Efficient Photocatalytic Partial Oxidation of Aromatic Alcohols by Using ZnIn2S4 under Green Conditions.

The ternary chalcogenide ZnIn2S4 (ZIS) has been synthesized by a simple hydrothermal method in which the carcinogen thiacetamide, universally used as a precursor, has been, for the first time, replaced successfully with the harmless thiourea. ZIS has been used as photocatalyst for the partial oxidation of different aromatic alcohols to their corresponding aldehyde in water solution, under ambient conditions and simulated solar light irradiation. The photocatalytic performance of ZnIn2S4 was better than TiO2 P25. In the presence of ZIS for 4-methoxybenzyl alcohol, piperonyl alcohol, and benzyl alcohol, a selectivity towards the corresponding aldehyde of 99% for a conversion of 46%, 75% for a conversion of 81%, and 87% for a conversion of 25%, respectively, was obtained. For the same alcohols a selectivity of 19% for a conversion of 41%, 19% for a conversion of 13%, and 16% for a conversion of 26%, was observed in the presence of TiO2 P25.

Pt-TiO2 catalysts for glycerol photoreforming: comparison of anatase, brookite and rutile polymorphs.

We compared the H2 production from glycerol photoreforming for different TiO2 polymorphs, highlighting an increase of activity in the order Pt-rutile < Pt-P25 ≈ Pt-anatase < Pt-brookite with a different distribution of the reaction intermediates. We show that the highest ability to adsorb water and the different distribution of Pt active sites in brookite can positively influence its photoactivity.

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

A set of metals modified TiO2 photocatalysts were prepared starting from titanium tetraisopropoxyde and different metal precursors to study the influence of the addition of the various foreign agents on the physico-chemical and photocatalytic properties of the catalysts. The powders were characterized by X-ray diffraction, Raman spectroscopy, specific surface area measurements, scanning electron microscopy, energy dispersive X-ray spectroscopy, UV-Vis diffuse reflectance spectroscopy, photoluminescence, temperature programmed desorption after CO2 adsorption. The photocatalytic activity was evaluated using as probe reactions the partial oxidation of three aromatic alcohols: benzyl alcohol (BA), 4-methoxy benzyl alcohol (4-MBA), and 4-hydroxy benzyl alcohol (4-HBA) under simulated solar light irradiation. Different oxidation and selectivity values were obtained for the three substrates depending not only on the type of metals but also on the nature and position of the substituent in the phenyl ring of benzyl alcohol. As a general behaviour, the doped samples allowed the achievement of a greater selectivity especially for 4-MBA even if sometimes with minor conversions. The presence of W or Nb was beneficial for both conversion and selectivity for all the substrates with respect to bare TiO2.

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 different concentrations, ranging between 0.1 and 2 mM, were analyzed by means of ion chromatography. Splitting two partially merged chromatographic peaks and considering each resulting area as originating from a single species produces "measured" concentration values which differ from the nominal ones. Such a procedure generates errors (one per species) which can be written as a function of the above mentioned "measured" concentrations and which can be graphically represented by means of a surface in a three-dimensional (3D) space. In this way, "measured" concentrations of bromide and nitrate ions can be corrected by calculating the errors generated under the experimental conditions at which the chromatographic separation is performed. Notably, this is analogous with the two-dimensional (2D) calibration normally carried out for analytical purposes. Indeed, both methods allow estimation of the unknown concentration of species in solution by correlating the instrumental response with the concentration of standard solutions.

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.

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

Heterogeneous photocatalysis and photoelectrocatalysis have been considered as oxidation technologies to abate unselectively noxious species. This article focuses instead on the utilization of these methods for selective syntheses of organic molecules. Some promising reactions have been reported in the presence of various TiO2 samples and the important role played by the amorphous phase has been discussed. The low solubility of most of the organic compounds in water limits the utilization of photocatalysis. Dimethyl carbonate has been proposed as an alternative green organic solvent. The recovery of the products by coupling photocatalysis with pervaporation membrane technology seems to be a solution for future industrial applications. As far as photoelectrocatalysis is concerned, a decrease in recombination of the photogenerated pairs occurs, enhancing the rate of the oxidation reactions and the quantum yield. Another benefit is to avoid reaction(s) between the intermediates and the substrate, as anodic and cathodic reactions take place in different places.

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

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.

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 both vanillin and the reactant (ferulic acid) are analyzed, since they ultimately affect the performances of the membrane reactor. The results show that diffusion of the aromatic compounds takes place in the presence of low concentration gradients, so that the process is controlled by other phenomena, in particular by the equilibrium with the vapor at the membrane-permeate interface. On this basis, it is demonstrated that the performances are enhanced by increasing the membrane thickness and/or the temperature, whereas the pH begins to limit the process only at values higher than 6.5.

