Heterogeneous photo-assisted catalytic hydration/dehydration reactions based on Keggin and Wells-Dawson type heteropolytungstates

Polyoxometalates (POMs) are a wide class of metal-oxygen clusters that can be applied in acid and oxidation catalysis, medicine, electrochemistry, materials design, or models for self-assembling nanoscale systems as long as green and cheap photocatalysts. Heteropolyacids (HPAs) are a POM subclass extensively used as homogeneous photocatalysts for the oxidation of organic substrates. Dispersing HPAs onto solid supports with a high surface area increases their specific surface area and hence (photo)catalytic activity. This chapter reports the use of selected HPAs, heteropolytungstates, immobilized on different supports as heterogeneous photocatalysts.

Iron oxide-based magnetic photocatalysts: Recent developments, challenges, and environmental applications

Abstract Magnetic separation of the solid photocatalyst from the reacting suspension has received great interest in recent research because it offers a suitable way for removing and recycling the heterogeneous photocatalytic material particles preventing the agglomeration and sedimentation during and after their use. The use of iron oxides such as heterogeneous photocatalysts is an appropriate choice to obtain a suitable photocatalyst easily separable from the fluid. This chapter presents a detailed investigation of iron oxide-based magnetic photocatalysts (IOMPs). We will discuss the required conditions for the synthesis of these photocatalysts, followed by their applications for the remov…

Comparison between catalytic and catalytic photo-assisted propene hydration by using supported heteropolyacid

Abstract 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 optimu…

Comparison between preparative methodologies of nanostructured carbon nitride and their use as selective photocatalysts in water suspension

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 nit…

Photoactivity of shape-controlled TiO2 in gas-solid regime under solar irradiation

Abstract Differently shape-controlled anatase TiO2 materials were tested as photocatalysts under both simulated and natural solar irradiation. Their photocatalytic activity in 2-propanol and propene partial oxidation and in the complete mineralization of acetaldehyde appears to increase with decreasing the shape control of the TiO2 material. This insight seems to be related to the residual presence of the templating species (fluoride anions) employed during the preparation of the shape-controlled TiO2 materials. In fact, the calcination of the powders, leading to levelling of the fluoride ions content, but also to a remarkable surface area decrease, gave rise to an increase of photocatalyti…

Photocatalytic oxidation of toluene on irradiated TiO2: comparison of degradation performance in humidified air, in water and in water containing a zwitterionic surfactant

Photocatalytic degradation of toluene was carried out both in gas–solid and in liquid–solid regime by using polycrystalline samples of TiO2 Merck and TiO2 Degussa P25. For the gas–solid regime two types of continuous photoreactor were used, a fixed bed one of cylindrical shape and a Carberry type photoreactor, both irradiated by near-UV light. The inlet reacting mixture consisted of air containing toluene and water vapours. The influence of the gas flow rate and the presence of water vapour on the photocatalytic process was investigated. CO2 and benzaldehyde were the toluene degradation products detected in the gas phase by using TiO2 Merck. In the presence of water vapour this catalyst exh…

Heterogeneous Photocatalysis for Selective Formation of High-Value-Added Molecules: Some Chemical and Engineering Aspects

This review deals with the parameters that influence heterogeneous photocatalysis (PC) for selective synthesis of high-value chemicals by itself or in combination with other technologies. In particular, the parameters related to the photocatalysts, such as crystallinity degree, type of polymorph, surface acid-base properties, exposure of particular crystalline facets, coupling of different semiconductors, position of the valence and conduction band edge, addition of doping agents, and those related to the reaction system, such as setup configuration and reactor geometry, type of solvent, type and amount of photocatalyst, affecting the selectivity toward specific products are described and d…

Azo-Dyes Photocatalytic Degradation in Aqueous Suspension of TiO2 Under Solar Irradiation

Abstract The photodegradation of two common and very stable azo-dyes, i.e. methyl-orange (C14H14N3SO3Na) and orange II (C16H11N2SO4Na), is reported. The photocatalytic oxidation was carried out in aqueous suspensions of polycrystalline TiO2 irradiated by sunlight. Compound parabolic collectors, installed at the “Plataforma Solar de Almeria” (PSA, Spain) were used as the photoreactors and two identical reacting systems allowed to perform photoreactivity runs for the two dyes at the same time and under the same irradiation conditions. The disappearance of colour and substrates together with the abatement of total organic carbon content was monitored. The main sulfonate-containing intermediate…

Synthesis of ZnO–Ag2CO3–Fe3O4@rGO core–shell structure: magnetically separable photocatalyst for degradation of MB using the Box–Behnken design

In this work, a simple microwave method was utilized to prepare ZnO sheet linked with Fe3O4@rGO core–shell and of Ag2CO3 through formation of the quadri-photocatalytic with high activity. The microstructure, morphology, spectroscopic, and magnetic characteristics of the prepared samples were assessed using XRD, SEM, PL, TEM, FT-IR, DLS, and VSM analysis. The photocatalytic activity of the material was evaluated for photodegradation of methylene blue dye under the UV and visible light with home-made photoreactor. The response surface method in a Box–Behnken design was utilized to design the experiments. The parameters affecting the efficiency of the degradation including, pH (5–9), photocata…

Supported Poly(Ionic Liquid)-Heteropolyacid Based Materials for Heterogeneous Catalytic Fructose Dehydration in Aqueous Medium

Two sets of four different supported catalyst materials were prepared. One set was obtained by polymerization of a bis-vinylimidazolium salt, which formed a poly(ionic liquid) coating on SiO2, TiO2, boron nitride BN, and carbon nitride C3N4. The other set was, instead, obtained by immobilizing Keggin heteropolyacid H3PW12O40 onto poly-imidazolium functionalized materials. All the catalysts, including the bare supports, were subjected to physical and chemical characterization by XRD, SEM, Specific Surface Area and pore size measurements, TGA, FTIR, and acidity-basicity measurements. The catalytic activity of the materials was tested versus the fructose dehydration in water solution at two di…

