photo-assisted catalytic reactions; indicating that the acidity of the clust…

TiO2 Nanocristalline samples used to photo-oxidize aromatic alcohols to aldehydes

Degradation of 4-nitrophenol (4-NP) using Fe-TiO2 as a heterogeneous photo-Fenton catalyst

H3PW12O40 SUPPORTED ON DIFFERENT OXIDES: INFLUENCE OF THE SUPPORT ON THE CATALYTIC AND CATALYTIC PHOTO-ASSISTED PROPENE HYDRATION

Efecto de la Fotocatálisis Heterogenea y la Ozonización sobre la Oxidación del Ion Oxalato en Suspensión Acuosa de TiO2

Reazione catalitica e fotocatalitica di disidratazione in fase gas-solido del 2-propanolo in presenza di eteropoliacidi "Keggin" e "Wells-Dawson" supportati

La disidratazione catalitica e fotocatalitica di 2-propanol a propilene è stata effettuata usando eteropoliacidi di Keggin H3PW12O40 (PW12) e Wells-Dawson H6P2W18O60 (P2W18). Sono stati utilizzati sia supportani che non. Materiali binari sono stati preparati per l'impregnazione degli eteropoliacidi su supporti commerciali: SiO2 (Aldrich) e TiO2 (Evonik P25). I materiali sono stati caratterizzati e la loro (foto) attività catalitica rispetto alla disidratazione 2-propanol evaluata in regime gas-solido utilizzando un reattore continuo a pressione atmosferica e un range di temperatura fra 60 e 120 ° C. Inoltre, per gli esperimenti fotoassititi il reattore è stato illuminato da un LED UV. Impor…

Degradation of Lincomycin in aqueous medium: coupling of solar photocatalysis and membrane separation

Abstract The photocatalytic oxidation of a common antibiotic, the lincomycin was carried out in aqueous suspensions of polycrystalline TiO 2 Degussa P25 irradiated by sunlight. In order to improve the performance of the lincomycin degradation a hybrid system consisting of a solar photoreactor with the photocatalyst in suspension coupled with a membrane module, used to confine both photocatalyst and pollutants in the reaction environment, was tested. A preliminary study was carried out in order to determine some kinetics parameters of the drug photodegradation. The influence of initial substrate concentration on the lincomycin photooxidation rate was investigated. The photooxidation rate fol…

Photocatalytic activity of nanocrystalline TiO2 (brookite, rutile and brookite-based) powders prepared by thermohydrolysis of TiCl4 in aqueous chloride solutions

Abstract Nanocrystalline TiO2 powders were synthesized by thermohydrolysis of TiCl4 in HCl or NaCl aqueous solutions. Rutile, mixtures of brookite and rutile or mixtures of anatase, brookite and rutile were obtained depending on the acidity of the medium. Crystalline phases and composition of the mixtures were identified by using XRD analysis. Pure brookite nanoparticles, separated from the mixtures of brookite and rutile by simple peptization with water, were stable against transformation to rutile up to 750 °C. The prepared TiO2 powders were characterized by thermal analysis, diffuse reflectance spectroscopy and BET surface area determinations. The band gap of bulky brookite was estimated…

Extruded Expanded Polystyrene Sheets Coated by TiO2 as New Photocatalitic Materials for Foodstuffs Packaging

Nanostructured, photoactive anatase TiO2 sol prepared under very mild conditions using titanium tetraisopropoxide as the precursor is used to functionalise extruded expanded polystyrene (XPS) sheets by spray-coating resulting in stable and active materials functionalised by TiO2 nanoparticles. Photocatalytic tests of these sheets performed in a batch reactor in gas-solid system under UV irradiation show their successful activity in degrading probe molecules (2-propanol, trimethylamine and ethene). Raman spectra ensure the deposition of TiO2 as crystalline anatase phase on the polymer surface. The presence of TiO2 with respect to polymer surface can be observed in SEM images coupled to EDAX …

Photocatalytic Degradation of 4-nitrophenol in aqueous suspension by using polycristalline TiO2 samples impregnated with a Cu(II)-phthalocyanine

