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

Catalytic and photocatalytic 2-propanol dehydration to propene at atmospheric pressure and a temperature range of 60–120 °C were carried out in gas-solid regime by using bare and supported Keggin H 3 PW 12 O 40 (PW 12 ) and Wells-Dawson H 6 P 2 W 18 O 62 (P 2 W 18 ) heteropolyacids (HPAs). Binary materials were prepared by impregnation of the HPAs on commercial SiO 2 and TiO 2 . The Wells-Dawson was in any case more active than the Keggin heteropolyacid and the differences were enhanced when the supported samples were used. In particular, Wells-Dawson HPA supported on TiO 2 and under irradiation showed the highest activity. The HPA species played the key role both in the catalytic and photo-assisted reactions. The acidity of the cluster accounts for the catalytic role, whereas both the acidity and the redox properties of the HPA species were responsible for the increase of the reaction rate in the photo-assisted catalytic reaction. The estimated apparent activation energy resulted always lower for the photocatalytic process than for the catalytic one.

In the present work we scrutinize the effect of substituents in the phenyl ring of the benzyl alcohol on its photo-oxidation to the corresponding benzaldehyde driven by polymeric carbon nitride photocatalyst in aqueous medium. It has been established that electron donating (ED) substituents in para- and ortho-position with respect to the CH2OH-group promote the reactivity of the substrate without compromising the selectivity towards benzaldehyde formation, maintaining it in the range of 84–98 %, if compared to the unsubstituted molecule. The same observation is true for meta-substituted benzyl alcohol with an electron withdrawing (EW) group. On the other hand, the presence of ED-group in meta-position or EW-group in para-position with respect to the CH2OH-group reduces the reactivity as well as the selectivity towards the aldehyde production, resulting in the values of selectivity ranging from 40 to 80 %. Quantum chemical calculations have allowed to establish that the reactivity correlates with the positive charge on the benzylic carbon in benzyl alcohol cation intermediate, while the selectivity, most probably, is conditioned by a negative charge on the carbon atoms in the phenyl ring being a target for an electrophile attack. The modification of the polymeric C3N4 photocatalyst with H2O2 reduces the unselective benzyl alcohol oxidation, thus favouring the higher selectivity towards benzaldehyde production.

Commercial and home prepared bare and Pt-supported TiO2 samples were used as the photocatalysts for the aqueous photo-conversion of glucose at ambient pressure and temperature. Aerobic and anaerobic conditions were used to study the products of glucose degradation both in the liquid (arabinose, erythrose, gluconic acid, glucaric acid, fructose and formic acid) and gaseous (H2 and CO2) phases. The distribution of these molecules was different in the presence of the various powders, depending on the structural and physico-chemical properties of the materials, and Pt resulted essential for the anaerobic production of H2. The home prepared samples resulted more active than the commercial ones. The rutile and brookite polymorphs were the most active samples both for glucose conversion and H2 formation (about 1700 μmol of H2 were produced over 7 h of irradiation in the presence of Pt-brookite materials).

Strontium titanate-based perovskites have been prepared in the presence of Y and Co with the aim to substitute Sr and Ti, respectively, in the ST crystalline structure. The obtained samples have been characterized by XRD, Raman spectroscopy, FE-SEM, XPS and tested as photocatalysts in two gas-solid regime reactions: (i) 2-propanol complete mineralization and (ii) propene partial oxidation, using a system simulating solar irradiation. All the tested samples resulted active as photocatalysts but with significant differences. The lattice substitution of Sr by Y displays a beneficial effect on the 2-propanol photodegradation. Conversely, the partial presence of cobalt on the ST surface, as Co-oxide nanodispersed clusters with a dominant Co(II) phase, plays a substantial detrimental effect on the photo-degradation process of 2-propanol, but favours the photocatalytic partial oxidation of propene to propene oxide. (c) 2014 Elsevier Inc. All rights reserved.

Binary materials composed of the oxides SiO2, TiO2 and N-doped TiO2 and the Keggin heteropolyacid (PW12) were prepared and physicochemically characterized. They were used as catalysts and photocatalysts for the hydration of propene to 2-propanol. The characterization of the samples, particularly the electron paramagnetic resonance (EPR) spectroscopy results and the acidity properties, were useful to explain the key role played by the PW12 in the composite materials in the thermal and photoassisted catalytic processes. The simultaneous pres-ence of heat and UV light improved the activity of PW12 in the thermal process, and the binary materials showed better (photo)catalytic activities than that of the bare PW12 in almost all cases. For the first time, this work evidenced through EPR spectroscopy that the increase of reactivity under irradiation could be attributed to the ability of photoexcited PW12 to trap electrons, particularly if the PW12 is supported. Moreover, the effect of water on the reactivity was also studied.

