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In this work the photocatalytic (PC) and photoelectrocatalytic (PEC) reforming of furfuryl alcohol (FA) under environmental friendly conditions was investigated. Both H2 evolution and partial oxidation to furfuraldehyde were followed. For the first time TiO2 based photocatalysts were studied and the photocatalytic activity of home prepared photocatalysts was compared with that of commercial ones under both UVA and simulated solar irradiation. PEC tests were performed by using home prepared TiO2 nanotubes (TiO2 NTs) as photoanode and Pt free Ni foam as cathode to improve the Hydrogen Evolution Reaction (HER). Both the partial FA oxidation reaction rate and H2 evolution rate were normalized for the lamp specific power to account for the different photon flux and the rates were higher for PEC process. PEC is a promising strategy for the valorization of biomasses with simultaneous H2 production in spite of the cost of the bias.

Partial photocatalytic oxidation of salicyl alcohol (2-hydroxybenzyl alcohol) to salicylaldehyde in water was investigated under environmental friendly conditions in the presence of home-prepared and commercial TiO2 (Merck and Aeroxide P25) samples under UVA irradiation. The photocatalysts were characterized by using BET, XRD, SEM and/or TEM techniques. The effects of crystallinity degree, pH (3–11) and presence of a hole trap (ethanol) on the photocatalytic activity and product selectivity were investigated. 4-Hydroxybenzyl alcohol was also used to study the influence of the position of the substituent group in the aromatic ring. High alcohols conversion and product selectivity values were obtained at pH = 11 by using well crystallized TiO2 samples. The conversion values significantly decreased by increasing the hole trap concentration, whereas the selectivity values increased slightly. The selectivity towards the corresponding aldehyde after 30% of alcohol conversion was significantly higher for 4-HBA (48%) than for 2-HBA (32%), due to the role of the para position of the substituent group. In order to clarify the different selectivity of the products, various experiments have been also performed starting from the products; these results indicate that the selectivity is also strongly dependent on the stability of the formed products under the experimental conditions used. By concluding, this article reports that the conversion and selectivity values for the studied reaction depend both on the TiO2 type and on the substrate.

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 photocatalytic ozonation with photocatalysis with definite cycle allowed to severely limit the presence of the organic compounds, which otherwise could accumulate in the system, and at the same time to control the formation of bromate, the ozonation side-product of main concern. In addition, the values of other parameters, which are important for water quality, remained at satisfactory values. It was also verified that the prepared photocatalytic films maintained a good photocatalytic activity even after several months of utilization in seawater. These results demonstrate that photocatalytic ozonation is a good candidate for water purification in recirculating systems in view of sustainable aquaculture.

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 selectivity were very high at low pH values for all of TiO2 catalysts, and the crystalline samples showed to be more active than the poorly crystalline ones. At pH= 1 the photoactivity of Degussa P25 was the highest one, and 88% selectivity at 50% conversion was determined. At acidic pH values, selectivity and activity were higher in the presence of HCl than H2SO4 or H3PO4. For VA oxidation, high selectivity values were obtained at high pH’s for all of the samples, and the crystalline samples showed higher activity at the alkaline pH values with respect to that observed at the acidic ones. Experiments starting from the obtained products, that are p-anisaldehyde and vanillin, showed that the selectivity depends on the resistance of those compounds to be subjected to further oxidation under the experimental conditions used.

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 membrane reactor obtained by the effective coupling of dialysis with the photocatalytic reaction improved the production yield. For instance, with the utilized experimental set up, the total amount of vanillin produced after 5 h in the membrane reactor was more than one-third higher than in the photocatalytic reactor without dialysis. The results obtained with a mathematical model agree with the experimentally observed behavior. The model allowed estimating vanillin diffusivity in the membrane and showed that concentration polarization might limit the process.

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 interdisciplinary competences and collaborations are often required in this field. However, we hope that a survey of the recently reported examples may inspire researchers for future developments and new opportunities.