In this paper, the preparation of polycrystalline TiO2 samples impregnated with a modified Cu(II)-phthalocyanine (TiO2–CuPc) is reported along with an investigation on the photocatalytic behavior of this system compared with bare TiO2 (both in the anatase and rutile form) and with TiO2 samples impregnated with not functionalized commercial phthalocyanine (TiO2–CuPc) or with metal free phthalocyanine (TiO2–Pc). The photocatalytic degradation of 4-nitrophenol (4-NP) was studied as a probe reaction. The presence of modified CuPc showed to be beneficial only for TiO2 (anatase) while the commercial not functionalized CuPc also slightly for both TiO2 (anatase) and TiO2 (rutile). The metal free Pc…

Effect of titanium dioxide crystalline structure on the photocatalytic production of hydrogen

The effect of the crystalline phase of TiO 2 (anatase, rutile and brookite) on its photocatalytic activity in hydrogen production from methanol-water vapours has been investigated by testing a series of both home-made and commercial TiO 2 photocatalysts, either bare or surface-modified by deposition of a fixed amount, i.e. 1 wt%, of platinum as co-catalyst. For all of the TiO 2 samples the rate of hydrogen production increased by one order of magnitude upon Pt deposition, because of the ability of Pt to enhance the separation of photoproduced electron-hole pairs. Under irradiation in the 350-450 nm wavelength range, brookite and anatase showed similar photoactivities, both superior to that …

Hyperactive TiO2 Photocatalyst Obtained by Microwave Treatment

Riduzione Fotocatalitica di CO2 in Presenza di Catalizzatori Compositi GaP/TiO2

Optical properties of TiO2 suspensions: Influence of pH and powder concentration on mean particle size

WOS: 000250584100025

Photocatalytic conversion of glucose in aqueous suspensions of heteropolyacid-TiO2 composites.

Commercial and home prepared TiO2 samples were functionalized with a commercial Keggin heteropolyacid (HPA) H 3PW12O 40 (PW12) or with a hydrothermally home prepared K 7PW11O 39 salt (PW11). All the materials were characterized by specific surface area measurements (BET), XRD analyses, Raman, DRS along with SEM observations and they have been used for glucose photocatalytic conversion in an aqueous suspension. Different reaction extents and distribution of intermediate oxidation products were observed depending on the photocatalyst. Gluconic acid, arabinose, erythrose and formic acid were observed as oxidation products when bare TiO2 or HPA/TiO2 composite materials were used. Glucose isomer…

Preparation of polycrystalline TiO2 photocatalysts impregnated with various transition metal ions : characterization and photocatalytic activity for the degradation of 4-nitrophenol

A set of polycrystalline TiO2 photocatalysts loaded with various ions of transition metals (Co, Cr, Cu, Fe, Mo, V, and W) were prepared by using the wet impregnation method. The samples were characterized by using some bulk and surface techniques, namely X-ray diffraction, BET specific surface area determination, scanning electron microscopy, point of zero charge determination, and femtosecond pump-probe diffuse reflectance spectroscopy (PP-DRS). The samples were employed as catalysts for 4-nitrophenol photodegradation in aqueous suspension, used as a probe reaction. The characterization results have confirmed the difficulty to find a straightforward correlation between photoactivity and si…

Selective photocatalytic oxidation of aromatic alcohols in water by using P-doped g-C3N4

A set of bare and P-doped graphitic carbon nitride (g-C3N4) photocatalysts has been prepared by thermal condensation of melamine, urea or thiourea. For the sake of comparison, a g-C3N4 sample obtained in the presence of cyanuric acid and thermally exfoliated C3N4 powders were also studied. The materials were physicochemically characterized and their photocatalytic activity was studied for the selective oxidation of benzyl alcohol (BA), 4-methoxy benzyl alcohol (4-MBA) and piperonyl alcohol (PA) in water suspension both under UV and visible light irradiation. The influence of the type and position of the substituents on conversion and selectivity to aldehyde was remarkable. The presence of P…

Photocatalytic degradation of dyes by using a membrane reactor

Abstract Dyes are organic compounds used in textile, food and drug industries, and their abatement represents one of the main problems in the treatment processes because generally they are very stable toxic compounds. In this work, two commercial azo-dyes, i.e. Congo Red (C32H22N6Na2O6S2) and Patent Blue (C27H31N2NaO6S2), in aqueous solution were degraded in a photocatalytic membrane reactor by using TiO2 Degussa P25 as the catalyst. Different system configurations and irradiating sources were studied, and the influence of some operational parameters such as the pressure in the membrane cell and the initial concentration of the substrates was determined. A comparison between suspended and e…