Graphitic carbon nitride assisted partial photocatalytic oxidation of 5-hydroxymethyl-2-furfural (HMF) in aqueous medium was investigated. Different carbon nitride precursors were considered, being melamine the one yielding the most efficient photocatalyst. The obtained 30% selectivity of HMF oxidation to 2,5-furandicarboxaldehyde (FDC) is higher than those reported up to now. A further thermal exfoliation of the g-C3N4 samples showed under artificial light irradiation both an enhanced photocatalytic activity in conversion of HMF, and selectivity (ca. 42–45%) to FDC. The performance of the catalysts increased when the experiments were carried out under real outdoor illumination, reaching 50% of selectivity versus FDC formation at 40% of HMF conversion. The utilization of radical scavengers revealed that O2− was the main reactive species responsible for HMF oxidation to FDC. The photocatalytic test carried out under natural solar irradiation resulted in higher yields of FDC compared to that observed in the laboratory UV irradiated set-up, thus demonstrating the applicability of the exfoliated carbon nitride material in real-life conditions., University of Oviedo gratefully acknowledges financial support from the MINECO (MAT2013-40950-R), FEDER-FICyT (GRUPIN14-060) and CTQ2014-52956-C3-1-R. IK thanks for the support the Ministry of Education and Science of the Russian Federation (grant No 16.2674.2014/K).

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

General considerations on the differences and similarities between heterogeneous photocatalysis and thermal catalysis are presented. Some research papers are reviewed where a reaction has been carried out in the presence of an inorganic material used both as catalyst and photocatalyst. The existing literature often compares catalytic reactions undertaken with the contemporaneous presence of radiation, showing only that photocatalytic reactions can occur under milder experimental conditions and at much lower temperatures. Nevertheless, differences in mechanistic aspects, conversions and selectivities between catalytic and photocatalytic reactions should also be highlighted. These are due to various reasons, relating to the effects of the interaction of light with the solid surface, adsorption-desorption of species involved in the (photo)reactions, and activation energy.

Catalytic and photocatalytic 2-propanol dehydration was carried out by using a supported Keggin heteropolyacid H3PW12O40 (PW12). Binary materials were prepared by impregnation and/or solvothermal treatment by using commercial supports: SiO2 (Mallinckrodt), TiO2 (Evonik P25) and multiwall carbon nanotubes (Sunnano) or home solvothermically prepared SiO2 and TiO2. All the materials have been characterized by X-ray diffraction (XRD), scanning electron microscopy observations (SEM) coupled with EDX microanalysis, specific surface area measurements, diffuse reflectance spectroscopy (DRS), FTIR and Raman spectroscopy. (Photo)catalytic 2-propanol dehydration was studied in gas-solid regime by using a continuous (photo)reactor working at atmospheric pressure and 80 °C. FTIR spectra of the gas-phase over the PW12-support composites, where 2-propanol had been previously adsorbed, were recorded. Propene and diisopropyl ether were the main reaction products. For the continuous photo-assisted runs the reactor was also illuminated with UV light. The apparent activation energy of 2-propanol catalytic and photocatalytic dehydration was determined in the range 60–120 °C. The irradiance increased significantly the dehydration reaction rate. Important differences were observed between the different supported materials. The Keggin heteropolyacid species played a key role both for the catalytic and the photo-assisted catalytic reactions; in fact, the acidity of the cluster accounts for the catalytic role, whereas both the acidity of the cluster and the oxidant ability of PW12 were responsible for the increase of the reaction rate of the photo-assisted catalytic reaction. Moreover, the photo-generated electrons on the solid semiconductor conduction band can account for a further increase of the reaction rate, when the heteropolyacid was supported on TiO2. Formation of a pseudo-liquid phase played an important role to determine the (photo)activity.

Hybrid materials have been prepared by impregnation of the heteropolyacid H 3 PW 12 O 40 on commercial TiO 2 . The polyoxometalates (POM) amount deposited was 15, 30, 50 and 70% with respect to the weight of the TiO 2 support. Moreover two samples containing a POM amount of 15, and 50% with respect to the weight of SiO 2 were also prepared for the sake of comparison. All prepared samples were efficient catalysts for the hydration of propene to 2-propanol in gas–solid regime at atmospheric pressure and at temperatures ranging between 50 and 85 °C. The study carried out on the hybrid TiO 2 based materials evidenced that, as far as the catalytic activity is concerned, exists an optimum in the amount of POM. Notably the contemporary presence of heat and UV light improved the activity of the POM/TiO 2 and POM/SiO 2 materials, although POM/TiO 2 showed better catalytic and catalytic photo-assisted activity than POM/SiO 2 . POM species played a key role in both the catalytic and photo-assisted catalytic reactions, due to its surface acidity and ability to form strong oxidant species under UV irradiation. The presence of TiO 2 under UV irradiation improved the heteropolyacid performance supplying conduction band electrons to the POM.