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.

In this paper, the first photoelectrocatalytic (PEC) 3-pyridinemethanol oxidation to 3-pyridinemethanal and vitamin B-3 was investigated. To meet this aim, efficient nanotube structured TiO2 on a Ti plate as a photoanode was prepared by an anodic oxidation method in ethylene glycol and characterized by XRD, SEM, and photocurrent techniques. The effect of nanotube morphology, applied potential, Na2SO4 concentration, stirring speed of solution, and pH on the reaction activity and product selectivities were investigated. The TiO2 phase of all of the anodes was mainly the anatase one. The PEC activity, the intensity of the XRD peak and the photocurrent increased by increasing the nanotube length. The activity decreased by decreasing both the Na2SO4 concentration and the applied potential, whereas 3-pyridinemethanal selectivity increased. By increasing the stirring speed of the solution, both the activity and the 3-pyridinemethanal selectivity increased. A lower or no activity was observed for photocatalytic (PC) and electrocatalytic runs, respectively, which were carried out for the sake of comparison. No PC activity was obtained in the presence of N-2, but PEC reactions in the presence of N-2 were faster than those in the presence of O-2. The produced 3-pyridinemethanal in both N-2 and O-2 atmosphere was reduced at the cathode in the PEC reaction, but its oxidation appeared to be much more favourable. The PC reactions could not be carried out under acidic conditions, whilst the PEC ones could be performed in the pH range of 2-12. Moreover, the results indicate that the PEC method allows higher conversions and selectivities to vitamin B-3 to be obtained at pH 7 with respect to those reported in the literature.

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.

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.

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 and at alkaline pHs, cis-caffeic acid cyclized to esculetin both in the absence and in the presence of irradiation.

The use of microreactors in (photo)catalytic processes offers new possibilities for studying and optimizing many mass and photon transfer limited reactions. In this study, we propose a scalable computational fluid dynamics (CFD) model for the prediction of photocatalytic degradation of a model pollutant (4-nitrophenol) using immobilized N-doped TiO2 grown over reduced graphene oxide (N-TiO2/rGO) in a photocatalytic microreactor working in continuous flow-recirculation mode. The mode of operation used in this study allows the reduction of mass transfer limitations inherent to heterogeneous photocatalytic reactions taking place on immobilized catalysts. A CFD model was developed for effective prediction of experimental results using COMSOL multi-physics. The experiment and the model results clearly showed a good agreement. The model parameters were determined through fitting the model with the experimental data, adsorption rate constants were estimated to be 1.76 × 104 m3 mol−1 h−1 and 0.0252 h−1 for monolayer (kads,m and kdes,m), 1.76 × 104 m3 mol−1 h−1 and 0.0126 h−1 for multilayer (kads,n and kdes,n); and the intrinsic rate constant (ks) was 2.02 h−1. This proposed model herein could serve as a practical tool to improve and optimize an extensive number of photocatalytic reactions for (waste)water applications in microreactors operating in recirculation mode.

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 discussed. The presented results highlight that a precise evaluation of the efficiency of the process is a challenging but necessary task to be approached in order to allow real applications of photocatalytic processes.

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 with H 2 production. In the presence of the sonicated samples the 4-nitrophenol degradation and the glucose conversion increased of ca. 40% and 11%, respectively. A good H 2 evolution was, moreover, observed in the latter case. The Pt-loaded samples showed the highest photoactivity for H 2 production and it can be explained by taking into account the highest value of its working function. The obtained results open new perspectives for the synthesis of novel nano-TiO 2 -based photocatalysts capable to degrade water or airborne pollutants under visible light irradiation.