EPR investigations of polymeric and H2O2 -modified C3N4 -based photocatalysts

The C3N4 -based nanopowders prepared by thermal condensation of melamine (MCN) with subsequent thermal etching (MCN-TE) and H2O2 -treatment were investigated by Q- and X-band EPR spectroscopy in dark and upon in situ UVA or visible-light exposure. Lorentzian signal at g = 2.003, more pronounced in the case of the thermally etched material, dominates EPR spectra of MCN and MCN-TE. More complex spectra were found for H2O2 -treated photocatalysts revealing the presence of signals attributed to the radicals produced via H2O2 interaction with C/N sites in the C3N4 polymeric network. The X-band spectra monitored upon in situ irradiation of the C3N4 -based photocatalysts evidenced the intensity gr…

Photocatalytic degradation of organic compounds in aqueous systems by transition metal doped polycrystalline TiO2

Abstract 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 p…

Heterogeneous photocatalytic materials for sustainable formation of high-value chemicals in green solvents

Abstract The most investigated materials used as heterogeneous photocatalysts for the formation of high-value chemicals under mild experimental conditions are presented in this survey. Only papers reporting reactions carried out in harmless solvents such as water, the green solvent par excellence, are reported. Metal oxides have been used often, but carbon-based materials such as carbon nitride and graphene, metal nanoparticles, sulphides and selenides also have received a great attention mainly due to their good performances both in partial oxidations and reductions. The results presented indicate that an appropriate choice of the photocatalytic material is the main problem to be faced to …

Preparation in mild conditions of photocatalytically active nanostructured TiO2 rutile

Abstract 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.

Photocatalytic CO<inf>2</inf> Valorization by Using Ti<inf>O2</inf>, ZrO2 and Graphitic Based Semiconductors

In this century, a broad scientific interest has been devoted to fulfill sustainable industrial processes and climatic change remediation. In this prospective, various green technologies have been studied to valorize CO 2• The aim of this research is the CO 2 reduction in presence of water by using the photocatalytic technology with nanomaterials as the photocatalysts. The present work overviews the main outcomes obtained by using graphitic and oxide based photocatalysts both in gas/solid and liquid/solid batch reactors under simulated solar light. In all gas/solid regime tests the major products detected were methane, carbon monoxide, and acetaldehyde.

ZrO2 Based materials as photocatalysts for 2-propanol oxidation by using UV and solar light irradiation and tests for CO2 reduction

Abstract Bare ZrO2, Ce doped ZrO2 and Er doped ZrO2 samples have been prepared by a hydrothermal process and have been used as photocatalysts for 2-propanol oxidation reaction in gas solid regime. Moreover, some preliminary tests have been carried out for CO2 reduction. The samples were physico-chemically characterized and both bare and doped ZrO2 based materials resulted active for oxidation and reduction reactions by using UV and solar irradiation. The reactivity results have been correlated with the compositional, structural and morphological features of the photocatalysts.

Surface characterisation of metal ions loaded TiO2 photocatalysts: structure–activity relationship

Abstract 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 p…

Keggin heteropolyacid H3PW12O40 supported on different oxides for catalytic and catalytic photo-assisted propene hydration

Catalytic and catalytic photo-assisted hydration of propene to form 2-propanol in gas–solid regime at atmospheric pressure and 85 1C were carried out by using a heteropolyacid (POM) supported on different oxides. Binary materials were prepared by impregnation of H3PW12O40 on different commercial and home prepared supports (TiO2, SiO2, WO3, ZrO2, ZnO, Al2O3). Some of the composites were active both for catalytic and catalytic photo-assisted reactions. The Keggin type POM was completely and partially degraded, when supported on ZnO and Al2O3, respectively, and these binary solids always resulted as inactive for both catalytic and catalytic photo-assisted reactions. The supported Keggin POM sp…

Selective photocatalytic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxaldehyde by polymeric carbon nitride-hydrogen peroxide adduct

Abstract Polymeric carbon nitride-hydrogen peroxide adduct (PCN-H2O2) has been prepared, thoroughly characterised and its application for selective photocatalytic conversion of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxaldehyde (FDC) in aqueous suspension has been studied. The PCN-H2O2 adduct is stable in aqueous suspension under UV and solar irradiation up to 100 °C. It is also stable up to 200 °C if heated in air, while at temperatures close to 300 °C its decomposition takes place. Based on the obtained characterisation data it has been proposed that H2O2 attaches to the non-polymerised carbon nitride species and to the heptazine nitrogen atoms, thus producing strong hydrogen bond…

Photocatalytic degradation of 4-Nitrophenol by g-C3N4-MCy: Mechanism study and kinetic modeling

Abstract A graphitic carbon nitride (g-C3N4-MCy) photocatalyst was prepared by thermal condensation of melamine and cyanuric acid with equal proportions. The photocatalyst was characterized by Fourier transform infrared spectroscopy (FTIR), Specific surface area (SSA), X-ray diffraction (XRD), Field Emission Scanning Electron Microscope (FESEM), Transmission electron microscope (TEM), and DRS–UV–Vis spectroscopic methods. We studied the photo-degradation kinetics of 4-nitrophenol using a g-C3N4-MCy. Four parameters were applied including initial concentration of 4-nitrophenol, amount of catalyst, dissolved oxygen content, and photon flux. The reaction rate constant was shown to be correlate…

Photocatalytic oxidation of gaseous toluene on polycrystalline TiO2: FT-IR investigation of surface reactivity of different types of catalysts