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

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

2-Propanol was photocatalytically oxidized in the presence of binary materials composed by mixtures of home-prepared active carbon and commercial TiO 2 or ZnO. Remarkable beneficial improvements of the photocatalytic activity were observed in the presence of activated carbon (AC). In particular the presence of AC along with TiO 2 in the binary materials enormously increased the photocatalytic ability of the bare semiconductor to completely oxidize the substrate, indicating a synergy between the semiconductor and AC. Probably, when AC was present in the binary materials, the majority of the substrate and of the intermediates were reversibly adsorbed onto the AC surface. Due to the presence of a contact interface between TiO 2 and AC, a continuous transfer of the species from the AC to the TiO 2 surface was possible. On the other hand, the presence of AC avoided the deactivation of TiO 2 that occurred instead for the bare semiconductor. The reaction rate in the presence of ZnO based materials was always lower with respect to that observed for the corresponding TiO 2 ones, although the presence of AC improved the photoactivity of bare semiconductor in this case also.

Commercial and home prepared TiO2 samples impregnated with tungstophosphoric acid (H3PW12O40) were used for the photo-assisted degradation of 2-propanol in gas–solid regime. The characterization results evidenced a good coverage of the polyoxometalate (POM) onto the surface of TiO2 along with a marginal effect of the presence of the POM on the specific surface area, morphology and cristallinity of the samples. Propene was the main intermediate product revealed in 2-propanol photocatalytic degradation by using as photocatalysts the samples containing the POM, whereas propanone was mainly obtained when the photocatalysts was bare TiO2, both commercial or home prepared. Acetaldehyde was also found as an intermediate product along with traces of isopropyl ether, mesityl oxide and isobutyl-methyl-ketone that were also detected as gaseous products in all the runs. Carbon dioxide and water were the ultimate oxidation products.

Photocatalytic degradation of 2-propanol was carried out as a probe reaction both in gas–solid and in liquid–solid systems in the presence of TiO2 both bare and impregnated with lanthanide (Sm, Gd, Ho) bis-phthalocyanines (LnPc2) used as sensitizers. Continuous and batch photo-reactors, irradiated with an equal flux of photons, were used in gas–solid and in liquid–solid systems, respectively. Propanone and acetaldehyde were the main intermediates found in both systems during 2-propanol oxidation, whereas carbon dioxide and water were the final oxidation products exclusively in the gas–solid regime. The photocatalysts exhibited significantly higher activity in the liquid–solid system than in the gas–solid one. Samples impregnated with the sensitizers were apparently more photoactive than bare TiO2. The highest photoactivity was shown by the 1.85 HoPc2–TiO2 sample.

The present work reports the preparation of samples based on Millennium PC-500 TiO 2 loaded with different amounts of tungstophosphoric acid (up to 30% in weight) and their characterisation by means of different physicochemical techniques: powder X-ray diffraction, N 2 adsorption–desorption at −196 °C, transmission electron microscopy, UV–vis and FT-IR spectroscopies and thermogravimetric analyses. The acidity of samples was evaluated by FT-IR using pyridine as probe molecule, and the catalysts activity was tested for the photodegradation of 4-nitrophenol in aqueous solution and for the photo-oxidation of propan-2-ol in vapour phase. The results show a noticeable improvement (8 and 2.5 times faster in the photodegradation rate of 4-nitrophenol and propan-2-ol, respectively), in both regimes for these specific substrates, when tungstophosphoric acid is dispersed over the oxide up to a certain amount (20% in weight). A partial leaching of the polyoxometalate was also detected in solution for samples loaded with the largest amounts on this compound.

Citrate–nitrate auto-combustion synthesis is used to prepare an iron, a cobalt and a cerium-perovskite. The influence of different synthesis conditions on the combustion process, phase composition, textural and morphological properties is studied in detail by X-ray diffraction, nitrogen adsorption and scanning electron microscopy. Results show that the combustion intensity increases from iron, to cerium, to cobalt-perovskite. Conversely, the combustion intensity decreases and thus the safety and the gain of the combustion process increase by using high fuel/oxidant ratios, low pH values or combustion reactors with high heat dispersion capacity. High fuel/oxidant ratios increase particle size and may enhance dopant segregation. Low citric acid/metal nitrates ratios may cause precipitation of the most insoluble compounds or segregation of the dopant. High citric acid/metal nitrates ratios increase the formation temperature of the perovskite-type structure. Low pH values are deleterious for the phase composition and/or for the morphology of the final product, although at high pH values dopant segregation may occur.