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 since these laws usually predict very similar behaviors. In the case of “photodifferential” reactors, kinetic analysis can be carried out considering just the measured average rates of reaction without utilizing the mathematical model. For instance, it is shown that, with a photodifferential reactor, the fitting of the average rate of reaction vs. the substrate concentration gives a satisfactory appraisal not only of the kinetic parameters but also of the average rate of photon absorption. A sufficiently low value of the optical thickness (less than 2.5) is the main requirement to approach the photodifferential condition. Anyway, a strategic choice of the experimentally investigated values of the independent variables (e.g. substrate concentration and irradiance to the reactor) is important for the comprehensiveness of the kinetic analysis.

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 process bromate ions are not produced as long as some oxidizable organics are present. © 2013 Elsevier Ltd.

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.

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.

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 2-NBA was oxidised very fast, although no corresponding carbonyl product was obtained. The possible catalytic role of 2-MBAD was investigated for the photolytic oxidation of 4-methoxybenzyl alcohol (4-MBA), 4-nitrobenzyl alcohol (4-NBA), 2-CIBA, 2-HBA, 2-MeBA and ferulic acid (FA). The results showed that 2-MBAD acts as a catalyst only for 4-MBA, 2-HBA and FA. The photocatalytic oxidation of OSBAs in the presence of powdered TiO2 has been also carried out in order to investigate the mutual influences, if any, between homogeneous and heterogeneous processes. The reactivity runs were carried out with TiO2 photocatalyst in water and under near-UV irradiation; a home-prepared (HP) TiO2 sample was used along with Degussa P25. HP catalyst showed the best performance: the 2-MBA half-life time was 5 times smaller and the selectivity to aldehyde 13 times higher than in the presence of Degussa P25. (C) 2016 Elsevier B.V. All rights reserved.

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 and of the operating conditions (recirculation flow rate, optical thickness) are studied. For instance, it is shown that the average values of the reaction rate and of the rate of photon absorption give no direct insight on the intrinsic kinetic if the reactor is not uniformly illuminated and the optical thickness is beyond a given value, which is significantly higher than the one usually suggested in literature for a “safe” kinetic analysis. Furthermore, the estimation of the average rate of photon absorption must take into account the backscattering of radiation from the reactor. In any case, the utilization of a proper mathematical model allows carrying out a sound kinetic analysis also in critical situations as those which can arise with an illumination by LEDs.

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 CO2 derived from the mineralization, was made for all of the substrates at irradiation times corresponding to the highest selectivity to vanillin. High closure of the carbon balance was obtained with vanillyl alcohol (ca. 90%) and trans-ferulic acid (ca. 80%).

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-substituted aromatic compounds, investigated to better understand the influence of the substituent group on the reactivity of these species and on the distribution of oxidized products. The second aspect investigated is the possibility of using heterogeneous photocatalysis for the selective oxidation of alcohols to aldehydes and ketones. The partial oxidation of alcohols to produce carbonyl compounds is of great industrial importance; generally, it is performed in environmentally harmful organic solvents at high temperatures and pressures by using stoichiometric oxygen donors that not only are expensive and toxic, but also produce large amounts of dangerous waste

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%) and 41% (MBA conversion: 65%), about four times higher than those of commercial TiO2. The addition of an aliphatic alcohol (methanol, ethanol, 2-propanol or tert-butanol) in small amounts with respect to water decreased the overall oxidation rate of aromatic alcohols but enhanced the selectivity for aldehyde formation up to 1.5 times. The reactivity results suggest that: (i) the aromatic alcohol molecules interact with the TiO2 surface in different ways that eventually determine two parallel reaction pathways (partial oxidation or mineralization); (ii) the aliphatic alcohols preferentially compete with aromatic alcohols for the mineralizing pathway.

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 the HP catalyst showing the highest selectivity and the commercial titania showing the highest activity towards benzyl alcohol oxidation (Degussa P25 TiO2) was carried out. The ATR-FTIR results indicate that HP and Degussa P25 surfaces show a very dissimilar hydrophilicity and different ability for adsorbing the organic compounds deriving from benzyl alcohol photocatalytic oxidation. Results show moreover that the improved selectivity to aldehyde by adding ethanol is due to competition between the substrate and the hole trap for adsorption on reactive sites.