The Photocatalytic Activity of Novel, Substituted Porphyrin/TiO2-Based Composites

Four novel porphyrins, 5-[3-(3-phenoxy)-propoxy]phenyl porphyrin, 5,15-di-[3-(3-phenoxy)-propoxy] phenyl porphyrin, 5,10,15-tri-[3-(3-phenoxy)-propoxy]phenyl porphyrin, 5,10,15,20-tetra-[3-(3-phenoxy)- propoxy]phenyl porphyrin, and their corresponding Cu(II) porphyrins, were synthesized and characterized spectroscopically. The photodegradation of 4-nitrophenol in aq. suspension was used to determine the photocatalytic activity of polycrystalline TiO2 samples which had been impregnated with the Cu(II) porphyrins, as sensitizers. The photocatalytic activity of the composite depends mainly on the amount of sensitizer on the TiO2 surface rather than the nature of the substituted porphyrins.

Electron transfer in ZnO–Fe2O3 aqueous slurry systems and its effects on visible light photocatalytic activity

ZnFex (x = 0.025, 0.05, and 0.1) nanocomposites and pure ZnO and Fe2O3 photocatalysts were synthesized by a simple sol–gel route and characterized by means of specific surface area (SSA) analysis, X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), and transmission electron microscopy/energy dispersive X-ray spectroscopy (TEM/EDS). Their photocatalytic activity was investigated under visible light by using methylene blue (MB) and benzoic acid (BA) as model compounds. Coupling ZnO and Fe2O3 results in higher photocatalytic activity with respect to the pure materials. Photoelectrochemical characterization performed in slurry systems allowed the elucidation of the electronic struc…

Three-Dimensional Calibration for Routine Analyses of Bromide and Nitrate Ions as Indicators of Groundwater Quality in Coastal Territories

Nitrate and bromide ions are generally considered indicators of anthropogenic pollution and seawater intrusion, respectively, in the groundwater of coastal territories. The analysis of these species is generally carried out with routine chromatographic analyses which generally afford partially merged or poorly resolved peaks. In the present paper a simple method for the correct evaluation of their concentration in water is reported. This method does not imply utilization of other instruments or technologies, only the mathematical elaboration of the data obtained from routine analysis of standard solutions containing the two species. Standard binary solutions of nitrate and bromide ions at d…

Inverse opal TiO2 as visible-light driven photocatalysts

Semiconductor photocatalysts have attracted a great deal of attention due to their potential application in environmental remediation. Titanium dioxide has been extensively investigated as the most promising photocatalyst. To improve the optical response of TiO2 in the visible region, Inverse Opal TiO2 has been recognized as an efficient photocatalyst due to its unique properties in terms of uniformly ordered and interconnected macroporous architecture.

Studies on various reactor configurations for coupling photocatalysis and membrane processes in water purification

General aspects and perspectives of heterogeneous photocatalysis for the treatment of polluted aqueous effluents are presented. Some experimental results obtained by using various configurations of photocatalytic membrane reactors (PMRs) are reported. The configurations studied were: (i) irradiation of the cell containing the membrane, with three sub-cases: (i1) catalyst deposited on the membrane; (i2) catalyst in suspension, confined by means of the membrane; (i3) entrapment of the photocatalyst in a PSF membrane; (ii) irradiation of the re-circulation tank and catalyst in suspension confined by means of the membrane. In the case “(i)”, a preliminary investigation of membrane stability und…

Features and application of coupled cold plasma and photocatalysis processes for decontamination of water

Dielectric barrier discharge plasma and photocatalysis have been proposed as tools for decontamination of process water, especially in food industry. The present investigation aims to redefine and identify the features of coupling the two technologies in terms of degradation efficiency of a model compound. Results show that, when the process is carried out in plasma activated water in the presence of irradiated TiO2, the efficiency of the integrated process is lower than the sum of the two processes acting separately. It is proposed that afterglow species, e.g. hydrogen peroxide and/or peroxynitrites could be activated by UVA light irradiation producing hydroxyl radicals in the liquid phase…

TiO2-CeO2 based catalysts for photocatalytic oxidation of VOC and water splitting reactions

Photocatalysis with TiO2 is one of the most promising green process for the decomposition of organic pollutants and the hydrogen production . Photo-oxidation of 2-propanol, representative of volatile organic compounds (VOC) and photo-catalytic water splitting for H2 production were investigated over TiO2 catalysts doped with a metal (Au and Ag at 1wt. %) and/or ceria (10 wt.%).