Commercial TiO 2 Merck and TiO 2 Degussa P25 powders were employed as the catalysts for the photo-oxidation of toluene. By using TiO 2 Merck benzaldehyde was found in gas phase as the main product of the toluene partial oxidation. After an initial transient period, this catalyst exhibited a high stability in the presence of water vapour in the gaseous mixture, whereas the photoproduction of benzaldehyde sharply decreases after removal of H 2 O from the feed IR spectra of the used catalyst revealed that in the absence of water vapour benzaldehyde is molecularly held on the catalyst surface. This feature was confirmed by co-adsorbing benzaldehyde and water on the fresh catalyst. By contrast, …

Photocatalytic and Catalytic Reactions in Gas–Solid and in Liquid–Solid Systems

Abstract Heterogeneous photocatalytic and thermal-catalytic reactions are here presented focusing the differences and similarities between the two processes. When possible, the comparison was made for the same chemical reaction in the presence of an inorganic material playing the role of both catalyst or/and photocatalyst. Several examples are presented where a catalytic reaction can occur at milder experimental conditions and, particularly, at lower temperature when the system is also irradiated by UV and/or visible light. The differences in mechanistic aspects, conversions, and selectivities between catalytic and photocatalytic reactions will be also considered because these occurrences a…

Photodegradation of lincomycin in aqueous solution

Aqueous solutions of lincomycin were irradiated with UV light in homogeneous and heterogeneous systems. Lincomycin disappeared in both systems but the presence ofTiO2noticeably accelerated the degradation of the antibiotic in comparison with direct photolysis. The rate of decomposition was dependent on the concentration of lincomycin and followed a pseudo-first-order kinetics. Photolysis involved only the oxidation of lincomycin without mineralization. Differently, the treatment withTiO2and UV light resulted in a complete mineralization of the antibiotic. The degradation pathways involved S- and N-demethylation and propyldealkylation. The mineralization of the molecule led to the formation …

Preparation, Characterization and Photocatalytic Activity of TiO2 Impregnated with the Heteropolyacid H3PW12O40: Photo-assisted Degradation of 2-propanol in Gas-Solid Regime

Abstract 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 o…

Carbon nitride as photocatalyst in organic selective transformations

Abstract Graphitic carbon nitride (g-C3N4) is a metal-free conjugated polymer which has become a new research hotspot in photocatalysis. It can be used for solar energy exploitation like in solar energy organic synthesis, one of the most new and appealing green applications of heterogeneous photocatalysis. This chapter resumes the state-of-the-art and progresses in the application of heterogeneous visible light photocatalysis in organic selective transformations by using C3N4 as photocatalyst.

CO2 to Liquid Fuels: Photocatalytic Conversion in a Continuous Membrane Reactor

The photocatalytic reduction of CO, into value-added chemicals using sunlight is a promising approach to promote energy-bearing products, mitigating the adverse effects of anthropogenic CO2 emissions. In this work, exfoliated C3N4 was incorporated into Nafion matrix and used in a continuous photocatalytic reactor for converting CO2 into liquid fuels. Comprehensive structural and morphological diffuse reflectance spectroscopy (DRS), FT-IR, ATR-IR, and SEM measurements were performed for C3N4-loaded Nafion membrane and then compared with those of a Nafion membrane without any catalyst. The synergic effect of C3N4 organic catalyst embedded in a Nafion dense matrix and a continuous operating mo…

Heteropolyacid-Based Heterogeneous Photocatalysts for Environmental Application

Polyoxometalates (POMs) are a wide class of discrete nanosized transition metal–oxygen clusters. The synthesis of POMs has received great interest not only because they present intriguing architectures but also because they have potential applications in catalysis, medicine, electrochemistry, materials design or models for self-assembling nanoscale systems. Recently, POMs have also been studied as green and cheap photocatalysts. The potentialities of POMs are attributed to their unique structural features; indeed, POMs are photostable and non-toxic, have oxygen-rich surfaces and excellent redox properties and possess photochemical characteristics similar to those of the semiconductor photoc…

Carbon Nitride-Based Catalysts for High Pressure CO2 Photoreduction

In the current research, the productivity of CO2 photoreduction has been boosted by performing the reaction in an innovative photocatalytic reactor, which allows for operation up to 20 bar. A set of photocatalysts were used, including three types of pristine TiO2, i.e., one commercially prepared (Evonik P25), one home-prepared by flame spray pyrolysis (FSP), and one obtained by the hydrolysis of TiCl4 (TiO2exCl), a bare thermo-exfoliated carbon nitride (C3N4-TE), and binary materials composed of TiO2 and C3N4-TE. The photoreduction was carried out in water at pH 14 and in the presence of Na2SO3 as a hole scavenger. Hydrogen and very small amounts of CO were detected in the head space of the…

Photoactivity of Nanostructured TiO2 Catalysts in Aqueous System and their Surface Acid-Base, Bulk and Textural Properties

This work reports on the characterisation and determintion of the photocatalytic activity of some TiO2 catalysts prepared using TiCl4 as precursor. The samples, consisting of suspensions, dispersions or powders of nanonstructured anatase or rutile phases, were obtained in very mild conditions, i.e., by boiling the solution obtained after hydrolysis of TiCl4 at atmospheric pressure: it is worth noting that no calcination was necessary to obtain photoactive phases. The samples were characterised by X-ray diffraction (XRD), determination of the BET specific surface area (SSA), scanning electron microscopy (SEM) observations and diffuse reflectance spectroscopy (DRS). FT-IR spectroscopy was use…

SrTiO 3 -based perovskites: Preparation, characterization and photocatalytic activity in gas–solid regime under simulated solar irradiation

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-o…

Preparation of photocatalysts by chemical methodologies

Abstract The synthesis of photocatalytic materials is an important task for obtaining better results in terms of activity and/or selectivity in photocatalysis. This chapter reports an overview of the main methodologies using physical techniques to obtain bulky, supported powders or films and coatings to be used as heterogeneous photocatalysts. The classical chemical methodologies for the preparation of photocatalytic materials are presented in the previous chapter, so the information presented here complements the aforementioned one. Materials scientists and engineers have made significant progresses in the improvement of methods of synthesis of nanomaterial solids by developing different a…

