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…

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…

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…

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.

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

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…

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

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.

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…

Ferulic Acid Oxidation Through Visible Light Induced TiO2 Photocatalysis

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

Influence of biochar on the physical, chemical and retention properties of an amended sandy soil

Soil porosity plays an important role in soil-water retention and water availability to crops, potentially affecting both agricultural practices and environmental sustainability. The pore structure controls fluid flow and transport through the soil, as well as the relationship between the properties of individual minerals and plants. Moreover, the anthropogenic pressure on soil properties has produced numerous sites with extensive desertification process close to residential areas. Biochar (biologically derived charcoal) is produced by pyrolysis of biomasses under low oxygen conditions, and it can be applied for recycling organic waste in soils and increase soil fertility, improving soil st…

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 …

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 …

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 …

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…

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-…

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.

Photokatalytische Funktionalisierung von Alkanen

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

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 …

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…

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…

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

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…

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…

TiO2-induced photoisomerization of caffeic acid

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

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

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…

Nanostructured anatase TiO2 densified at high pressure as advanced visible light photocatalysts

This study reports on characterization and photoactivity of nanostructured TiO2 samples, which have been permanently densified under high pressures, up to 2.1 GPa. Commercial Mirkat 211 anatase has been used as a benchmark sample, in order to investigate the effect of unidirectional high pressure on structural, optical and photocatalytic properties of TiO2. Vibrational Raman spectroscopy shows that the treatment does not cause transitions among the different crystalline phases of titanium dioxide. UV-vis diffuse reflectance spectra reveal that increasing pressure gives rise to a shift of the absorption onset towards higher wavelength enhancing the photoactivity under visible radiation. Samp…

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

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…

Preparation of Sm-loaded brookite nanoparticles and thin films

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 …

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…

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

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: 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%)…

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.

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.

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

Effect of biochar on the physical and structural properties of a sandy soil

Abstract Biochar application to soil can be considered as a means to improve soil quality, thereby optimizing irrigation management and reducing irrigation needs, especially in dryland regions. This paper is aimed at investigating the effect of biochar (BC) on a desert sandy soil (Al Foah, United Arab Emirates) in terms of bulk density, porosity, water retention, plant available water (AWmax), aggregate stability (AS) and specific surface area (BET-SSA). BC was produced from forest biomass (Italy). Soil water retention was measured by the High Energy Moisture Characteristic (HEMC) and by pressure plate measurements, by using BC fractions equal to 0 (soil only), 0.014, 0.091, 0.23, 0.33 and …

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…

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…

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…

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…

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…

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…

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

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…

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…

Economical aspects, toxicity, and environmental fate of cerium oxide

Abstract The present chapter reports some economical aspects of the cerium oxide market. Porter’s and PESTEL analyses have been used to evidence the strengths and weaknesses of the ceria market, along with the potentiality and opportunities within the years to come. The wide use of CeO2 nanoparticles in many applications requires to consider also issues related to their toxicity and environmental fate. In this regard, some contradictory reports in the relevant literature have been surveyed, thus highlighting the need for further and detailed investigation on these topics in order to propose effective strategies of risk assessment and environmental remediation.

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

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…

(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…

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.

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…

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…

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.

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.

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…

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…

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…

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…

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…

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…

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…

Biochar amended soils and water systems: Investigation of physical and structural properties

There are significant regional differences in the perception of the problems posed by global warming, water/food availability and waste treatment recycling procedures. The study illustrates the effect of application of a biochar (BC) from forest biomass waste, at a selected application rate, on water retention, plant available water (PAW), and structural properties of differently standard textured soils, classified as loamy sand, loam and clay. The results showed that soil water retention, PAW, and aggregate stability were significantly improved by BC application in the loamy sand, confirming that application of BC to this soil was certainly beneficial and increased the amount of macropores…

Photocatalytic ozonation under visible light for the remediation of water effluents and its integration with an electro-membrane bioreactor

Abstract Photocatalysis and photocatalytic ozonation under visible light have been applied for the purification of a complex aqueous matrix such as the grey water of Masdar City (UAE), by using N-doped brookite-rutile catalysts. Preliminary runs on 4-nitrophenol (4-NP) solutions allowed to test the reaction system in the presence of a model pollutant and to afford the relevant kinetic parameters of the process. Subsequently, the remediation of grey water effluent has been evaluated in terms of the reduction of total organic carbon (TOC) and bacterial counts. The concentration of the most abundant inorganic ionic species in the effluent has been also monitored during reaction. Photocatalytic…