Liotta, L. F. Ousmane, M. Di Carlo, G. Pantaleo, G. Deganello, G. Marci, G. Retailleau, L. Giroir-Fendler, A.; Co3O4, CeO2 and Co3O4-CeO2 mixed oxides with Co/Ce nominal atomic ratio 0.1:5, prepared by co-precipitation method with sodium carbonate, were tested in the oxidation of propene under lean condition and the catalyst stability was checked by performing three consecutive heating-cooling cycles. Characterization of the textural properties were performed by surface area measurement BET, X-ray diffraction (XRD) and scanning electron microscopy (SEM) measurements. Among the Co3O4-CeO2 mixed oxides, Co3O4 (30 Wt%)-CeO2 (70 wt%) gives the best activity attaining full propene conversion at 250 degrees C. This sample is characterized by the presence of Co3O4 particles well dispersed and in good contact with ceria according to BET and XRD data and as evidenced by SEM micrographs. Oxygen temperature-programmed desorption (O-2-TPD) and C3H6-temperature-programmed reduction (C3H6-TPR) experiments were carried out in order to study the surface and bulk oxygen mobility and to correlate it to the activity. At temperature around 200 degrees C, O-2-TPD experiments showed the desorption of mobile surface oxygen species for the most active samples, Co3O4 and Co3O4 (30 wt%)-CeO2 (70 wt%). C3H6-TPR experiments for both of the oxides also evidenced a high reactivity at low temperature, especially, for Co3O4 (30 wt%)-CeO2 (70 wt%) giving at 345 degrees C an intense peak of CO2 formation. Conversely, the ceria sample showed by C3H6-TPR much less pronounced oxygen bulk mobility, starting to react with propene above 500 degrees C and forming only CO. In this case, the catalytic activity of ceria was explained in terms of formation of surface oxygen vacancies which are relevant to the propene oxidation in presence of gaseous oxygen. (c) 2008 Elsevier B.V. All rights reserved.

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

The photoassisted oxidative transformation of the highly recalcitrant cyanuric acid was examined in the liquid−solid regime at pH 3 and natural pH 7.5 under UV irradiation in oxygen- and ozone-saturated ZnO suspensions using ZnO as a photomediator. Loss of cyanuric acid was assayed by HPLC UV absorption spectroscopy, whereas intermediates and final products were determined by HPLC ion chromatography (IC), by MS techniques using an electrospray ionization mass spectrometer operated in the negative-ion mode, and by FT-IR spectroscopy. Final reaction products were CO2 gas and NO3- ions. The measure of nitrate in solution quantified the degree of mineralization of the substrate; its concentration in solution was lower than indicated by the loss of cyanuric acid owing to adsorption of the latter to the ZnO surface. Some degree of corrosion of ZnO occurred as evidenced by the quantity of Zn2+ present in acidic and near-neutral aqueous media before and during the photoassisted process. The possible site(s) and m...

Commercial and home prepared TiO2 samples were functionalized with a commercial Keggin heteropolyacid (HPA) H 3PW12O 40 (PW12) or with a hydrothermally home prepared K 7PW11O 39 salt (PW11). All the materials were characterized by specific surface area measurements (BET), XRD analyses, Raman, DRS along with SEM observations and they have been used for glucose photocatalytic conversion in an aqueous suspension. Different reaction extents and distribution of intermediate oxidation products were observed depending on the photocatalyst. Gluconic acid, arabinose, erythrose and formic acid were observed as oxidation products when bare TiO2 or HPA/TiO2 composite materials were used. Glucose isomerization to form fructose was also observed and in some runs traces of glucaric acid and glyceraldehyde were also found. The carbon mass balance was accomplished in the presence of the commercial Evonik P25 TiO2 powder and the composites where TiO2 was present, whereas the presence of the solvothermically prepared TiO2 gave rise to a carbon unbalance, due to strong adsorption of the products on the photocatalyst surface. No reactivity was observed in the presence of PW12 alone while PW11 induced only isomerization of the glucose.

(Photo)catalytic propene hydration to 2-propanol and glycerol dehydration to acrolein were carried out by using Keggin heteropolyacids (HPAs) supported on TiO 2 . Binary materials have been prepared by impregnation of H 3 PW 12 O 40 , H 3 PMo 12 O 40 and H 4 SiW 12 O 40 , on TiO 2 Evonik P25. Moreover, a binary material consisting of H 4 SiW 12 O 40 and TiO 2 was prepared via a hydrothermal treatment and tested for the same reactions. All the materials were characterized by X-ray diffraction (XRD), scanning electron microscopy observations (SEM) coupled with energy dispersive X-ray (EDX) measurements, diffuse reflectance spectroscopy (DRS), Raman spectroscopy and Fourier transform infrared spectroscopy (FTIR). The supported Keggin HPA species played a key role both for the catalytic and for the photo-assisted catalytic reactions due to their strong acidity and ability to form strong oxidant species under UV irradiation.

