0000000000095862
AUTHOR
Vincenzo Augugliaro
Environmentally Friendly Photocatalytic Oxidation of Aromatic Alcohol to Aldehyde in Aqueous Suspension of Brookite TiO(2)
WOS: 000260509000008
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.
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
Oxidation of aromatic alcohols in irradiated aqueous suspensions of commercial and home-prepared rutile TiO(2): a selectivity study.
WOS: 000256241700021
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…
Alkaline treatment as a means to boost the activity of TiO(2)in selective photocatalytic processes
In this work, the activity enhancement of TiO(2)photocatalysts by alkaline treatment has been investigated. Commercial (BDH, U.K., anatase phase) TiO(2)samples, treated in alkaline solutions of NaOH at different concentrations and temperatures, were tested for the photocatalytic partial oxidation of 3-pyridinemethanol in water under UVA irradiation to form vitamin B-3. Photocatalyst characterization has been carried out by XRD, BET, TEM, TGA, photoluminescence, FTIR, Raman, DRS, EPR and photocurrent measurements. The alkaline-treated samples showed an increased activity of up to 7 times (by considering first order rate constant values) compared to untreated BDH and the superior performance …
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 …
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
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.
Current Problems in the Modelling of Photochemical Reactors
Photochemical reactors are examined from the point of view of the main problems connected to their modelling. By distinguishing the diverse meanings of kinetic models and the varied objectives in establishing models, a particular attention is devoted to the following aspects of homogeneous photoreactors: steady state condition, effect of stirring and mixing, effect of the shape of the reactor and of the position of the light source, light emission models, scale up. For the heterogeneous systems only general considerations on kinetic models in heterogeneous photocatalysis and on the problems related to the use of fluidized bed photoreactors are done.
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…
Production of Aldehydes by Oxidation in Aqueous Medium with Selective Recovery of the Product by Means of Pervaporation
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.
Photocatalytic membrane reactors
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…
The influence of the anatase nanoparticles boundaries on the titania activity performance
Metal oxides structures, formed by ordered self-assembling of crystalline nanoparticles aggregates, are attracting growing attention in fields such as catalysis or solar cells. The properties of these structures are influenced not only by their morphology and nanoparticles composition but also by the assembled particles boundaries. In order to determine the influence of these boundaries on the structures properties, the present investigation has been devoted to study the characteristics of anatase nanoparticles boundaries in titania aggregates prepared by TiCl4 hydrolysis at low temperature. Proton magic angle spinning nuclear magnetic resonance and high resolution transmission electron mic…
Optical Properties and Quantum Yields Determination in Photocatalytic Suspensions
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
Graphite-supported TiO2 for 4-nitrophenol degradation in a photoelectrocatalytic reactor
WOS: 000274769500044
Photocatalytic degradation of organic pollutants by using polycrystalline TiO2: case studies for environment remediation
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…
Photocatalytic oxidation of nitrobenzene and phenylamine: Pathways and kinetics
WOS: 000245150800018
Sintesi di Piperonale tramite fotocatalisi eterogenea in condizioni green
Photocatalytic inactivation of Legionella Pneumophila and aerobic bacteria consortium in water over TiO2/SiO2 fibres in a continuous reactor
A continuous photoreactor, working in a total recycle mode and irradiated by a low-pressure Hg lamp, has been used to study the bactericidal effect of a photocatalyst, formed by TiO2 embedded in SiO2 fibres, on Legionella pneumophila and a consortium of common gram-negative aerobic bacteria: (Escherichia coli, Klebsiella sp., Pseudomona sp. and Proteus sp.) in water. The kinetic modeling of the inactivation process, carried out with the measured values of viable bacteria concentration at the outlet of photoreactor, evidenced that for each pass inside the photoreactor the ratio between the outlet and inlet cell concentrations was of order of 0.01 for the inactivation of L. pneumophila. For t…
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…
Comparison of Different Photocatalytic Systems for Acetonitrile Degradation in Gas-Solid Regime
Concerning“An Opinion on the Heterogeneous Photoreduction of N2 with H2O”: First Letter
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…
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, …
A quantitative method of photoadsorption determination for irradiated catalyst in liquid–solid system
WOS: 000266963000002
Anatase photocatalyst with supported low crystalline TiO2: The influence of amorphous phase on the activity
Abstract In a previous study on commercial TiO2 nanoparticles (J. Soria et al.) we had shown that the superficial disordered layers influence their textural and reactivity features. In the present work we used well crystallized anatase particles (commercial TiO2, BDH) as support of different amounts of titania powders, prepared by TiCl4 hydrolysis and constituted by nanocrystals diluted into an amorphous matrix. The reactivity of these photocatalysts has been tested for the selective oxidation of 4-methoxybenzyl alcohol to aldehyde in aqueous suspension. The catalyst characteristics have been studied using adsorption-desorption isotherms, TEM, HRTEM, TGA, PL, DRIFT-IR, and 1H MAS-NMR spectr…
Film di TiO2 da idrolisi di TiCl4: preparazione, caratterizzazione e fotoattività
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.