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 (λ > 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.

Advances in selective conversions by heterogeneous photocatalysis.

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

Home-prepared anatase, rutile, and brookite TiO(2) for selective photocatalytic oxidation of 4-methoxybenzyl alcohol in water: reactivity and ATR-FTIR study.

TiO(2) 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, CO(2) 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.

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

The photocatalytic oxidation of benzyl alcohol (BA) and 4-methoxybenzyl alcohol (MBA) has been performed in pure water by using commercial TiO(2) samples (Sigma-Aldrich, Merck, Degussa P25) and rutile TiO(2) prepared from TiCl(4) at low temperature. Particular attention has been devoted to the identification of the produced aromatic compounds along with the formed CO(2). Oxidation products such as the corresponding aromatic aldehyde and acid, as well as mono- and dihydroxylated aldehydes have been detected. The home-prepared rutile sample showed a marked selectivity towards the formation of the aromatic aldehyde (38 and 60 % for BA and MBA, respectively), resulting in a three- to sevenfold improvement relative to commercial samples, with the only byproduct being CO(2). This catalyst was found to be the most selective in the formation of aldehyde in water. By using the commercial or the calcined home-prepared samples, many hydroxylated aromatic compounds were detected besides the aldehyde and the acid. This finding points to a higher selectivity performance of the home-prepared rutile relative to the commercial TiO(2) samples. Some of the home-prepared samples were also dialysed to check the influence of the presence of Cl(-) species on catalyst reactivity and selectivity. We have attempted to explain the different reaction rate and selectivity observed for MBA and BA.

Influence of the substituent on selective photocatalytic oxidation of aromatic compounds in aqueous TiO2 suspensions.

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

Photocatalytic oxidation of methyl-orange in aqueous suspension: comparison of the performance of different polycrystalline titanium dioxide.

The photocatalytic oxidation of methyl-orange (C14H14N3SO3Na) dye was carried out in aqueous suspensions of polycrystalline TiO2 irradiated with artificial light until its complete mineralization was achieved. The performances of two widely used semiconductor powders were studied for comparison purposes. The dependence of dye photo-oxidation rate on various experimental parameters, including substrate concentration, semiconductor amount, and pH was investigated by using both catalysts. The observed dye degradation rates followed pseudo-first order kinetics with respect to the substrate concentration under the experimental conditions used. The two investigated TiO2 powders (Degussa P25 and Merck) showed different photoactivities. TOC analyses confirmed the complete mineralization achievable using both photocatalysts. Three main transient products still maintaining the chromophoric azo group were identified prior to their transformation into other degradation products which are non-absorbing in the visible region.

Azo-dyes photocatalytic degradation in aqueous suspension of TiO2 under solar irradiation.

The photodegradation of two common and very stable azo-dyes, i.e. methyl-orange (C14H14N3SO3Na) and orange II (C16H11N2SO4Na), is reported. The photocatalytic oxidation was carried out in aqueous suspensions of polycrystalline TiO2 irradiated by sunlight. Compound parabolic collectors, installed at the "Plataforma Solar de Almería" (PSA, Spain) were used as the photoreactors and two identical reacting systems allowed to perform photoreactivity runs for the two dyes at the same time and under the same irradiation conditions. The disappearance of colour and substrates together with the abatement of total organic carbon content was monitored. The main sulfonate-containing intermediates were found to be in lower number in respect to those obtained under artificial irradiation. In particular there were no more evidence of the presence of hydroxylated transients. The dependence of dye photooxidation rate on: (i) substrate concentration; (ii) catalyst amount; and (iii) initial pH was investigated. The influence of the presence of strong oxidant species (H2O2, S2O8(2-)) and some ions (Cl-, SO4(2-)) on the process was also studied.

Photocatalytic degradation of actual textile industrial wastewater in aqueous suspensions of polycrystalline TiO2.

Heterogeneous photocatalytic oxidation of contaminants present in wastewater produced by a textile industry was carried out. The samples were withdrawn from the plant before and after a traditional biological treatment. The effluents were named A and A' (before the biological treatment), B and B' (after the biological treatment). Polycrystalline TiO2 (Degussa P25) was used as the catalyst in a batch photoreactor with immersed lamp. An almost complete decolorization was observed after about 0.5 divided by 1 hours for both kinds of effluents, but the decrease of the total organic carbon (TOC) concentration occurred more slowly. The influence of some chemical oxidants, i.e. ozone, hydrogen peroxide and peroxydisulfate on the photo-oxidation rate was also investigated. After addition of H2O2 or S2O8(2-) TOC decreased more quickly only for B and B'. The runs performed by using O3 as bubbling gas showed a mineralization rate higher than that observed in the presence of O2.