Studio delle proprietà acido-base superficiali e fotoattività di catalizzatori nanostrutturati costituiti da TiO2

Photoassisted Mechanisms in Heterogeneous Catalysis: The Role of Surface OH in the Decomposition of Ethanoic Acid on Magnesium Oxide

The photodecomposition of adsorbed ethanoic acid was studied on a number of pure and mixed insulator and semiconductor systems having a wide range of acid-base features. MgO appeared to be much more active than any other oxide when oxygen was not present in the reactant mixture. On the basis of infrared, U.V.-Vis. reflectance and photoluminescence data it is suggested that in this case the surface hydroxy-groups which are known to absorb at wavelengths longer than 300 nm are involved in the photodecomposition process.

Preparation of photocatalytic nanostructured TiO2 thin films

A Collection of Chemical Reaction Engineering Solutions in Photocatalysis

There are problems in photocatalysis that researchers cannot disregard in a rigorous study of photocatalytic systems. The purpose of the present work is to show how chemical reaction engineering can answers to the previous questions, thus helping scientists to face researches on photocatalysis more successfull and consistenty

Selective oxidation of phenol and benzoic acid in water via home-prepared TiO2 photocatalysts: Distribution of hydroxylation products

Abstract The hydroxylation of phenol (a substrate containing an electron donor group) and of benzoic acid (a substrate containing an electron withdrawing group) has been carried out by the photocatalytic method in aqueous suspensions containing commercial or home prepared TiO2 samples. The aim of the work was to study the distribution of hydroxylation products when different photocatalysts were used and to correlate the selectivity to some physico-chemical features of the powders. The samples were characterized by X-ray diffraction, thermogravimetry, determination of crystalline phase percentage, specific surface area and zero charge point. The photoreactivity results indicate that the prod…

Partial photoelectrocatalytic oxidation of 3-pyridinemethanol by Pt, Au and Pd loaded TiO2 nanotubes on Ti plate

Abstract The photoelectrocatalytic (PEC) oxidation of 3-pyridinemethanol to 3-pyridinemethanal and vitamin B3 was investigated by using Pt, Au and Pd loaded (as single or bimetallic) nanotube structured TiO2 on Ti plate in water under UVA irradiation. Nanotube structured TiO2 on Ti plate samples were prepared as anode by anodic oxidation method in ethylene glycol solution in different times, and then they were calcined at 500 °C to be obtained in crystalline form. The anodes were loaded with noble metals by electrochemical reduction method and characterized by XRD, XPS, SEM, and photocurrent techniques. The TiO2 on the plates was in the anatase phase. The loaded metals were in metallic form…

Tuning the photocatalytic activity of bismuth wolframate: Towards selective oxidations for the biorefinery driven by solar-light

The sol–gel entrapment of nanostructured Bi2WO6 enhances the activity and the selectivity of the short-gap semiconductor in the sunlight-driven photo-oxidation of trans-ferulic and trans-cinnamic acid dissolved in water with air as the primary oxidant. Valuable products such as vanillin, benzaldehyde, benzoic acid and vanillic acid are obtained. This provides the proof of concept that photocatalysis could be a promising technology in tomorrow's solar biorefineries.

Photodegradation of Pharmaceuticals in Water by Using a Nanofiltration Membrane Reactor

Cu-substituted lanthanum ferrite perovskites: Preparation, characterization and photocatalytic activity in gas-solid regime under simulated solar light irradiation

Lanthanum orthoferrites LaFeO3 nanopowders doped with 20 mol% of Sr and 0-10-20 mol% of Cu were prepared by citrate auto-combustion synthesis and investigated in terms of crystal structure, morphology, surface area and optical properties by using several characterization techniques. The band gap energy values were found to range from 2.35 eV for LaFeO3 to 1.86 eV for the samples with the highest content of copper, this trend reflects the decrease of the particle size. All powders showed photocurrent response, the highest photocurrent was obtained for undoped orthoferrite calcined at 600°C. Their physical-chemical properties were related to photoelectrochemical behaviour. The the position of…

Carbon and nitrogen-doped TiO2: preparation, characterisation and visible light photocatalytic activity

Optimization of coupled advanced oxidation processes and activated carbons for purification of salt water

Photocatalysis, ozonation and activated carbons were investigated separately and in combination as tools for the purification of polluted salt water. Coupling different processes enables to overcome many drawbacks related to the use of the single technologies and at the same time to exploit possible synergistic effects. In this work a kinetic analysis was performed for modelling the degradation of 4-nitrophenol (4NP) as a probe pollutant molecule in synthetic seawater. Thus, the optimum synergistic conditions of the three processes acting together were determined and discussed.