Catalytic and photocatalytic epoxidation of limonene: Using mesoporous silica nanoparticles as functional support for a Janus-like approach

Abstract Mesoporous silica nanoparticles (MSN) were used as a platform to design novel active materials for the catalytic and photocatalytic epoxidation of limonene. Binary systems comprised of TiO2 and MSN were used for the catalytic reaction when doped with manganese, and for the photocatalytic reaction when functionalised with hexadecyl chains or imidazolinyl groups. All of the MSN based systems were synthesized by condensation in emulsion. A thorough characterization of the powders has been performed by means of Inductively Coupled Plasma – Optical Emission Spectroscopy (ICP-OES), X-ray diffraction (XRD), FT-IR, Raman and EPR Spectroscopy, Fluorescence and diffuse reflectance UV–vis (DR…

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…

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…

Semiconductor-photocatalyzed sulfoxidation of alkanes.

Preparazione di fotocatalizzatori a base di TiO2 brookite drogati con samario

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

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…

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

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…

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…

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.

C-H Activation through Semiconductor Photocatalyzed Sulfoxidation of Alkanes

Au/CeO2 Photocatalyst for the Selective Oxidation of Aromatic Alcohols in Water under UV, Visible and Solar Irradiation

Au nanoparticles supported on CeO2 have been prepared and investigated as photocatalysts for the photocatalytic selective oxidation of benzyl alcohol and 4-methoxybenzyl alcohol to the correspondent benzaldehydes, in aqueous suspensions and room conditions under UV, visible and natural solar light irradiation. Au nanoparticles have been supported by impregnation (1 and 3 wt.%) on two types of CeO2 (i.e., a commercial one and a home prepared oxide obtained in the presence of NaOH as precipitation agent). The Au impregnated samples showed strong visible radiation absorption at 565–570 nm associated to localized surface plasmon resonance (LSPR). The bare CeO2 samples are activated by UV light …

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.

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…

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

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 …

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.

Visible Light Photocatalysis by a Titania-Rhodium (III) Complex

Functionalization of mesoporous silica nanoparticles through one-pot co-condensation in w/o emulsion

In this work, three different functionalized mesoporous silica nanoparticles (MSNs) were synthesized through the co-condensation synthesis in oil/water emulsion. Hexadecyltrimethoxysilane, triethoxy-3-(2-imidazolin-1-yl)propylsilane and (3-mercaptopropyl)triethoxysilane were used as organo-substituted silica precursors with variable molar ratio with respect to tetraethylorthosilicate (TEOS, 1:4, 1:9, 1:19). The occurred functionalization was investigated by Infrared Spectroscopy and FT-Raman and 29Si {1H} CP-MAS-NMR spectroscopy. Results show that the three materials were successfully functionalized. The influence of the different pendant groups and their concentration on the mesostructured…

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…

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

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…

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…

Visible-light driven oxidation of gaseous aliphatic alcohols to the corresponding carbonyls via TiO2 sensitized by a perylene derivative

Sensitized P25 TiO2 was prepared by wet impregnation with a home-prepared perylene dye, i.e., N,N?-bis(2-(1- piperazino)ethyl)-3,4,9,10-perylene-tetracarboxylic acid diimide dichloride (PZPER). Energy levels of PZPER were found to be compatible with those of TiO2 allowing fast electron transfer. The obtained catalyst has been characterized and used in the gas-phase partial oxidation of aliphatic primary and secondary alcohols, i.e., methanol, ethanol, and 2- propanol. The reaction was carried out under cut-off (?> 400 nm) simulated solar radiation in O2 atmosphere. The perylene derivative allowed a good absorbance of visible radiation thanks to its low optical energy gap (2.6 eV) which was …

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

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.

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…

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.

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…

Visible Light Induced Sulfoxidation of Alkanes in the Presence of Titania

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.

Kinetic Aspects of Heterogeneous Catalytic Versus Photocatalytic Reactions

Abstract Kinetics aspects of heterogeneous catalysis and photocatalysis are reported together with the most used models developed for both fields. The chapter describes the main mechanisms involved in the different processes and the parameters used to determine their performances. A comparison of the behaviors and kinetics features of heterogeneous catalysis and photocatalysis is presented.

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…