Photocatalytic degradation of 4-nitrophenol in aqueous suspension by using polycrystalline TiO2 impregnated with functionalised Cu(II)-porphyrin or Cu(II)-phthalocyanine

The photocatalytic activity of polycrystalline TiO2 samples impregnated with functionalized Cu(II)- or metal-free porphyrins has been investigated. A probe reaction, i.e., 4-nitrophenol (4-NP) photodegradation in aqueous suspension, has been used. The results indicated that the presence of the sensitizers is beneficial for the photoactivity and suggest an important role of Cu(II). A comparison with similar samples impregnated with modified Cu(II)- and metal-free phthalocyanines showed that the presence of porphyrin is more beneficial both for the decomposition rate of 4-nitrophenol and for the disappearance of nonpurgeable organic carbon (NPOC). Experiments were carried out by using cutoff …

Comparison of the photocatalytic degradation of 2-propanol in gas–solid and liquid–solid systems by using TiO2–LnPc2 hybrid powders

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…

Preparation of Photocatalytic Nanostructured TiO<sub>2</sub> Thin Films

Photoactive films consisting of pure anatase, brookite or rutile were deposited on glass slides by a dip coating process from water dispersions or solutions obtained by using TiCl4 as the precursor. The films were characterized by X-ray diffraction, scanning electron microscopy and atomic force microscopy. The photocatalytic activity of the various samples was evaluated by using the photooxidation of 2-propanol in gas solid regime as probe reaction. Brookite and anatase films showed a good photoactivity degrading the substrate and the propanone produced during the reaction.

ChemInform Abstract: Inorganic Materials Acting as Heterogeneous Photocatalysts and Catalysts in the Same Reactions

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 …

Preparation and photoactivity of nanostructured TiO2 particles obtained by hydrolysis of TiCl4

This work reports the preparation of nanostructured polycrystalline TiO2 photocatalysts obtained by hydrolysis of TiCl4 in very mild conditions. Several samples were prepared as suspensions or colloidal dispersions by using TiCl4/H2O volume ratios ranging between 1:1 and 1:100. The samples were characterised by X-ray diffraction analysis, specific surface area determination, diffuse reflectance spectroscopy and scanning electron microscopy. 4-Nitrophenol photodegradation was used as probe reaction to test the photoactivity of the catalysts. Some samples revealed a photoactivity higher than that of Degussa P25 in similar experimental conditions and the most photoactive one was that prepared …

Zn,Al hydrotalcites calcined at different temperatures: Preparation, characterization and photocatalytic activity in gas–solid regime

Abstract 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 het…

Photocatalytic thin films of TiO2 formed by a sol-gel process using titanium tetraisopropoxide as the precursor

Abstract Thin TiO 2 films were prepared with the dip-coating technique by using sols deriving from titanium tetraisopropoxide. TiO 2 films were formed on glass substrates previously covered by a SiO 2 layer obtained from a tetraethylortosilicate sol. The films, after a thermal treatment at 673 K, mainly consisted of TiO 2 anatase. The samples were characterised by X-ray diffraction, UV–Vis spectroscopy, scanning electron microscopy and atomic force microscopy. The photoactivity of the various films was tested by using as probe reaction the photo-oxidation of 2-propanol in gas-solid regime. The photoreactivity results indicated that the TiO 2 films were efficient for degrading 2-propanol und…

Photocatalytic oxidation mechanism of benzonitrile in aqueous suspensions of titanium dioxide

Abstract The photocatalytic oxidation of benzonitrile was carried out in aqueous suspensions (pH 11) of commercial polycrystalline TiO 2 (Merck and Degussa P25) irradiated by ultraviolet light. The rate of decomposition was dependent on the concentration of benzonitrile and followed a pseudo-first order kinetics. The complete mineralization of a 0.70 mM benzonitrile solution was achieved in ca. 8 h by using TiO 2 Degussa P25, whereas the substrate was only partially mineralized even after 14 h of irradiation in the presence of TiO 2 Merck. The final oxidation products were carbonate and nitrate. The appearance and the evolution of organic and inorganic intermediate species were also investi…

Photocatalytic Solar Light H 2 Production by Aqueous Glucose Reforming

Photocatalytic CO2 reduction in gas–solid regime in the presence of H2O by using GaP/TiO2 composite as photocatalyst under simulated solar light

GaP/TiO2 composites exhibited a remarkable photocatalytic activity for CO2 reduction in the presence of water vapor producing methane. By decreasing the GaP:TiO2 mass ratio an increase in the photocatalytic activity of the composite was observed for up to a 1:10 mass ratio. The photocatalytic activity of the composite can be attributed to the band structures of the solids as well as to the efficient charge transfer between GaP and TiO2 heterojunction.

Enhanced (photo)catalytic activity of Wells-Dawson (H6P2W18O62) in comparison to Keggin (H3PW12O40) heteropolyacids for 2-propanol dehydration in gas-solid regime

Abstract 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 …

Effect of Urea–Hydrogen Peroxide Content on the Photocatalytic Activity of Zinc Oxide Nanoparticles

ZnO nanoparticles (NPs) were synthesized using zinc acetate dihydrate, ethanol, and oxalic acid as precursor, solvent, and complexing agent, respectively, and urea–hydrogen peroxide (UHP) as, simultaneously, nitrogen precursor and oxygen donor. The structural, morphological, textural, and optical properties of ZnO photocatalysts were investigated using different characterization methods such as XRD, SEM, BET, and UV-Vis-DRS. The XRD patterns showed that the products consisted of ZnO and revealed the presence of nitrogen. SEM images revealed the agglomeration and aggregation of NPs. The photocatalytic activity of ZnO samples was estimated based on the photo-oxidation of 2-propanol under UV i…