Aqueous selective photocatalytic oxidation of salicyl alcohol by TiO2 catalysts: Influence of some physico-chemical features

Abstract Partial photocatalytic oxidation of salicyl alcohol (2-hydroxybenzyl alcohol) to salicylaldehyde in water was investigated under environmental friendly conditions in the presence of home-prepared and commercial TiO2 (Merck and Aeroxide P25) samples under UVA irradiation. The photocatalysts were characterized by using BET, XRD, SEM and/or TEM techniques. The effects of crystallinity degree, pH (3–11) and presence of a hole trap (ethanol) on the photocatalytic activity and product selectivity were investigated. 4-Hydroxybenzyl alcohol was also used to study the influence of the position of the substituent group in the aromatic ring. High alcohols conversion and product selectivity va…

Fotocatalizzatori Ottenuti per Termoidrolisi di TiCl4

Guidelines for the Assessment and the Validation of the Rate Law of Slurry Photocatalytic Reactions

The assessment of the rate law of slurry photocatalytic reactions appears to be a hard task, mainly because in this type of reactions the average rate of reaction, which is experimentally observed in a real reactor, could be very different from the “true” (intrinsic) rate of reaction, which cannot be measured directly. In the present work, it is shown how a proper mathematical model allows the utilization of the differential and/or the integral methods of kinetic analysis. The mathematical model must take into account not only the momentum and the mass balances, but also the radiative transfer equation. However, the discrimination among different proposed kinetic laws remains difficult sinc…

Membranes for photocatalysis in wastewater treatment

Tuning The Selectivity To Aldehyde Via Ph Regulation In The Photocatalytic Oxidation Of 4-Methoxybenzyl Alcohol And Vanillyl Alcohol By Tio2 Catalysts

Abstract The influence of pH on the photocatalytic partial oxidation of 4-methoxybenzyl alcohol (MBA) and vanillyl alcohol (VA) to their corresponding aldehydes in aqueous suspension under UVA irradiation was investigated by using poorly crystalline home-prepared and crystalline commercial TiO2 (BDH, Merck and Degussa P25) photocatalysts. The results clearly show as tuning pH can strongly impart selectivity and activity to photocatalytic processes which are often quite unselective in aqueous suspensions. It was found that pH effect on reaction rate and product selectivity strongly depended on TiO2 crystallinity and substrate type. In the case of MBA oxidation, photoreactivity and selectivit…

Genotoxicity of citrus wastewater in prokaryotic and eukaryotic cells and efficiency of heterogeneous photocatalysis by TiO(2).

Abstract The presence of (±)α-pinene, (+)β-pinene, (+)3-carene, and R-(+)limonene terpenes in wastewater of a citrus transformation factory was detected and analyzed, in a previous study, by using Solid Phase Micro-extraction (SPME) followed by GC analyses. Purpose of that research was to compare the genotoxic responses of mixtures of terpenes with the genotoxicity of the individual compounds, and the biological effects of actual wastewater. Genotoxicity was evaluated in the Salmonella reversion assay (Ames test) and in V79 cells by Comet assay. Ames tests indicated that the four single terpenes did not induce an increase of revertants frequency. On the contrary, the mixtures of terpenes ca…

Photolytic and TiO2-Assisted Photodegradation of Aqueous Solutions of Tetracycline

Aqueous solutions of tetracycline were UV-irradiated in homogeneous and heterogeneous systems. Tetracycline disappeared in both systems, but the presence of TiO2 accelerated the photodegradation of the antibiotic in comparison with direct photolysis. The rate of decomposition was dependent on the concentration of tetracycline and its degradation on the surface of TiO2 can be described by means of a pseudo-first order kinetics. Photolysis involved only the photodeamination of tetracycline and a partial mineralization. Unlikely, the treatment with TiO2 and UV-light resulted in a complete mineralization of the antibiotic drug.