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.

Temperature-programmed reduction (TPR) and temperature-programmed oxidation (TPO) have been used to study the various cobalt species formed in a cobalt catalyst (Co 1 wt.%) supported on alumina-baria, with composition Al2O3(80 wt.%)–BaO (20 wt.%). The catalyst was synthesized by incipient-wetness impregnation of the support with a water solution of cobalt acetylacetonate and calcined at 550 °C for 5 h. In order to investigate the structure and morphology of the sample, XRD, BET and SEM analyses were performed. Depending on the temperature and nature of pre-treatment (reductive or oxidative) different Co species (Co3O4, Co3+, surface Co2+, CoAl2O4) were formed. Activity tests in the reduction of NO by CO were carried out in order to investigate the effectiveness of the catalyst depending on the redox pre-treatment. Highly dispersed Co3O4 particles, formed after a TPR up to 1100 °C and successive TPO up to 550 °C are active for the NO reduction at low temperature, N2O being the major product at 250 °C, while N2 formation was favored at temperature higher than 400 °C. The as prepared sample, calcined at 550 °C for 5 h, exhibits significant activity only at temperature > 400 °C, giving selective formation of N2. The nature of the active species in the supported catalyst was confirmed by studying the CO + NO reaction and NO decomposition over Co3O4 and CoO oxides as reference materials. On Co3O4 the NO reduction occurs with different selectivity to N2O/N2, depending on the reaction temperature: at low temperature only N2O was detected, whereas at temperature >350 °C also N2 formation was observed. Then at temperature ≥450 °C only the reaction NO→N2 takes place. Over CoO the reaction starts at ∼400 °C and N2 is the only nitrogen product detected in the whole range of temperature investigated. Hundred percent of NO conversion into N2 is reached at 600 °C.

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.

Transition metal loaded TiO 2 powders were characterised and tested for the photodegradation of some organic acids. Both Lewis and Bronsted surface acid sites were present in the samples containing large amounts of Mo, V and W. The Bronsted sites are associated to the presence of the transition metals as they do not exist in the unloaded support, and in particular to the presence of these metals in high oxidation states. The trend of the pzc values of the various powders matches rather well both with the surface acidity of the samples experimentally determined by NH 3 adsorption and with a scale of acidity/basicity for bulk binary oxides. XPS investigation indicates that only the presence of Cu(II) is able to modify the TiO 2 valence band spectrum. The photodegradation results have confirmed that the presence of transition metal ions generally reduces the photocatalytic activity of TiO 2 . Surface acidity addresses the reactivity for the degradation of methanoic and benzoic acid: the more basic the surface of the powders the higher the rate of substrate disappearance. No relation with the acidity has been found in the case of ethanoic acid.

Ceria-zirconia mixed oxides of nominal composition Ce0.6Zr0.4O2 were prepared by sol-gel method. The structural and morphological modifications of these materials due to calcination and redox treatments up to 1000°C were studied by X-ray diffraction (XRD) and Rietveld refinements, specific surface area measurements (BET), oxygen storage capacity (OSC), TEM and SEM analyses. The materials maintain high OSC after several hours of treatments at 1000°C in oxidizing and reducing atmosphere, showing good resistance to the thermal ageing. An improvement of the OSC is manifested after repetitive redox cycles, even though textural characterization shows that reduction/oxidation processes induce sintering of the crystallites.

Some probe catalytic photooxidation reactions with aliphatic and aromatic organic compounds having different acid strengths, i.e. methanoic acid, ethanoic acid, benzoic acid and 4-nitrophenol, were carried out in aqueous systems by using polycrystalline TiO2 powders doped with various transition metal ions (Co, Cr, Cu, Fe, Mo, V and W). The Co-doped powder showed to be more photoactive than the bare TiO2 for methanoic acid degradation while the behaviour of TiO2/Cu and TiO2/Fe was similar to that of the support. TiO2/W was the most efficient sample for the photodegradation of benzoic acid and 4-nitrophenol, TiO2 the most active powder for ethanoic acid. A tentative explanation is provided by taking into account: (i) the dissociation constants (Ka) of the different acids used as substrates; (ii) their aliphatic or aromatic nature; (iii) the points of zero charge (PZC) of the photocatalysts; (iv) their relative rate constants for photoelectron–hole recombination (kr) determined by femtosecond pump-probe diffuse reflectance spectroscopy.