WOS: 000246040000026, The photocatalytic oxidation of 4-methoxybenzyl 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 exhibited a PAA yield higher than that of commercial ones. The only by-products present were traces of 4-methoxybenzoic acid and aliphatic products, carbon dioxide being the other main oxidation product.

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 varying alcohol, aldehyde and oxygen concentrations in both aqueous and organic media suggest that the alcohol oxidation is initially favored by the presence of oxygen. Once the formed aldehyde competes for photon absorption, the oxidation is driven by aldehydes alpha cleavage leading to reactive oxygenated species in aqueous medium. An excess of oxygen quenches the latter processes thus inhibiting/slowing down the reaction. (C) 2015 Elsevier B.V. All rights reserved. tAn unusual autocatalytic photooxidation of 2-methoxybenzyl alcohol has been observed under UV irradi-ation in aqueous medium. The homogeneous oxidation is catalyzed by the corresponding aldehyde that isalso the main oxidation product. The trend of alcohol disappearance rate matches the typical shape of anautocatalytic 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, whilehigher amounts of oxygen reduce the alcohol oxidation rate until the aldehyde reaches a concentrationhigh enough to speed up the alcohol’s conversion. Experiments performed by varying alcohol, aldehydeand oxygen concentrations in both aqueous and organic media suggest that the alcohol oxidation is ini-tially favored by the presence of oxygen. Once the formed aldehyde competes for photon absorption,the oxidation is driven by aldehydes alpha cleavage leading to reactive oxygenated species in aqueousmedium. An excess of oxygen quenches the latter processes thus inhibiting/slowing down the reaction.

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‐methoxybenzyl alcohol to 4‐methoxybenzaldehyde under UV irradiation in water at room temperature. The corresponding aldehyde was obtained with unprecedented high selectivity (up to 86 %). The method is general and opens the route to fabrication of photocatalytic composites based on titanium dioxide functionalized with shuttle organic molecules and metal nanoparticles for a variety of oxidative conversions.

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 compound. The benefits of the coupling of photocatalysis to ozonation are not limited to the increase of the oxidation rate, but include also the control of the ozonation by-product of main concern (bromate). The effect of the pH, of the presence of oxidizable organic compounds, of the presence of nitrogen on the formation or on the reduction of bromate are experimentally studied and discussed. The obtained results have relevance for the practical applications of PO, since on these bases it is possible to identify proper operating conditions.

A study of the photodegradation of different pharmaceuticals [furosemide, ranitidine (hydrochloride), ofloxacine, phenazone, naproxen, carbamazepine and clofibric acid] in aqueous medium at various pHs by using a batch photoreactor and a photocatalytic membrane reactor working in recirculation regime was carried out. Polycrystalline TiO 2 was used as the photocatalyst, and different membranes (NTR 7410, PAN GKSS HV3/T, N 30 F, NF PES 10) were tested. A different adsorption of the substrates onto the catalyst surface was observed owing to the hydrophilic/hydrophobic character of the catalyst, depending on the pH. The photodegradation of the seven molecules in the batch reactor was successfully carried out and the behaviour was in accordance with pseudo-first order kinetics. Furosemide and ranitidine were selected to carry out the study of rejection and photodegradation in the hybrid membrane system. The permeate flux of the treated water was in the 31.5–60.0 L/(h m 2 ) range for NTR 7410 membrane, whereas rejection values in the range 10–60% for furosemide and 5–30% for ranitidine in the dark (without photoreaction) were found. The degradation in the hybrid membrane photoreactor showed that the photocatalyst was retained by the membrane in the reaction ambient, while the membrane rejection towards the pollutants was not very satisfactory. A net decrease of the rejection down to 0 was observed in the contemporary presence of light, photocatalyst and oxygen.