Selective oxidation of aromatic alcohols in the presence of C3N4 photocatalysts derived from the polycondensation of melamine, cyanuric and barbituric acids

AbstractA set of C3N4 samples has been prepared by using melamine, cyanuric acid and barbituric acid as the precursors. The materials were subjected both to physical and chemical characterization and were used as photocatalysts for the selective oxidation of aromatic alcohols in water suspension under UV and visible irradiation. The photoactivity of the materials versus the partial oxidation of four substituted benzyl alcohols was investigated. The type and position of the substituents in the aromatic molecule influenced conversion and selectivity to the corresponding aldehyde. The presence of barbituric and cyanuric acids in the preparation method has changed the graphitic-C3N4 structure, …

Photocatalytic Degradation of 4-Nitrophenol in Aqueous Suspension by Using Polycrystalline TiO2 Impregnated with Lanthanide Double-Decker Phthalocyanine Complexes

The photocatalytic activity of polycrystalline TiO2 samples impregnated with rare-earth-metal diphthalocyanines was investigated. The 4-nitrophenol (4-NP) photocatalytic degradation in aqueous suspension was used as a probe reaction. Commercial anatase TiO2 was impregnated with home-prepared double-decker phthalocyanine complexes of the lanthanide metals, such as Ce, Pr, Nd, Sm, Ho, and Gd. In particular, the impregnation with Ho, Sm, and Nd complexes, acting as sensitizers, proved beneficial for the photoactivity of the studied systems. Significant improvements of the TiO2-based catalytic system appeared possible in terms of lower impregnation loading, enhanced photoreactivity under solar …

ChemInform Abstract: Advances in Selective Conversions by Heterogeneous Photocatalysis

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

Photoassisted Oxidation of the Recalcitrant Cyanuric Acid Substrate in Aqueous ZnO Suspensions

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 concentrati…

La1-xSrxCo1-yFeyO3-delta perovskites: Preparation, characterization and solar photocatalytic activity

Abstract LaCoO3 perovskites substituted by Sr at the A site and/or by Fe at the B site have been prepared by the citrate method. Characterizations by several techniques, such as specific surface area (BET method), XRD, TPR, SEM, UV–vis in DRS mode, XPS and TGA analyses, have been performed. The so prepared La1−xSrxCo1−yFeyO3−δ perovskites are semiconductor materials showing band gap energy values from 1.9 to 3.2 eV. They displayed solar photocatalytic activity for the 2-propanol degradation in gas–solid regime. The photocatalytic results suggest that the perovskites containing Fe are less active and the activity decreases by increasing the Fe content, however the presence of iron avoids the…

Photocatalytic Partial Oxidation of 5-hydroxymethyl-2-furfural Under UV and Natural Solar Irradiation in Aqueous Suspension of K Containing C3N4

Background: The influence of the potassium metal cation on the graphitic carbon nitride (g-C3N4) photocatalyst has been studied in the partial oxidation of 5-hydroxymethyl-2-furfural (HMF) to 2,5-furandicarboxaldehyde (FDC). Objective: The aim of this study was to understand if the presence of K in C3N4 could increase the oxidative conversion of HMF to high added value species. Methods: Two sets of photocatalysts were prepared by following two different methodologies. In both series of the materials, the precursor of C3N4 was melamine with different types of the K containing species including KCl and KOH in one case and KNO3 alone in the other case. However, for both series of photocatalys…

ChemInform Abstract: Heteropolyacid-Based Materials as Heterogeneous Photocatalysts

Invited for the cover of this issue is the group of Giuseppe Marci and Leonardo Palmisano at the Universita degli Studi di Palermo, Italy. The cover image shows one aspect of the photocatalytic use of heteropolyacids: dye bleaching by irradiation with sunlight.

Polycrystalline TiO2 impregnated with cardanol-based porphyrins for the photocatalytic degradation of 4-nitrophenol

Hydrogenated cardanol (3-n-pentadecylphenol), a renewable organic resource obtained by vacuum distillation of roasted “cashew nut shell liquid” (CNSL), a by-product of the cashew industry, has been used to synthesize novel lipophilic porphyrins. Polycrystalline TiO2 impregnated with these novel “cardanol-based” porphyrins as sensitizers has been investigated in the photodegradation of 4-nitrophenol (4-NP) in aqueous suspension. The results indicated that the presence of the sensitizer enhances the photoactivity of polycrystalline bare TiO2 in the process. The activating effect was higher in the case of the Cu-complex.

Photocatalytic formation of H2 and value-added chemicals in aqueous glucose (Pt)-TiO2 suspension

Abstract 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 commerci…

Titania–Silica Materials for Enhanced Photocatalysis

Mesoporous titania–organosilica nanoparticles comprised of anatase nanocrystals crosslinked with organosilica moieties have been prepared by direct co-condensation of a titania precursor, tetrabuthylortotitanate (TBOT), with two organosilica precursors, 1,4-bis(triethoxysilyl) benzene (BTEB) and 1,2-bis(triethoxysilyl) ethane (BTEE), in mild conditions and in the absence of surfactant. These hybrid materials show both high surface areas (200–360 m2 g−1) and pore volumes (0.3 cm3 g−1) even after calcination, and excellent photoactivity in the degradation of rhodamine 6G and in the partial oxidation of propene under UV irradiation, especially after the calcination of the samples. During calci…

A survey of photocatalytic materials for environmental remediation

Abstract Heterogeneous photocatalysis is an advanced oxidation process which has been the subject of a huge amount of studies related to air cleaning and water purification. All these processes have been carried out mainly by using TiO 2 -based materials as the photocatalysts and ca. 75% of the articles published in the last 3 years is related to them. This review illustrates the efforts in the search of alternative photocatalysts that are not based on TiO 2 , with some exceptions concerning particularly innovative modifications as nanoassembled TiO 2 or TiO 2 composites with active carbon, graphite and fullerene. Papers reporting preparation, characterization and testing of binary, ternary…

Heteropolyacid‐Based Materials as Heterogeneous Photocatalysts (Eur. J. Inorg. Chem. 1/2014)

Photo-assisted degradation of 2-propanol in gas–solid regime by using TiO2 impregnated with heteropolyacid H3PW12O40

Abstract 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 w…

Keggin heteropolyacid supported on TiO2 used in gas-solid (photo)catalytic propene hydration and in liquid-solid photocatalytic glycerol dehydration

Abstract (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 …

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.