Two probe photocatalytic reactions, i.e. ethanoic acid and 4-nitrophenol photooxidation, were carried out in different experimental conditions by using suspensions of transition metal (Co, Cr, Cu, Fe, Mo, V and W) doped polycrystalline TiO2 powders in aqueous systems. A beneficial influence of the presence of metal species was observed only with the samples containing copper and tungsten. In particular, theTiO2/Cu powders showed to be more photoactive of bareTiO2for the ethanoic acid oxidation while theTiO2/W samples were more efficient for 4-nitrophenol degradation. A tentative interpretation is provided on the basis of the values of the points of zero charge of the powders and of the rate constants of recombination of photogenerated electrons and holes, determined by femtosecond pump-probe diffuse reflectance spectroscopy (PP-DRS).

A set of TiO2 and Pt-TiO2 polycrystalline samples were prepared by sol-gel method hydrolysing a modified alkoxide titanium precursors under acidic conditions. The Pt-TiO2 samples gave an homogeneous nanometric metal dispersion after drying heat treatment forming platinum particles in the range 2–4 nm. All the samples have been characterised using several techniques, namely thermogravimetric analysis, gas-chromatography, mass spectrometry, thermogravimetric analysis combined with mass spectrometry or with gas chromatography/mass spectrometry, X-ray diffraction coupled with a Rietveld refinement procedure, X-ray photoelectron spectroscopy and determination of specific surface area. Moreover, the samples have been employed as catalysts for 4-nitrophenol photodegradation in aqueous suspension used as a “probe” reaction. Characterisation results indicate that the thermal and chemical treatments of the catalysts influenced the photocatalytic activity. In the Pt-TiO2 samples both Pt(0) and Pt(II) species are present in the catalyst particles and the most abundant phase is anatase for all of the samples. Doping with Pt beneficially influences the photo-oxidant properties of TiO2 while the presence of organic residual species on the surface, deriving from the preparation procedure of the catalyst particles interferes negatively in the kinetics of the photocatalytic process.

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.

A series of polycrystalline WOx/TiO2 samples were prepared by means of a conventional impregnation method. The samples were characterized by means of X-ray diffraction, Vis-UV diffuse reflectance and Raman spectroscopies, nitrogen adsorption at 77 K for determining specific surface areas and surface texture, scanning electron microscopy, and FT-IR monitoring of pyridine adsorption for measuring the surface acidity. Catalytic activity of the samples has been assessed by carrying out as a ``probe'' reaction the photodegradation of 4- nitrophenol in aqueous medium. The results obtained indicate that incorporation of tungsten on titania leads to formation of different surface species, depending on the tungsten loading. Tungsta microcrystals were detected by X-ray diffraction when the nominal molar W/Ti ratio reached a value of 8.0%. FT-IR investigation indicated that the presence of tungsten induces formation of Bronsted and Lewis surface acid sites. The photoactivity results confirm the beneficial effect of tungsten in TiO2 for 4-nitrophenol photodegradation in aqueous medium. The reaction rates are higher than those reported in literature for another set of samples and maximum photoactivity was achieved for a sample containing 1.96 moles of W per 100 moles of Ti.

A set of tungsten oxide/TiO2 polycrystalline samples (W/Ti) prepared by the sol–gel method has been characterised using several techniques, namely thermogravimetric analysis, gas-chromatography, mass spectrometry, thermogravimetric analysis combined with mass spectrometry or with gas chromatography/mass spectrometry, X-ray diffraction, X-ray photoelectron spectroscopy, determination of specific surface area, scanning electron microscopy, Fourier-transform infrared spectroscopy and monitorisation of pyridine adsorption for surface acidity. Moreover the samples have been empolyed as catalysts for 4-nitrophenol photodegradation in aqueous suspensions used as a ‘probe’ reaction. Characterisation results indicate that the surface of the W/Ti particles is enriched with homogeneously dispersed tungsten as well as microcrystalline or amorphous species. Maximum photoactivity for 4-nitrophenol photodegradation was achieved for a sample containing 1.7 mol W per 100 mol Ti.

The photocatalytic degradation of Monuron (3-(4-chlorophenyl)-1-1-dimethylurea) in aqueous TiO2 dispersions irradiated in the near-UV region has been investigated by using a Pyrex batch photoreactor. The Monuron and total organic carbon concentrations were determined; several reaction intermediates were also identified using HPLC. The influence on the degradation kinetics of the initial Monuron concentration, of the TiO2 concentration, and of the initial pH of dispersion was studied. A pseudo-first order kinetics of Langmuir-Hinshelwood type was found to satisfactorily describe the Monuron degradation. The mineralization of the pollutant was virtually complete in the 3–9 pH range while at pH = 1.0 and 11.0 only a partial mineralization was reached even after a long irradiation time. The quantum yield values of Monuron degradation were determined by measuring the photon flow transmitted by the dispersion and applying a macroscopic photon balance on the photoreactor. The quantum yields were found to increase by increasing the pH of the dispersion.