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 regime used a batch photoreactor with an immersed lamp (the same as for the gas–solid regime). The oxidation products detected in the solution were cyanide, cyanate, nitrite, nitrate, methanoate, and carbonate ions. The Langmuir–Hinshelwood kinetic model fit the photoreactivity data obtained in both regimes and allowed us to determine the rate constant and equilibrium adsorption constant values. The adsorption constant and kinetic constant value were lower in the liquid–solid regime than in the gas–solid regime. The Merck catalyst had higher values of these parameters for both regimes than the Degussa P25 catalyst. An evaluation of the possible competition between acetonitrile and water molecules for the surface sites of the photocatalyst (Ti 4 + ions and hydroxyl groups) revealed that for high H2O/CH3CN ratios, as is typical for the photo-oxidation process carried out in a liquid/solid regime, acetonitrile molecules were not able to provide a specific interaction with the surface sites of TiO2, remaining dissolved in the interface water molecular layers. In contrast, for low H2O/CH3CN ratios, as is typical for the photo-oxidation process carried out in a gas–solid regime, acetonitrile could win the competition with water for surface hydroxyls.  2005 Elsevier Inc. All rights reserved.

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 order kinetics with respect to acetonitrile and NPOC concentrations, respectively. The presence of S2O82− and solar irradiation determined the occurrence of homogeneous degradation of acetonitrile and NPOC. In the presence of irradiated catalyst, a significant synergetic effect was observed for NPOC degradation while for the acetonitrile oxidation this effect was not evident. H2O2 did not affect the process while ClO− affected negatively the acetonitrile oxidation rate and it inhibited the NPOC degradation.

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 degradation with oxygen; and (iv) photocatalytic degradation with ozone. The rate of cyanide oxidation by heterogeneous photocatalytic mechanism is enhanced by ozone with respect to that observed in the presence of neat oxygen. A kinetic model based on Langmuir–Hinshelwood equations describes adequately the photoreactivity results and provides the values of the kinetic constants and equilibrium adsorption constants for the catalytic and photocatalytic reactions contributing to cyanide oxidation. In order to gain further information on the interaction of ozone with TiO2 surfaces, either in the dark or under UV-irradiation, an ESR study has been also carried out. The results indicate that ozone strongly interacts with TiO2, leading mainly to the formation of ozonide radicals.

This special issue of Catalysis Today Journal, is dedicated to the career of Prof. Vincenzo Augugliaro, University of Palermo, Italy, in the occasion of his retirement in 2015. Prof. Vincenzo Augugliaro was Full Professor of Transport Phenomena at the University of Palermo (Italy) since 1994. He contributed to the fol- lowing research fields: chemical absorption kinetics, biochemical reactor modelling, diffusional kinetics in metallizing alloys and heterogeneous photocatalysis; in this last field he investigated on chemical kinetics of heterogeneous photocatalytic systems, modelling of heterogeneous photoreactors, radiation field in absorbing-reacting media and application of heterogeneous pho- tocatalysis to syntheses processes. He published more than 150 papers in prestigious journals and many chapters in books and is co-author of 4 patents. Prof. Augugliaro was appreciated not only for his important achievements in the field of heterogeneous photocatalysis, but also for his great effort as mentor of many master and PhD chemical engineering students. This special issue contains twenty-four original papers by researchers involved in various aspects of heterogeneous photocatalysis.

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 the catalyst occurred. FTIR investigations indicated that benzaldehyde is photoproduced on the TiO2 surface even in the absence of water vapour, but exposure of the catalyst to the UV light in a dry atmosphere results in an irreversible consumption of surface hydroxyl groups. As these species play a key role in the photoreactive process, this dehydroxylation should be the reason of the catalyst deactivation observed in the catalytic runs carried out in the absence of water vapour.