Heteropolyacid‐Based Materials as Heterogeneous Photocatalysts

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 an…

CO2 reduction by C3N4-TiO2 Nafion photocatalytic membrane reactor as a promising environmental pathway to solar fuels

Abstract We investigated CO2 photocatalytic reduction coupling, for the first time in literature, the assets offered by the continuous operating mode using C3N4-TiO2 photo-catalyst embedded in a dense Nafion matrix. The reactor performance was analyzed under UV–vis light in terms of productivity, selectivity and converted carbon. Reaction pressure was specifically investigated for its effect as a “driver” in determining reactor performance, modulating products removal from the reaction volume. In addition, the membrane reactor performance was explored as a function of H2O/CO2 feed molar ratio and contact time. The higher feed pressure (5 bar) led to a lesser MeOH production and a greater am…

Fine chemistry by TiO2 heterogeneous photocatalysis

Abstract Heterogeneous TiO2 photocatalysis is a promising technology based on the capability of the semiconducting material to generate charges upon irradiation of suitable energy. The photogenerated electrons and holes, in turn, induce redox reactions involving species adsorbed on the surface of the photocatalyst, giving rise to chemical transformations. The presence of highly oxidizing radicals, thus generated, has long led to consider TiO2 photocatalysis only a nonselective oxidation process. In fact, so far it is possible to find in the literature many examples of its use in the field of environmental remediation aimed at the degradation of harmful molecules, although the studies are al…

Mechanistic aspects of oxalic acid oxidation by photocatalysis and ozonation

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.

Fundamentals of photocatalysis: The role of the photocatalysts in heterogeneous photo-assisted reactions

Abstract This chapter provides some general definitions of heterogeneous photocatalysis and evaluates its performance, which is influenced by the parameters most closely related to the properties of the solid material that acts as a photocatalyst. It also discusses aspects of heterogeneous photocatalytic reactions and explains the properties that influence photoactivity. Finally, the chapter examines thermodynamic and kinetic features, including mechanistic details and parameters to define the reaction rate and correlates them to the effects of the interaction of light with the photocatalyst surface and adsorption-desorption of species involved in heterogeneous photo-assisted reactions.

Removal of drugs in aqueous systens by photoassisted degradation

Aqueous solutions of tetracycline, lincomycin and ranitidine were irradiated with UV light in homogeneous and heterogeneous systems. Two commercial polycrystalline TiO2 powders (Degussa P25 and Merck) were used as photocatalysts. After 5A h, an appreciable photolytic degradation of tetracycline and ranitidine was observed while the degradation of lincomycin was noticeably lower. As far as the mineralization is concerned, a small decrease of the TOC values was measured in the case of tetracycline whereas negligible variations were found for lincomycin or ranitidine. The presence of the photocatalysts greatly enhanced the degradation rates of the drugs with respect to those observed during th…

Photocatalytic oxidation of acetonitrile in aqueous suspension of titanium dioxide irradiated by sunlight

The photocatalytic oxidation of acetonitrile (CH3CN) was carried out in aqueous suspensions of polycrystalline TiO2 P25 Degussa irradiated by sunlight. A plug flow photoreactor in a total recycle loop was used for carrying out reactivity experiments in which the concentrations of acetonitrile, of its intermediate oxidation products and of not-purgeable organic carbon (NPOC) were monitored. The influence of the presence of strong oxidant species (H2O2, S2O82−, ClO−) on the process rate was studied. The dependence of acetonitrile photo-oxidation rate on the substrate concentration and on the catalyst amount was also investigated. The photodegradation rate of substrate and NPOC followed first …

Effect of Substituents on Partial Photocatalytic Oxidation of Aromatic Alcohols Assisted by Polymeric C3N4

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 me…

Photocatalytic CO2 Reduction in Gas-Solid Regime in the Presence of Bare, SiO2 Supported or Cu-Loaded TiO2 Samples

Both commercial and home prepared (HP) TiO2 samples have been tested for the photocatalytic reduction of CO2. (HP) TiO2 powders were prepared by using TiCl4 or Ti(OC4H9)4 as the precursors to obtain HP1 and HP2 samples, respectively. Also HP Cu-loaded and SiO2 supported TiO2 powders were prepared. The HP samples were more active than the commercial ones for the photoreduction of CO2 with and without water vapour. HP1 produced mainly formaldehyde, HP2 principally methane. Acetaldehyde was found to be the primary product obtained when HP1 was supported on SiO2. The addition of Cu increased the photocatalytic reactivity either of bulk and SiO2-supported HP1. In particular, 1 wt % of Cu improve…

Inorganic materials acting as heterogeneous photocatalysts and catalysts in the same reactions

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 …

Photoelectrochemical and EPR features of polymeric C 3 N 4 and O-modified C 3 N 4 employed for selective photocatalytic oxidation of alcohols to aldehydes