Polymers of Limonene Oxide and Carbon Dioxide: Polycarbonates of the Solar Economy

Limonene epoxide (1,2 limonene oxide) readily reacts with carbon dioxide in a ring opening copolymerization reaction with insertion of CO2 and formation of polycarbonates of exceptional chemical and physical properties. Both poly(limonene carbonate) and poly(limonene dicarbonate) can be synthesized using low cost Zn or Al homogeneous catalysts. This study addresses selected relevant questions concerning the technical and economic feasibility of limonene and carbon dioxide polymers en route to the bioeconomy.

Membranes for photocatalysis in water and wastewater treatment

Abstract: The chapter reports the basic principles of heterogeneous photocatalysis together with a brief presentation of the types of membranes and membrane operations most widely used in this type of application. Coupling the two technologies with the aim of obtaining synergistic effects for conversion in liquid–solid systems is discussed and the relevant papers together with some case studies in pollutants abatement and reaction of synthesis are highlighted.

A method for determining optical properties of photocatalytic suspensions

Photodegradation of 4-Nitrophenol in Aqueous Suspension by Using Polycrystalline TiO2 Samples Impregnated with Lipophilic Porphyrins Obtained from Renewable Resources

Interesting synthetic routes from the reinvestigation of the reaction of the M(CO)6 (M=Cr, Mo and W) species with KOH

Reinvestigation of the reaction of M(CO)6 (M=Cr, Mo or W) with KOH has been found to provide a very convenient route to the K[M2H(CO)10] compounds (M=Cr, Mo or W). The reaction involving Cr(CO)6 yields new potassium derivatives containing [Cr2(CO)10]2− and [HCr(CO)5]− species; also K[Cr2D(CO)10] is produced from the Cr(CO)6/KOD interaction in C2D5OD. The reaction involving two different group 6 metal carbonyls yields [MM′(CO)10(μ-H)]− (MM′=CrMo, CrW or WMo) species as their K+ and PPN+ [bis(triphenylphosphine)iminium] salts.

TiO2 Impregnato con Poliossometallato Utilizzato come Fotocatalizzatore nella Degradazione di 2-Propanolo in Fase Vapore

Home-prepared anatase, rutile, and brookite TiO2 catalysts for selective photocatalytic oxidation of p-methoxybenzyl alcohol in water: reactivity and ATR-FTIR study

Supported H3PW12O40 for 2-propanol (photo-assisted) catalytic dehydration in gas-solid regime: The role of the support and of the pseudo-liquid phase in the (photo)activity

Abstract Catalytic and photocatalytic 2-propanol dehydration was carried out by using a supported Keggin heteropolyacid H3PW12O40 (PW12). Binary materials were prepared by impregnation and/or solvothermal treatment by using commercial supports: SiO2 (Mallinckrodt), TiO2 (Evonik P25) and multiwall carbon nanotubes (Sunnano) or home solvothermically prepared SiO2 and TiO2. All the materials have been characterized by X-ray diffraction (XRD), scanning electron microscopy observations (SEM) coupled with EDX microanalysis, specific surface area measurements, diffuse reflectance spectroscopy (DRS), FTIR and Raman spectroscopy. (Photo)catalytic 2-propanol dehydration was studied in gas-solid regim…

Preparation characterization and photocatalytic activity of polycrystalline ZnO/TiO2 systems. 2. Surface, bulk characterization, and 4-nitrophenol photodegradation in liquid-solid regime

Electron spin resonance spectroscopy (ESR), Fourier transform infrared spectroscopy (FTIR), and monitoring of pyridine (py) and boric acid trimethyl ester (BATE) adsorption for determining surface acidity and basicity, respectively, were used to carry out further characterization of mixed ZnO/TiO2 polycrystalline solids prepared by different methods. Moreover, the powders were tested in a batch photoreactor for a probe reaction, i.e., 4-nitrophenol photodegradation in aqueous medium. ESR results indicated the presence of signals attributable to Zn+ species in ZnO/TiO2 (anatase) solids, while in ZnO/TiO2 (rutile) samples the presence of zinc induced only the formation of signals probably due…