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 the other aerobic bacteria, which are usually taken as reference in photocatalytic bacteria inactivation studies, this ratio was of order of 0.3 for the first hour of illumination, while upon prolonged irradiation (up to 9 h) this ratio increased to 0.7. Several factors inducing this latter decrease of efficiency are possible, as e.g. competition for photocatalytic attack between microorganisms and organic compounds released by damaged bacteria or photoinduced alteration of a small fraction of still viable bacteria making them less interactive with the photocatalyst. The inactivation mechanism normally proposed for common bacteria involves an initial attack of the photogenerated radicals to the outer membrane; the consequent membrane dispersion allows the radicals to damage the cytoplasmic membrane. The higher lethality of the photocatalytic method observed towards Legionella: (in comparison to the other aerobic bacteria) is explained considering that the radicals attack the Legionella secretion system, which is adapted for high virulence and would become activated for and through adhesion to the TiO2 surface. This attack would then be able to inactivate L. pneumophila without dispersing the outer membrane. Apart from this, the water flow through the catalyst fibres can facilitate the bacteria transport towards the anatase surface, and additionally the generated shear stress may help adhesion, at least for some bacteria as E. coli, contributing further to improve the photokilling efficiency; both factors may contribute to the efficiency of this photoreactor configuration.

In this paper the preparation and some bulk and surface characterizations of set of Al2O3 supported TiO2 photocatalysts are reported. The powders were home prepared by a wet impregnation method using titanium (IV) isopropylate. The impregnation was followed by thermal treatments and this procedure was repeated several times in order to obtain samples with different amounts of TiO2. The solids were characterized by X-ray diffraction, specific surface area determination, scanning electron microscopy coupled with an electron microprobe used in an energy-dispersive mode and diffuse reflectance spectroscopy. Moreover, all of them were tested as photocatalysts by using different kinds of batch photoreactors for 4-nitrophenol photodegradation in aqueous medium chosen as a ‘probe’ reaction. The characterization results indicate that a layer of anatase TiO2 formed on the surface of Al2O particles, its extent depending on the number of impregnations. The photoactivity of the powders increased by increasing the number of impregnations up to seven times. For samples obtained by impregnating seven times, the photoreactivity was higher, but not much different from that observed by using samples impregnated five times. The photoactivities of the samples obtained with five and seven impregnations were found to be not much lower than that of a pure home prepared TiO2 sample, but quite lower than that of a Degussa P25 TiO2 sample. Finally, it is worth noting that the alumina supported TiO2 catalysts are easily separated from water by decantation and no significant deactivation due to disaggregation of the particles and/or erosion of their surface was shown to occur in some of the used experimental conditions, i.e. when photoreactors coupled with an electric impeller were used.

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 power of irradiation while it is independent of the initial cyanide concentration and the pH. The detrimental effect of chloride ions on cyanide photooxidation rate is not determined by a competition mechanism of chloride ions with cyanide ions or oxygen molecules for adsorption on active sites. Chloride ions affect the photoreaction rate by lowering the concentration of dissolved oxygen to values for which oxygen may become a rate limiting reactant. The Langmuir–Hinshelwood kinetic model well fits all the photoreactivity results. The reaction pathway was also investigated; cyanate, nitrate, and carbonate were found to be the main oxidation products. A mass balance on nitrogen was also successfully carried out. Specific experiments were carried out in a particular setup for measuring both the photon flow absorbed by the reacting suspension and the cyanide photoreaction rate; for these particular conditions the quantum yield value was calculated.

Two different photo-catalysts consisting of tungsten oxide supported on zirconia and niobia have been studied. The photoactivity of the samples has been investigated in both the absence and presence of H2O2 for the photo-oxidation of 4-nitrophenol in aqueous suspensions and compared to that of WO3 and of the pure ZrO2 and Nb2O5 supports. Both catalysts were found to be photoactive, although no beneficial influence of the presence of tungsten oxide on the reaction rate was observed in the absence of H2O2. The presence of hydrogen peroxide was observed to be beneficial for all of the samples. Scanning electron microscopy, X-ray diffraction, diffuse reflectance and laser Raman spectroscopies, surface area and porosity determination, as well as Fourier transform infra-red spectroscopy monitoring of surface acidity were used to characterize the catalysts.