Four different C 3 N 4 specimens have been prepared, a bulk one (MCN), a thermally etched (MCN-TE), a solid prepared by hydrothermally treating MCN with H 2 O 2 (MCN-H 2 O 2 ) and a polymeric carbon nitride-hydrogen peroxide adduct (MCN-TE-H 2 O 2 ). The principal aim of this work was to correlate the capability of the prepared material to generate reactive oxygen species (ROS), under irradiation, with their photocatalytic activities in terms of conversion and selectivity for partial oxidation reactions. Photoelectrochemical studies revealed that MCN-TE represented the best material in terms of photoconductivity, whereas MCN-H 2 O 2 was defective and evidenced a poor mobility of carriers. E…

Heteropolyacids supported on boron nitride and carbon nitride for catalytic and catalytic photo-assisted alcohol dehydration

Keggin H3PW12O40 (PW12) and Wells-Dawson H6P2W18O60 (P2W18) heteropolyacids (HPAs) are photo(catalysts) for various acid-promoted and redox catalytic reactions. Their activity increases if they are deposited on certain supports as metal oxides or carbon materials. Although the surface area and acid-base interactions of the HPAs with supports are considered as key factors for the performance of the binary material, the role of the local structure changes in the HPAs upon their immobilization on solids must be also of primary importance, directly affecting both acidity and photoredox properties. Here, the (photo)catalytic performance of Keggin and Wells-Dawson heteropolytungstates supported o…

Local Structure of Supported Keggin and Wells-Dawson Heteropolyacids and Its Influence on the Catalytic Activity

[EN] Keggin [PW12O40]3– and Wells–Dawson [P2W18O62]6– heteropolyanions are nanosized transition-metal-oxygen clusters belonging to the heteropolyacids (HPAs) family. They are widely used as catalysts due to their high Brønsted acidity, and their dispersion on solid supports favors the accessibility to their acid sites generally increasing the catalytic activity. A series of binary materials composed of Keggin or Wells–Dawson HPAs and SiO2, TiO2, and ZrO2 have been prepared by impregnation or solvothermal methods. Remarkable differences have been found in the catalytic activities among the unsupported and supported HPAs. These differences have been correlated in the past to the structural ch…

TiO2-based photocatalysts impregnated with metallo-porphyrins employed for degradation of 4-nitrophenol in aqueous solutions: role of metal and macrocycle

Photodegradation of organic compounds in water solutions by means of economically advantageous and environment-friendly processes is a topic of growing interest. In recent years a great attention has been devoted to TiO2-based photocatalysts for the oxidative degradation of various organic pollutants. In this context, we have prepared new photo-catalytic polycrystalline TiO2 systems impregnated with sensitizers, i.e., copper, iron or manganese porphyrins, and investigated their photoactivity for 4-nitrophenol oxidation compared with that of bare TiO2. A significant improvement of the photoreactivity was observed in the case of TiO2 impregnated with copper porphyrin, while only a slight bene…

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.

Superparamagnetic recoverable flowerlike Fe3O4@Bi2O3 core–shell with g-C3N4 sheet nanocomposite: synthesis, characterization, mechanism and kinetic study of photo-catalytic activity

In the present research study, a simple method was developed for the synthesis of three-dimensional flowerlike Fe3O4@Bi2O3 core–shell with g-C3N4 sheet nanocomposites. The X-ray diffraction, Fourier transform infrared spectroscopy, scanning electronic microscopy, transmission electron microscope, vibrating sample magnetometer, dynamic laser scattering analyzer and UV–Vis diffuse reflection spectroscopy were employed for the characterization of structure, purity and morphology of the resultant samples. The degradation of indigo carmine as a model of organic dye pollutant is applied for photo-catalytic activity. The parameters which are affecting the efficiency of various parameters, such as;…

Nanosponge-C3N4 composites as photocatalysts for selective partial alcohol oxidation in aqueous suspension

A set of four composite materials was prepared, consisting of a nanosponge matrix based on beta-cyclodextrin in which carbon nitride was dispersed. The materials were characterized by the presence of diverse cross-linker units joining the cyclodextrin moieties, in order to vary the absorption/release abilities of the matrix. The composites were characterized and used as photocatalysts in aqueous medium under UV, visible and natural solar irradiation for the photodegradation of 4-nitrophenol, and for the selective partial oxidation of 5-hydroxymethylfurfural and veratryl alcohol to the corresponding aldehydes. The nanosponge-C3N4 composites showed higher activity than the pristine semiconduc…

Selective photocatalytic oxidation of 5-hydroxymethyl-2-furfural in aqueous suspension of polymeric carbon nitride and its adduct with H2O2 in a solar pilot plant

Abstract This work reports a study on the reactivity of polymeric carbon nitride (PCN) and PCN-H2O2 adduct samples for sunlight photocatalytic selective oxidation reactions. The characterization of these materials was reported in a previous paper where the reactivity towards the partial oxidation of 5-hydroxymethylfurfural (HMF) was studied by using two different laboratory scale photoreactors; one irradiated by UV lamps and the other one by natural sunlight. In the present study it has been confirmed the effectiveness of these C3N4 based materials for the selective partial oxidation of HMF to FDC (2,5-furandicarboxaldehyde) in aqueous medium in a pilot plant photoreactor irradiated by natu…

Selective photocatalytic oxidation of 5-hydroxymethyl-2-furfural to 2,5-furandicarboxyaldehyde in aqueous suspension of g-C3N4

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…

Oxidation of oxalate ion in aqueous suspensions of TiO2 by photocatalysis and ozonation

Abstract Oxalate anion has been oxidized in aqueous alkaline solution by using ozonation and photocatalysis in the presence of TiO 2 . A batch annular reactor has been used for carrying out reactivity runs in the presence of air/ozone, air/ozone/near UV irradiation, air/ozone/TiO 2 , air/near UV-irradiated TiO 2 and air/ozone/near UV-irradiated TiO 2 . The Langmuir–Hinshelwood kinetic model adequately describes the photocatalytic results obtained at different reaction conditions and allows determining the values of the kinetic and equilibrium adsorption constants. The contemporary presence of photocatalysis and ozonation shows a significant improvement of the process performance as the oxid…