Telloruro di Cadmio: Eldorado del fotovoltaico o insidia ambientale?
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 …
4-Nitrophenol Oxidation in a Continuous Fixed Bed Photoreactor Containing Titanium Dioxide Supported on Glass Beads
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
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…
Clean by Light Irradiation: Practical applications of supported TiO2
Arbeitsmethoden und Versuche: Abschnitte 8.4.2 (Versuche 37 - 43) - 8.6
Ozone enhanced activity of aqueous titanium dioxide suspensions for photocatalytic oxidation of free cyanide ions
The ozonization and the heterogeneous photocatalytic method are contemporarily applied for the oxidation of free cyanide ions. A batch photoreactor with immersed lamp was used for treating aqueous suspensions containing polycrystalline TiO2 powders irradiated in the near-UV region. Air or ozone–air mixtures were used as oxidation reactants. At the used experimental conditions, the photoreaction proceeds at a measurable rate until low values of cyanide concentration. In the presence of ozone (O3) several parallel reaction routes are contributing to the overall cyanide degradation: (i) homogeneous oxidation by ozone; (ii) heterogeneous catalytic reaction by ozone; (iii) photocatalytic degrada…
The effect of the surface disordered layer on the photoreactivity of titania nanoparticles
It is well known that the surface of metal oxide catalysts presents, usually, non-crystalline species containing impurities and low coordinated cations, which are observed in HRTEM images as a disordered layer of amorphous phase. Despite of being these species more accessible and less stable than the crystalline catalysts components, they have been rarely considered when analysing the catalyst activity. In this work, we have studied the effect of a treatment with HCl solution at pH = 0 on the characteristics of the disordered layer in two commercial anatase TiO2 samples, using techniques such as TGA, 1H MAS-NMR and HRTEM, and by determining these sample photocatalytic activity for the 4-nit…
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...
Preparation, characterization and photocatalytic activity of Phtalocyanine-doped TiO2/ORMOSIL thin films
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…
TiO2 Nanomaterials Used as Photocatalysts for Selective Heterogeneous Syntheses of Alcohols to Aldehydes in Water
Ozone absorption in aqueous phenol solutions
Abstract The rate of ozone absorption in aqueous solutions of phenol was measured in a wetted-wall laboratory absorber. The liquid and gas flow rates were fixed as well as the pH and temperature. The phenol concentration was varied in the range 2–300 ppm and the ozone partial pressure over an eight fold range. The gas phase resistance to mass transfer was determined by absorbing SO2 from an SO2N2 mixture in KOH aqueous solutions. The results have been interpreted by means of a simple kinetic assumption.
A Method for Determining Optical Properties and Quantum Yields of Photocatalytic Suspensions
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...
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 …
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…
Studio di processi fotocatalitici: dalla preparazione del fotocatalizzatore alla comprensione della cinetica e del meccanismo di reazione
Sintesi di Vanillina tramite Reazione di Ossidazione Fotocatalitica con TiO2 in Fase Acquosa
Photocatalytic Oxidation of Acetonitrile
Photocatalytic synthesis of piperonal in aqueous TiO2 suspensions
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
Oxidación Fotocatalítica de Acetonitrilo en Regimen Gas-Sólido y Líquido-Sólido
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…
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…
Synergistic effect of ozone and photocatalytic oxidation over TiO2 on the removal of free cyanide ions
Photocatalytic Selective Oxidation of 4-Methoxybenzyl Alcohol to Aldehyde in Aqueous Suspension of Home-Prepared Titanium Dioxide Catalyst
WOS: 000246040000026
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…
Kinetics of photocatalytic degradation of pharmaceuticals in aqueous TiO2 suspension
Studio della Fotodegradazione di Antibiotici in Ambiente Acquoso
ESR study of photo-oxidation of phenol at low temperature on polycrystalline titanium dioxide
The formation of oxygen radicals on hydrated TiO 2 (anatase) samples irradiated at 77 K in the near-UV region and their interaction with adsorbed phenol molecules have been studied by electron spin resonance. The results indicate that the irradiation determines the generation of O 2 H · and O − radicals which react with adsorbed phenol molecules. Phenol-derived radicals are generated after warming the sample at room temperature. A reaction mechanism is proposed on the basis of the observed species.