Ceria nanosized oxides with high surface area were synthesized by means of a templating approach, using a porous silica xerogel with surface area as high as 718 m2/g. After impregnation of the silica template with the cerium salt solution and further calcination at 600 °C, the final ceria oxide was recovered by dissolving the silica framework in NaOH solution. The effect of cerium counteranion, nitrate or chloride, on the textural and reduction properties of the ceria oxide was examined. Characterizations by BET and pore size distribution, XRD, TPR and SEM/EDX techniques were performed. The silica xerogel templated approach resulted in the preparation of ceria with surface area of 205 m2/g and very small particle size (∼5 nm), when cerium chloride precursor was used. An enhanced reducibility, at temperature

Both commercial and home prepared TiO2 samples impregnated with tungstophosphoric acid (H3PW12O40) were prepared and used for the photo-assisted degradation of 2-propanol in gas–solid regime. The characterization results evidenced a good coverage of the polyoxometalate (POM) onto the surface of both types of TiO2 samples along with a marginal effect of the presence of ethanol or HCl during the POM impregnation step on the specific surface area, porosity, morphology, crystallinity and acidity of the samples. Propene was the main intermediate product found in 2-propanol photocatalytic degradation by using the samples containing POM as the photocatalyst, whereas propanone was mainly obtained when the photocatalyst was bare TiO2. Acetaldehyde was also an intermediate product and its amount was always significantly smaller with respect to propanone and propene (when formed). Carbon dioxide and water were the ultimate oxidation products. The selectivity to propene has been attributed to the acidity of the POM supported samples.

Photocatalytic degradation of acetonitrile and toluene was carried out both in gas-solid and in liquid-solid regimes by using commercialTiO2samples (Merck and Degussa P25). The investigation was mainly aimed to study the influence of water present in the reaction environment on the mechanism and degradation rate of two probe molecules. In gas-solid regime, the reacting mixture consisted of toluene or acetonitrile, oxygen, nitrogen, and water vapour. The main degradation product of toluene wasCO2with small amounts of benzaldehyde. In the presence of water vapour, the activity ofTiO2Merck remained stable but greatly decreased if water was absent.TiO2Degussa P25 continuously deactivated, even in the presence of water vapour. With both catalysts, the photodegradation products of acetonitrile wereCO2and HCN; the activity was stable and was independent of the presence of water vapour in the reacting mixture. The production of HCN represents a drawback of acetonitrile photocatalytic degradation but the elimination of HCN is not actually a problem. In liquid-solid regime, the main intermediates of toluene photodegradation werep-cresol and benzaldehyde; traces of pyrogallol and benzyl alcohol were also found. Benzoic acid, hydroquinone, and trans, trans muconic acid were detected only whenTiO2Merck was used. The photodegradation products of acetonitrile were cyanide, cyanate, formate, nitrate, and carbonate ions.

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

This work reports the preparation of nanostructured polycrystalline TiO2 photocatalysts obtained by hydrolysis of TiCl4 in very mild conditions. Several samples were prepared as suspensions or colloidal dispersions by using TiCl4/H2O volume ratios ranging between 1:1 and 1:100. The samples were characterised by X-ray diffraction analysis, specific surface area determination, diffuse reflectance spectroscopy and scanning electron microscopy. 4-Nitrophenol photodegradation was used as probe reaction to test the photoactivity of the catalysts. Some samples revealed a photoactivity higher than that of Degussa P25 in similar experimental conditions and the most photoactive one was that prepared by using the TiCl 4/H2O volume ratio equal to 1:50. A dialysis process was performed in some cases to reduce the amount of chloride ions present in the system. The presence of Cl- ions appeared to be dramatically detrimental for Degussa P25 while a lower influence was found for the home prepared samples.

Aqueous solutions of tetracycline, lincomycin and ranitidine were irradiated with UV light in homogeneous and heterogeneous systems. Two commercial polycrystalline TiO2 powders (Degussa P25 and Merck) were used as photocatalysts. After 5A h, an appreciable photolytic degradation of tetracycline and ranitidine was observed while the degradation of lincomycin was noticeably lower. As far as the mineralization is concerned, a small decrease of the TOC values was measured in the case of tetracycline whereas negligible variations were found for lincomycin or ranitidine. The presence of the photocatalysts greatly enhanced the degradation rates of the drugs with respect to those observed during the homogeneous experiments. The Langmuir-Hinshelwood kinetic model adequately describes the experimental results and both the pseudo-first order kinetic constants of the reactions and the adsorption constants were calculated. Merck TiO2 was more active than P25 Degussa for the photodegradation of tetracycline and ranitidine, whereas both photocatalysts showed similar performances for lincomycin. In the presence of TiO2 Degussa P25, tetracycline was almost completely mineralized, but the reduction of the initial TOC was ca. 60% in the case of lincomycin and ranitidine. A less significant mineralization was observed by using Merck TiO2.