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

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

Keggin heteropolyacid supported on BN and C3N4: Comparison between catalytic and photocatalytic alcohol dehydration

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…

Improved (photo)catalytic propene hydration in a gas/solid system by using heteropolyacid/oxide composites: Electron paramagnetic resonance, acidity, and role of water

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 t…

Degradation of Lincomycin in aqueous medium: coupling of solar photocatalysis and membrane separation

Abstract The photocatalytic oxidation of a common antibiotic, the lincomycin was carried out in aqueous suspensions of polycrystalline TiO 2 Degussa P25 irradiated by sunlight. In order to improve the performance of the lincomycin degradation a hybrid system consisting of a solar photoreactor with the photocatalyst in suspension coupled with a membrane module, used to confine both photocatalyst and pollutants in the reaction environment, was tested. A preliminary study was carried out in order to determine some kinetics parameters of the drug photodegradation. The influence of initial substrate concentration on the lincomycin photooxidation rate was investigated. The photooxidation rate fol…

Photocatalytic Degradation of 4-nitrophenol in aqueous suspension by using polycristalline TiO2 samples impregnated with a Cu(II)-phthalocyanine

In this paper, the preparation of polycrystalline TiO2 samples impregnated with a modified Cu(II)-phthalocyanine (TiO2–CuPc) is reported along with an investigation on the photocatalytic behavior of this system compared with bare TiO2 (both in the anatase and rutile form) and with TiO2 samples impregnated with not functionalized commercial phthalocyanine (TiO2–CuPc) or with metal free phthalocyanine (TiO2–Pc). The photocatalytic degradation of 4-nitrophenol (4-NP) was studied as a probe reaction. The presence of modified CuPc showed to be beneficial only for TiO2 (anatase) while the commercial not functionalized CuPc also slightly for both TiO2 (anatase) and TiO2 (rutile). The metal free Pc…

Photocatalytic conversion of glucose in aqueous suspensions of heteropolyacid-TiO2 composites.

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 isomer…

Selective photocatalytic oxidation of aromatic alcohols in water by using P-doped g-C3N4

A set of bare and P-doped graphitic carbon nitride (g-C3N4) photocatalysts has been prepared by thermal condensation of melamine, urea or thiourea. For the sake of comparison, a g-C3N4 sample obtained in the presence of cyanuric acid and thermally exfoliated C3N4 powders were also studied. The materials were physicochemically characterized and their photocatalytic activity was studied for the selective oxidation of benzyl alcohol (BA), 4-methoxy benzyl alcohol (4-MBA) and piperonyl alcohol (PA) in water suspension both under UV and visible light irradiation. The influence of the type and position of the substituents on conversion and selectivity to aldehyde was remarkable. The presence of P…

Catalytic Dehydration of Fructose to 5-Hydroxymethylfurfural in Aqueous Medium over Nb2O5-Based Catalysts

The catalytic dehydration of fructose to 5-hydroxymethylfurfural (HMF) in water was performed in the presence of pristine Nb2O5 and composites containing Nb and Ti, Ce or Zr oxides. In all experiments, fructose was converted to HMF using water as the solvent. The catalysts were characterized by powder X-ray diffraction, scanning electron microscopy, N2 physical adsorption, infrared and Raman spectroscopy and temperature-programmed desorption of NH3. Experimental parameters such as fructose initial concentration, volume of the reacting suspension, operation temperature, reaction time and amount of catalyst were tuned in order to optimize the catalytic reaction process. The highest selectivit…

Cu-substituted lanthanum ferrite perovskites: Preparation, characterization and photocatalytic activity in gas-solid regime under simulated solar light irradiation

Lanthanum orthoferrites LaFeO3 nanopowders doped with 20 mol% of Sr and 0-10-20 mol% of Cu were prepared by citrate auto-combustion synthesis and investigated in terms of crystal structure, morphology, surface area and optical properties by using several characterization techniques. The band gap energy values were found to range from 2.35 eV for LaFeO3 to 1.86 eV for the samples with the highest content of copper, this trend reflects the decrease of the particle size. All powders showed photocurrent response, the highest photocurrent was obtained for undoped orthoferrite calcined at 600°C. Their physical-chemical properties were related to photoelectrochemical behaviour. The the position of…

Supported H3PW12O40 for 2-propanol (photo-assisted) catalytic dehydration in gas-solid regime: The role of the support and of the pseudo-liquid phase in the (photo)activity

Abstract 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 regim…

Polymeric carbon nitride (C3N4) as heterogeneous photocatalyst for selective oxidation of alcohols to aldehydes

Abstract Polymeric carbon nitride (C3N4) is a semiconductor material which is a very promising green photocatalyst with good physico-chemical properties and stability. It is a metal-free carbon based non-toxic material which can be easily obtained from earth-abundant components. The robustness and versatility of C3N4 as a photo-redox catalyst allows its use for selective oxidations by heterogeneous photocatalysis. This paper reviews the state of art in the application of C3N4 as heterogeneous photocatalyst for selective oxidation of alcohols to the corresponding aldehydes.

Photocatalytic oxidation of acetonitrile in gas–solid and liquid–solid regimes

Il programma NON mi ha consentito di scaricare il PDF di questo articolo. Se lo volete ditemi come inviarlo ABSTRACT Photocatalytic degradation of acetonitrile was carried out in both gas–solid and liquid–solid regimes using two commercial TiO2 catalysts (Merck and Degussa P25). For the gas–solid regime, a continuous annular photoreactor was used. The influence on photodegradation kinetics of the gas flow rate and concentrations of acetonitrile, oxygen, and water was investigated. Acetonitrile degradation products detected in the gas phase included carbon dioxide and hydrogen cyanide. The same photoactivity was exhibited in the presence and in the absence of water vapour. The liquid–solid reg…