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…
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 …
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 of 4-methoxybenzyl alcohol to p-anisaldehyde in a fixed bed continuous reactor,
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.
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.
Selective Photocatalytic Production of Aldehydes
A reactor for photoelectrocatalytic oxidation of aromatic alcohols
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…
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…
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…
"Caratterizzazione ottica di sospensioni acquose di fotocatalizzatori utilizzati in processi di abbattimento di inquinanti organici
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…
Anatase nanoparticles boundaries resulting from titanium tetrachloride hydrolysis
An important factor that governs solar energy transformation into electrical or chemical energy, when using nanoparticles-based devices, is the spatial location of traps limiting electron transport. Evidences have been presented indicating that the electron diffusion is strongly influenced by nanoparticle boundaries, whose characteristics depend on the particles preparation. In the present work we have studied the role of hydrated excess proton structures in the formation of anatase nanoparticles boundaries in samples prepared by TiCl4 hydrolysis at low temperature and strong acidic conditions. The samples, constituted by anatase nanocrystals but, mainly, by amorphous titania, are studied b…
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…
Photoadsorption determination for irradiated catalyst in liquid-solid system
Two-Dimensional Modeling of an Externally Irradiated Slurry Photoreactor
Abstract A batch cylindrical photocatalytic reactor, externally irradiated by 1–6 UV fluorescent lamps and containing a stirred slurry of polycrystalline TiO2, was modeled by coupling a modified Langmuir–Hinshelwood kinetics together with a two-dimensional light intensity field. The radiation field has been determined on the main assumptions of diffuse radiation, isotropic scattering and negligible backward reflected photon flow. The model has been applied to the photocatalytic oxidation of organic substrates which do not undergo homogeneous photochemical degradation. The model is characterized by the following four parameters: the kinetic constants of substrate adsorption, desorption and d…
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
Degradazione Fotocatalitica Eterogenea di Acetonitrile e Toluene in Regime Gas-Solido e Liquido-Solido
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…
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.
Fourier Transform Infrared Study of the Performance of Nanostructured TiO2 Particles for the Photocatalytic Oxidation of Gaseous Toluene
Thermal and hydrothermal treatments have been applied to an amorphous TiO2 precursor for obtaining nanosized TiO2 particles (P11t and P11h, respectively) of different photocatalytic properties. The activity of these catalysts has been tested by performing the toluene oxidation in gas phase in a continuous photoreactor. A Fourier transform infrared (FTIR) investigation of the catalysts under conditions prevailing during the test photoreaction has also been carried out. The photoreactivity results showed that CO2 was the main oxidation product and benzaldehyde a stable intermediate. Anatase P11t photoactivity was similar to that observed for commercial photocatalysts, while anatase P11h prese…
Validation of a two-dimensional modeling of an externally irradiated slurry photoreactor
Abstract A two-dimensional model describing the behavior of a batch cylindrical photoreactor has been validated through a series of photocatalytic reactivity runs. The light intensity radiation field produced by 1–6 external UV fluorescent lamps was modeled together with Langmuir–Hinshelwood kinetics and 4-nitrophenol (NP) and Degussa P25 TiO 2 were used as the probe molecule and the catalyst, respectively. The experiments were carried out under different conditions of light intensity, photocatalyst amount and substrate concentration. The model parameters were the kinetic constant of substrate adsorption, desorption and degradation and the exponent of the power law expressing the kinetics d…
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
Combination of ozonation and photocatalysis for purification of aqueous effluents containing formic acid as probe pollutant and bromide ion
The treatment by advanced oxidation processes (AOPs) of waters contaminated by organic pollutants and containing also innocuous bromide ions may generate bromate ions as a co-product. In the present work heterogeneous photocatalysis and ozonation have individually been applied and in combination (integrated process) to degrade the organic compounds in water containing also bromide anions. The results show that: i) the sole photocatalysis does not produce bromate ions and in the case of its presence, it is able to reduce bromate to innocuous bromide ions; ii) the integration of photocatalysis and ozonation synergistically enhances the oxidation capabilities; and iii) in the integrated proces…
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
Photodegradation of Lincomycin in aqueous TiO2 suspension by using artificial or solar light
Degradation of Lincomycin in Aqueous Medium: Coupling of Solar Photocatalysis and Membrane Separation
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
TiO2 Heterogeneous Photocatalysis as a Selective Tool for Organic Green Syhtneses
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.