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 photocatalytic reactivity was positively influenced by the application of a small bias (0.75 V vs. saturated calomel electrode). By applying the previous bias the highest initial degradation rates, r(0), and selectivities to 4-methoxybenzaldehyde, S, were obtained in photoelectrocatalytic experiments by using Ti plate calcined at 500 degrees C (r(0) = 0.1507 mM h(-1), S=85%) or TiO2 film prepared by dip-coating and calcined at 700 degrees C (r(0) = 0.1339 mM h(-1), S=90%). In order to investigate the influence of the substituent groups on reactivity and selectivity, photoelectrocatalytic runs with benzyl alcohol, 2-methoxybenzyl alcohol, 3-methoxybenzyl alcohol, 2,4-dimethoxybenzyl alcohol, 2,3,4-trimethoxybenzyl alcohol, 4-nitrobenzyl alcohol and 4-hydroxybenzyl alcohol have been performed. The selectivity and reactivity values increased by increasing the electron-donor properties of the substituent groups. This positive effect, however, was obtained only if the electron-donor group is in para or ortho position with respect to the alcoholic group. (C) 2012 Elsevier B.V. All rights reserved.

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 evaluated by cyclic voltammetry. The optimal organic sensitizing amount was found to be 5.6 % w/w in terms of yield in carbonyl derivatives. Moreover, no change in reactivity/selectivity was observed after 10-h irradiation thus confirming the catalyst stability. Yields into formaldehyde, acetaldehyde, and acetone were 67, 70, and 96 %, respectively. No significant amounts of organic byproducts were detected but for methanol oxidation, whereas a minor amount of the substrate degraded to CO2.

The influence of incident light intensity and of some physical and chemical parameters on the absorbed and backward reflected photon flow and on the reactivity of a heterogeneous photocatalytic system was investigated. The oxidation of phenol in aqueous solution in the presence of polycrystalline TiO 2 powder was used as a test reaction. Home-prepared TiO 2 (anatase) specimens, subjected to various thermal treatments, were used for the experimental runs performed in a batch photoreactor directly irradiated. The physical parameters investigated were the surface area and the size of particles, while the chemical parameters studied were the initial pH of the suspension and the presence in the reacting medium of additives affecting the photoreactivity such as Cl − and H 2 O 2 . It was found that the ratio between backward reflected and incident photon flow does not depend on the used operative variables, while the apparent Napierian extinctance coefficient, which is a parameter related to the photon absorption rate, depends only on the particle size and decreases as the particle size increases. The photoreaction quantum yield, defined as the ratio between the phenol reaction rate and the photon absorption rate, was determined for the various experimental conditions used in this work. The results showed that at equivalent conditions the quantum yield is an intrinsic feature of the semiconductor material; the quantum yield varies only by varying the reaction rate which, in our case, was affected only by the initial pH of the suspension and by the presence of Cl − and H 2 O 2 .

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 only the photogenerated hole but also the OH radicals are involved in the oxidation of the substrates. (C) 2012 Elsevier B.V. All rights reserved.

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 products of the primary oxidation of phenol are the ortho- and para-mono-hydroxy derivatives while those of benzoic acid are all the mono-hydroxy derivatives independently of the catalyst. The selectivity toward mono-hydroxy derivatives shows a strong dependence on catalyst hydroxylation and crystallinity degrees: the highest selectivity values were obtained by using the commercial samples that resulted the least hydroxylated and the most crystalline ones. A kinetic model, taking into account the mineralization and the partial oxidation reaction routes, is proposed by using the Langmuir–Hinshelwood model.

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 crystallized catalysts – even if the last ones show a higher activity – and (ii) exploitation of solar light significantly increases the reaction selectivity. In addition, different light sources were also used in order to investigate the effect of radiation wavelength ranges on the reactivity and selectivity to aldehyde.