Tungstophosphoric acid supported on polycrystalline TiO2 for the photodegradation of 4-nitrophenol in aqueous solution and propan-2-ol in vapour phase

Abstract The present work reports the preparation of samples based on Millennium PC-500 TiO 2 loaded with different amounts of tungstophosphoric acid (up to 30% in weight) and their characterisation by means of different physicochemical techniques: powder X-ray diffraction, N 2 adsorption–desorption at −196 °C, transmission electron microscopy, UV–vis and FT-IR spectroscopies and thermogravimetric analyses. The acidity of samples was evaluated by FT-IR using pyridine as probe molecule, and the catalysts activity was tested for the photodegradation of 4-nitrophenol in aqueous solution and for the photo-oxidation of propan-2-ol in vapour phase. The results show a noticeable improvement (8 and…

Photocatalytic activity of nanocrystalline TiO2 (brookite, rutile and brookite-based) powders

Photocatalytic oxidation of phenol on TiO2 powders. A Fourier transform infrared study

Abstract In the present paper a detailed investigation of a well known photoreaction, i.e. phenol photodegradation in the presence of TiO2, has been carried out. The Fourier transform infrared (FT-IR) technique has been used to characterize the catalyst surface and to follow the photoprocess by “in situ” measurements in a gas—solid regime, simulating the aqueous liquid—solid regime in which this photodegradation reaction has been usually carried out. The influence on the photoprocess of the surface hydroxylation of the catalyst has been investigated and the presence of some reaction intermediates has been revealed by FT-IR. The experimental results have demonstrated that the chosen gas—soli…

Photoelectrochemical properties of doped lanthanum orthoferrites

Abstract LaFeO 3 powders doped with Sr (20 mol%) and Cu (0-10-20 mol%) were prepared by citrate auto-combustion synthesis and investigated in terms of crystal structure, morphology, surface area and optical properties. All powders showed photocurrent response in the form of a pasted and annealed electrode and as slurry electrode; the highest value was obtained for undoped orthoferrite calcined at 600 °C. Their physical–chemical properties were related to photoelectrochemical behaviour. The position of the quasi-Fermi level of electrons for all the photocatalysts calcined in the range 600–980 °C is about the same within experimental error (between −0.62 and −0.67 V with respect to Ag/AgCl re…

Photoelectrocatalytic selective oxidation of 4-methoxybenzyl alcohol in water by TiO2 supported on titanium anodes

The photoelectrocatalytic partial oxidation of 4-methoxybenzyl alcohol in aqueous solution irradiated by near-UV light was carried out in a three-electrode batch reactor. TiO2 films were either deposited by dip-coating of a TiO2 sol onto a Ti foil and subsequent calcination or generated on Ti plates by thermal oxidation in air at 400-700 degrees C. The effects of the anode preparation method and bias potential values on conversion and selectivity to the corresponding aldehyde were investigated. The photoelectrocatalytic results were compared with the photocatalytic and electrocatalytic ones. The results indicated that no reaction occurred during the electrocatalytic experiments, whereas the…

Polymeric carbon nitride (C3N4) as heterogeneous photocatalyst for selective oxidation of alcohols to aldehydes

Abstract Polymeric carbon nitride (C3N4) is a semiconductor material which is a very promising green photocatalyst with good physico-chemical properties and stability. It is a metal-free carbon based non-toxic material which can be easily obtained from earth-abundant components. The robustness and versatility of C3N4 as a photo-redox catalyst allows its use for selective oxidations by heterogeneous photocatalysis. This paper reviews the state of art in the application of C3N4 as heterogeneous photocatalyst for selective oxidation of alcohols to the corresponding aldehydes.

Selective Oxidation of Alcohols to Aldehydes by TiO2 Photocatalysis

RIDUZIONE FOTOCATALITICA DI CO2 IN SISTEMI GAS-SOLIDO IN PRESENZA DI TiO2 PURO E DROGATO CON RAME

Heterogeneous Photocatalysis and Catalysis

Abstract General definitions of heterogeneous catalysis and photocatalysis are reported together with parameters to assess the catalytic and photocatalytic performances. Some features of catalytic and photocatalytic reactions, the importance of amorphous and crystalline phases of the solid photocatalysts, and reactors and photoreactors with the most important kinetic aspects are presented.