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
Photocatalytic abatement of organic compounds using home prepared TiO2 as photocatalysts
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…
Self-assembled titania-silica-sepiolite based nanocomposites for water decontamination
WOS: 000264524200020
Oxidacíon fotocatalítica de alcoholes aromáticos. Influencia de la adicíon de atrapadores de huecos en la selectividad a aldehídos
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…
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
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.
Preparation, characterisation and photoactivity of nanostructured TiO2 catalysts
Optical characterization of TiO2 suspensions: influence of some operational parameter on mean particle size
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 …
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.
Photocatalytic Oxidation of Drugs by Using Artificial and Solar Irradiation
Preface
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).…
Ossidazione selettiva di alcoli aromatici ad aldeidi in sospensioni acquose di TiO2 anatasio e rutilo
Influenza del Sostituente sulla Ossidazione Fotocatalitica Selettiva di Composti Aromatici
Enhancing Selectivity of Photocatalytic Synthesis of p-Anisaldehyde in Water under Solar Irradiation by N- Doped TiO2
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…
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…
Heterogeneous photocatalysis: optical characterisation of polycrystalline photocatalysts for pollutant degradation in aqueous medium
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…
Nanomateriali a base di TiO2 come fotocatalizzatori per sintesi selettive di alcoli ad aldeidi in fase acquosa
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.
Autocatalytic Photo-Oxidation of 2-Methoxybenzyl Alcohol and O2 Quenching therein
Preparation, characterization and photocatalytic activity of TiO2 rutile
Room Temperature Home Prepared TiO2 Rutile Used for Selective Photocatalytic Oxidation of Aromatic Alcohols to Aldehydes in Aqueous Medium
Photocatalytic Oxidation of Acetonitrile in Aqueous Suspension of Titanium Dioxide Irradiated by Sunlight
Oxidación Fotocatalítica del Acetonitrilo en Régimen Gas-Sólido y Líquido-Sólido
Influence of Amorphous TiO2-x on Titania Nanoparticle Growth and Anatase-to-Rutile Transformation
Amorphous TiO2-x formed together with precursors and anatase nuclei, during TiCl4 hydrolysis at soft conditions, influences both crystal growth and phase stability. The highly defective nanoparticles of anatase grow by reaction of their basic hydroxyls with acidic ones of TiO2 precursor species. The growth of anatase crystals, however, is affected by their interactions with simultaneously formed amorphous TiO2-x which increasingly covers the particles hindering the anatase-precursor contact. The interactions among anatase and amorphous and precursor components have been studied by H-1-MAS (magic angle spinning) NMR spectroscopy. The interaction between acid and basic hydroxyls favors the fo…
Nanostructured rutile TiO2 for selective photocatalytic oxidation of aromatic alcohols to aldehydes in water
WOS: 000253100100022
Selective photocatalytic oxidation of 3-pyridinemethanol on platinized acid/base modified TiO2
TiO2 catalysts, modified with acidic or alkaline solutions and then platinized, were used for the partial photocatalytic oxidation of 3-pyridinemethanol to 3-pyridinemethanal and vitamin B-3 under environmentally friendly conditions. The reaction took place in water under UVA light and air oxygen. Catalysts were characterized by TEM, photoluminescence, DRIFT-IR, Raman, DRS, XPS, and photocurrent measurements. The photocatalytic activity results show that Pt loading of untreated samples leads to a significant activity improvement (hence product yield) as much as acid and alkaline treatments do. Moreover, the alkaline treated TiO2 samples exhibit a further increase in activity after loading w…
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
Preparazione di Fotocatalizzatori Nanostrutturati a Base di TiO2
ZrO2SiO2 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 ZrO2SiO2 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…
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…
Influence of the Preparation Temperature on the Photocatalytic Activity of 3D-Ordered Macroporous Anatase Formed with an Opal Polymer Template
Even if many aspects of three-dimensionally ordered macroporous (3DOM) titania have been extensively studied, the interplay between the amorphous and crystalline components of their skeleton wall has not attracted too much attention, although it should strongly influence the properties of these materials. In order to gain new insight on this interplay, we have studied in detail the wall structure of three 3DOM titania samples prepared by heating the 3DOM titania precursor at 673, 773, and 873 K by X-ray diffraction, thermogravimetric analysis, differential thermal analysis, N2 adsorption/desorption, pore-size distribution, high-resolution transmission electron microscopy, and IHmagic-angle-…
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 …
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…
Partial oxidation of aromatic alcohols via TiO2 photocatalysis: the influence of substituent groups on the activity and selectivity
Aromatic alcohols with substituent groups in different positions have been partially oxidised to the corresponding aldehydes in a photocatalytic system in order to investigate the influence of the substituents on reactivity and selectivity to aldehyde. To this aim benzyl alcohol, 2-methoxybenzyl alcohol, 3-methoxybenzyl alcohol, 4-methoxybenzyl alcohol, 2,4-dimethoxybenzyl alcohol, 4-hydroxybenzyl alcohol and 4-hydroxy-3-methoxybenzyl alcohol have been photocatalytically oxidised to their corresponding aldehydes in aqueous TiO2 suspensions under near-UV irradiation. Home-made and commercial rutile TiO2 samples were used as photocatalysts. The catalysts were characterized by XRD, BET, SEM, T…
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.