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 production and possibility of operating in a continuous mode with high values of the yield. (C) 2010 Elsevier B.V. All rights reserved.

WOS: 000280384800004, The photocatalytic oxidation of 4-methoxybenzyl alcohol in water was performed in a fixed bed continuous annular reactor by using a home-prepared TiO2 catalyst supported on Pyrex glass beads. The investigation was aimed to modeling the complex kinetics of the photoprocess which occurs through two parallel pathways: (i) partial oxidation to the corresponding aldehyde and (ii) total oxidation to CO2 and H2O. On these grounds, the influence of liquid flow rate, inlet concentrations of alcohol and oxygen, catalyst amount, and irradiation power on the photoreactivity were studied. A kinetic model like that of Langmuir-Hinshelwood satisfactorily fitted the experimental results and allowed determination of the values of model parameters. It was found that all these parameters are positively affected by an increase of radiant energy absorbed by the catalyst. All the reactivity results indicate that the partial oxidation pathway is favored by the low flux of absorbed photons and by low oxygen coverage on the TiO2 surface; opposite conditions favor the mineralization pathway.

2nd European Conference on Environmental Applications of Advanced Oxidation Processes -- SEP 09-11, 2009 -- Nicosia, CYPRUS, WOS: 000278720000005, The photo-oxidation of glycerol in aqueous suspensions containing commercial and home-prepared TiO2 samples in the anatase, rutile or anatase-rutile polymorphic phases was investigated by using two different batch photoreactors, an annular photoreactor and a cylindrical photoreactor. The glycerol oxidation products detected in the aqueous phase were: 1,3-dihydroxyacetone, glyceraldehyde, formic acid and carbon dioxide. Two unknown compounds were also detected by electrospray ionization mass spectrometry as peaks at m/z 268 and m/z 176. A plausible mechanism for their formation was suggested based on ESI-MS and MSn experiments. The results indicate that in both systems the commercial samples showed the best performances both for reaction rate and selectivity toward 1,3-dihydroxyacetone, glyceraldehyde, formic acid and CO2, Tech Univ Crete, Aristotle Univ Thessaloniki, Univ Cyprus

5th European Meeting on Solar Chemistry and Photocatalysis -- OCT 04-08, 2008 -- Palermo, ITALY, WOS: 000265890300014, PubMed ID: 19424540, TiO2 catalysts of anatase, rutile and brookite phase were prepared at low temperature and tested for carrying out the photocatalytic partial oxidation of 4-methoxybenzyl alcohol to 4-methoxybenzaldehyde (p-anisaldehyde) in organic-free water suspensions. Traces of 4-methoxybenzoic acid and open-ring products were the only by-products present, CO2 being the other main oxidation product. Rutile exhibited the highest yield to p-anisaldehyde (62% mol) at a rate of the same order of magnitude of that showed by the other samples. Commercial rutile and anatase photocatalysts were also used for the sake of comparison. The samples have been characterised by an in situ ATR-FTIR investigation carried out in conditions simulating the photoreaction ones.

WOS: 000264978500012, Home-prepared (HP) rutile TiO2 catalysts were prepared at room temperature by using H2O and TiCl4 in different ratios and without addition of additives. The catalysts were used for carrying out the selective photocatalytic oxidation of 4-methoxybenzyl alcohol to 4-methoxybenzaldehyde in aqueous suspension, free from any organic co-solvent. The selectivities showed by the home prepared catalysts were in the 45-74% range, up to four times higher than that of a commercial rutile TiO2 sample, the reaction rates being comparable. By using the most selective photocatalyst, the oxidation of benzyl, 4-methylbenzyl, and 4-nitrobenzyl alcohols was also carried out in order to investigate the influence of the substituent group on the oxidation rate and selectivity. The presence of an -OCH3 group positively influenced the selectivity whereas a -NO2 group showed to have a detrimental effect. The Hammett relationship effectively describes the influence of substituent group on the kinetic constant of partial oxidation of aromatic alcohols to aldehydes.