Unexpectedly ambivalent O-2 role in the autocatalytic photooxidation of 2-methoxybenzyl alcohol in water

An unusual autocatalytic photooxidation of 2-methoxybenzyl alcohol has been observed under UV irradiation in aqueous medium. The homogeneous oxidation is catalyzed by the corresponding aldehyde that is also the main oxidation product. The trend of alcohol disappearance rate matches the typical shape of an autocatalytic process, where a crucial and ambivalent role is played by the presence of molecular oxygen. Low oxygen concentrations give rise to a zero-order reaction since the beginning of irradiation, while higher amounts of oxygen reduce the alcohol oxidation rate until the aldehyde reaches a concentration high enough to speed up the alcohol's conversion. Experiments performed by varyin…

Influence of hydrogen peroxide on the kinetics of phenol photodegradation in aqueous titanium dioxide dispersion

Abstract The influence of hydrogen peroxide on the phenol photodegradation rate under near UV radiation was investigated in homogeneous and heterogeneous systems: the heterogeneous systems were aqueous dispersions of titanium dioxide (anatase). The hydrogen peroxide photodecomposition reaction was also investigated for all the systems used. The highest rate of phenol photodegradation was observed in the heterogeneous system for the contemporary presence of hydrogen peroxide and oxygen. The rate equations for phenol photodegradation and hydrogen peroxide photodecomposition for both systems were obtained. A mechanistic model able to explain the main experimental results is also proposed.

Thin-Film Photovoltaics 2011

Absolute crystallinity and photocatalytic activity of brookite TiO2 samples

Abstract This study reports a method to determine the absolute crystallinity of partly crystalline brookite TiO2 photocatalysts. A natural, a commercial and various home-prepared brookite powders were characterized by X-ray diffraction analysis, Raman spectroscopy, scanning electron microscopy, UV–vis diffuse reflectance spectroscopy and nitrogen adsorption measurements. The absolute crystallinity was calculated from the ratio between the full width at half maximum intensity of the (121) X-ray diffraction peaks of the brookite samples and the (111) peak of CaF2 as internal standard. The photocatalytic activity of the powders was tested employing the photodegradation of 4-nitrophenol as well…

Photocatalytic oxidation of acetonitrile in gas–solid and liquid–solid regimes

Il programma NON mi ha consentito di scaricare il PDF di questo articolo. Se lo volete ditemi come inviarlo ABSTRACT Photocatalytic degradation of acetonitrile was carried out in both gas–solid and liquid–solid regimes using two commercial TiO2 catalysts (Merck and Degussa P25). For the gas–solid regime, a continuous annular photoreactor was used. The influence on photodegradation kinetics of the gas flow rate and concentrations of acetonitrile, oxygen, and water was investigated. Acetonitrile degradation products detected in the gas phase included carbon dioxide and hydrogen cyanide. The same photoactivity was exhibited in the presence and in the absence of water vapour. The liquid–solid reg…

Au/TiO2-CeO2 Catalysts for Photocatalytic Water Splitting and VOCs Oxidation Reactions

Photocatalytic water splitting for H2 production and photocatalytic oxidation of 2-propanol, an example of volatile organic compounds, were investigated over TiO2 catalysts loaded with gold and/or ceria. In the water splitting reaction the presence of gold only slightly affected the performance of TiO2 whereas the presence of CeO2 had a more remarkable positive effect. In the 2-propanol oxidation Au/TiO2 was the most active sample in terms of alcohol conversion whereas Au/TiO2-CeO2 exhibited the highest CO2 yield. On the basis of characterization experiments (X-Ray Diffraction (XRD), Energy Dispersive X-ray Analysis EDX, surface area measurements, Diffuse Reflectance Spectroscopy (DRS) and …

Fundamentos de Química

Preface

This Special Issue of Catalysis Today includes selected papers presented at the 5th European Conference on Solar Chemistry & Photocatalysis: Environmental Applications (SPEA 5). The conference, held from 4th to 8th October 2008, was organized by Leonardo Palmisano and Vincenzo Augugliaro in Palermo (Italy). The 252 delegates (representing 757 authors) who came from many different European and non-European countries delivered four plenary lectures and 49 oral presentations. To emphasise the poster presentation, the 184 posters were briefly introduced by the appropriate Session Chairman before each oral sessions began. Both oral and poster presentations were divided into the following five to…