Selective photooxidation of ortho-substituted benzyl alcohols and the catalytic role of ortho-methoxybenzaldehyde
It has been recently reported by Palmisano et al. (2015) [1] that the oxidation of 2-methoxybenzyl alcohol (2-MBA) to 2-methoxybenzaldehyde (2-MBAD) proceeds in water under near-UV light with an unexpected catalytic effect of 2-MBAD. In order to investigate the catalytic role of aldehyde in photolytic oxidation of ortho-substituted benzyl alcohols (OSBAs), reactivity runs were carried out with 2-methylbenzyl alcohol (2-MeBA), 2-nitrobenzyl alcohol (2-NBA), 2-hydroxybenzyl alcohol (2-HBA) and 2-chlorobenzyl alcohol (2-CIBA) in the absence and in the presence of their corresponding aldehyde. None of those alcohols showed a measurable oxidation rate even in the presence of their aldehydes but …
Preparazione e caratterizzazione di film fotocatalitici
Solar Eneergy Conversion to Chemical Photocatalytic Selective Oxidation of 5-(Hydroxymethyl)-2-furaldehyde to 2,5-furandicarbaldehyde in Water by Using TiO2 Nanoparticles
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.
Combination of Photocatalysis and Ozonation for the treatment of Contaminated Water Containing Bromide Ions
TiO2 Nanocristalline samples used to photo-oxidize aromatic alcohols to aldehydes
Efecto de la Fotocatálisis Heterogenea y la Ozonización sobre la Oxidación del Ion Oxalato en Suspensión Acuosa de TiO2
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…
NanoMORALs: Metal Nanoparticles Doped with Organic Molecules
A new class of nanosized metal–organic alloys (MORALs) has been synthesized for the first time. Silver nanoparticles doped with Cu(II) and Fe(III) phthalocyanines were thus synthesized in the presence of sodium dodecyl sulfate (SDS). The resulting materials were characterized by means of XRD, SEM, TEM coupled to energy dispersive X-ray analysis, and thermogravimetric analysis. No leaching of the photoactive dopant species was observed in water or in common organic solvents.
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…
Diffusional kinetics of metalliding zinc into solid copper
The process of incorporation of zinc into a copper cathode has been experimentally studied in a molten salt system at 381±2° C and at various current densities. The process is shown to be kinetically controlled by the diffusion of Zn into the solid matrix. A galvanostatic pulse titration technique has been used to determine the chemical diffusion coefficient at various alloy compositions, and an exponential relationship has been found between the diffusivity and the third power of the zinc concentration in the alloy. This relationship was then used in the diffusion equation within the solid matrix and a numerical integration was performed. Very good agreement was found between the calculate…
Carbon and nitrogen-doped TiO2: preparation, characterisation and visible light photocatalytic activity
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…
N-Doped Anatase/Rutile Photocatalysts for the Synthesis of Aromatic Aldehydes Under Ultraviolet and Solar Irradiation
N-doped anatase/rutile photocatalysts were prepared by a sol-gel method, using TiCl4 as TiO2 precursor and urea as N-dopant source. The catalysts required a thermal treatment at temperature higher than 300 degrees C to achieve actual nitrogen doping; this treatment also allowed obtaining crystalline and hydrophobic samples. Moreover, nitrogen doping modified the surface of samples by increasing the anatase to rutile phase ratio and hydrophilicity. The catalysts were characterized by BET specific surface area, XRD, ESEM, TGA, FT-IR, DRS and XPS measurements, with particular attention to the assessment of the N-doping effect. It was found that XPS analysis should be used together with DRS and…
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.
A method for determining optical properties of photocatalytic suspensions
Home-prepared anatase, rutile, and brookite TiO2 catalysts for selective photocatalytic oxidation of p-methoxybenzyl alcohol in water: reactivity and ATR-FTIR study
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…
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…
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…
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…
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…