Various preparations of nanostructured TiO2 starting from Ti(iso-OC3H7)4 or TiCl4 are reported. The samples were characterized by X-ray diffractometry, specific surface area and porosity determinations, scanning and transmission electron microscopy, and diffuse reflectance spectroscopy. 4-Nitrophenol photodegradation in aqueous medium was employed as a probe reaction to test the photoactivity of the catalysts. The photoactivity of some samples derived from Ti(iso-OC3H7)4 was found comparable with that of commercial powders. Calcination after the hydrolysis process was necessary to achieve crystallization of the particles before using them as photocatalysts for the reaction studied. The samples deriving from TiCl 4 were the most photoactive among the home-prepared catalysts, and neither filtration nor calcination was needed to obtain a highly photoactive anatase phase.

Two Al 2 O 3 (24 wt%)–La 2 O 3 (76 wt%) supported Co–La oxides with Co loading 4 wt% and different La content (1 and 9 wt%) were prepared by co-impregnation of the support, the aluminum–lanthanum oxide, with cobalt and lanthanum nitrates in aqueous solution and successive calcination at 800 °C for 4 h. The alumina–lanthana was synthesized by the sol–gel method. The samples were characterized by X-ray diffraction (XRD) and Rietveld refinement in order to identify the crystalline phases and their relative weight. H 2 -TPR (Temperature Programmed Reduction) experiments were recorded with the aim to identify the different Co phases present. Co 3 O 4 and LaCoO 3 were formed for La loading of 1%, whereas at higher La loading (9%) LaCoO 3 and La 2 O 3 oxide prevailed. In both catalysts LaAlO 3 phase was also detected. As observed by BET and SEM characterizations, the morphology of the two catalysts was somewhat affected by La:Co atomic ratio and differed dramatically from those of the reference bulk oxides, Co 3 O 4 and the mixed phase LaCoO 3 /La 2 O 3 . Activity tests in C 3 H 6 and CH 4 combustion were carried out in order to discriminate the catalytic properties of different phases formed (Co 3 O 4 , LaCoO 3 , La 2 O 3 , LaAlO 3 ).

The photocatalytic degradation of acetonitrile was carried out in liquid–solid regime in a batch reactor by using two types of commercial TiO 2 powders (Merck and Degussa P25) as photocatalysts. The concentration of acetonitrile and non-purgeable organic carbon (NPOC) were monitored. The initial rate of acetonitrile conversion was found higher on TiO 2 Merck than on TiO 2 P25. FT-IR spectroscopy was used to investigate the molecular features of the adsorption and photo-oxidation of acetonitrile on the two TiO 2 powders in a fully surface hydrated form. Acetonitrile was found adsorbed on Ti 4+ surface ions and hydroxyl groups for both types of TiO 2 . This interaction appeared fully reversible in the case of the Merck photocatalyst, whereas acetonitrile was more strongly stabilized on Ti 4+ ions of TiO 2 P25. Furthermore, the adsorption of CD 3 CN⋯Ti 4+ on this type of photocatalyst resulted in the formation of acetamide-like species, because of the presence of nucleophilic surface O 2− and hydroxyl groups. The formation of these species, strongly bound to the TiO 2 surface and recalcitrant to the photo-oxidation, could result in the poisoning of a part of the photocatalytic sites of TiO 2 P25, accounting for its lower initial acetonitrile conversion rate.

Heteropolyacids (HPAs) that are often used as heteropolyanions are cheap and stable compounds that have been extensively used as acid and oxidation catalysts as a result of their strong Brønsted acidity and ability to undergo multielectron-transfer reactions. HPAs, which are very soluble in water and polar solvents, have been also used as homogeneous photocatalysts for the oxidation of organic substrates in the presence of oxygen, but their use in heterogeneous systems is by far desirable. Dispersing HPAs onto solid supports with high surface area is useful to increase their specific surface area and hence (photo)catalytic activity. Moreover, owing to the high energy gap between the HOMO and LUMO positions of the HPAs, these compounds are activated only by UV light. Consequently, only less than 5 % of the solar light can be used in photocatalytic reactions, which restricts the practical application of HPAs. This microreview is oriented to describe the reported literature on the use of HPA-based materials as heterogeneous photocatalysts for environmental purposes, that is, for the complete or partial oxidation or reduction of organic molecules.

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

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