Influence of some aromatic and aliphatic compounds on the rate of photodegradation of phenol in aqueous suspensions of TiO2

Abstract The influence of 3-nitrophenol, 4-nitrophenol, pentachlorophenol, ethanol, 2-propanol, ethanoic acid and ethanedioic acid on the photodegradation rate of phenol in an aqueous suspension of TiO2 (anatase) irradiated in the near-UV region was investigated. Binary mixtures of organic compound and phenol in molar ratios of 1:1 and 10:1 were used for the photoreactivity experiments performed in a batch reactor. The mineralization rate of all the mixtures was also monitored by measuring the total organic carbon (TOC) concentration. The reactivity results indicate that the photodegradation rate of phenol is mainly determined by the total amount of aromatic substrates present in the reacti…

Influence of operational variables on the photodegradation kinetics of Monuron in aqueous titanium dioxide dispersions

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.

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…

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

WOS: 000256241700021

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…

Titania Photocatalysts for Selective Oxidations in Water

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-substitute…

Dehydration of Fructose to 5-HMF over Acidic TiO2 Catalysts

Different solid sulfonic titania-based catalysts were investigated for the hydrothermal dehydration of fructose to 5-hydroxymethylfurfural (5-HMF). The catalytic behavior of the materials was evaluated in terms of fructose conversion and selectivity to 5-HMF. The surface and structural properties of the catalysts were investigated by means of X-ray diffraction (XRD), N2 adsorption isotherms, thermo-gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and acid capacity measurements. Special attention was focused on the reaction conditions, both in terms of 5-HMF selectivity and the sustainability of the process, choosing water as the solvent. Among the various process condition…

Adsorption and photocatalytic degradation of acetonitrile: FT-IR investigation

Abstract 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…

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…

Biological effects and photodegradation by TiO(2) of terpenes present in industrial wastewater.

Abstract The aim of this work was to study the biological effects of four monoterpenes, i.e. α-pinene, β-pinene, 3-carene and d -limonene present in the wastewater of a citrus transformation factory. The study was carried out by exposing V79 Chinese hamster cells to single terpene or to the mixture of four terpenes at concentrations corresponding to those in the wastewater evaluated by head space solid phase micro extraction and gas chromatography (HS-SPME-GC) analyses. Treatments with single or combined terpenes similarly affected cell vitality, but only the combined treatments induced the 6-thioguanine resistant mutants. Moreover the photocatalytic degradation of the four terpenes was suc…

Strontium and iron-doped barium cobaltite prepared by solution combustion synthesis: exploring a mixed-fuel approach for tailored intermediate temperature solid oxide fuel cell cathode materials

Ba0.5Sr0.5Co0.8Fe0.2O3-? (BSCF) powders were prepared by solution combustion synthesis using single and double fuels. The effect of the fuel mixture on the main properties of this well-known solid oxide fuel cell cathode material with high oxygen ion and electronic conduction was investigated in detail. Results showed that the fuel mixture significantly affected the area-specific resistance of the BSCF cathode materials, by controlling the oxygen deficiency and stabilizing the Co2+ oxidation state. It was demonstrated that high fuel-to-metal cations molar ratios and high reducing power of the combustion fuel mixture are mainly responsible for the decreasing of the area-specific resistance o…

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…

TiO2-Based Photocatalysis for Organic Synthesis

A major aim of the contemporary chemistry is to replace old environmentally hazardous processes with new, energy efficient routes allowing to reduce or totally avoid the use and production of harmful chemicals and to maximise the quantity of raw material that ends up in the final product. This chapter gives an account of TiO2-based selective photocatalysis as a green synthetic tool for the production of organics. Some case studies of the most common transformations carried out by means of photocatalytic reactions are illustrated in a midway perspective between photochemistry and organic chemistry.

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…

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…

Environmentally sustainable production of cellulose-based superabsorbent hydrogels

The development of new products and materials, especially those which are non-petrolchemical reserves and based on renewable organic resources, using innovative sustainable processes is nowadays of increasing interest and deserves the attention of both academic and industrial research. Cellulose and its derivatives, as renewable organic resources, have been used to synthesize novel superabsorbent hydrogels. Although the production of cellulose is one of the causes connected to deforestation, the production of suitably engineered cellulose superabsorbent hydrogel materials has been proposed to preserve water in typically arid areas in the world. Paradoxically, divinylsulfone (DVS), a small d…

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 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…

Influence of platinum on catalytic activity of polycrystalline WO3 employed for phenol photodegradation in aqueous suspension

Abstract A series of polycrystalline WO3 solids loaded with platinum (0.5; 1.0; 2.0 and 3.0 wt%) were prepared and characterised by X-ray diffraction, diffuse reflectance spectroscopy, scanning electron microscopy, specific surface areas determination, X-ray photoelectron spectroscopy. XPS and X-ray results indicate that the samples loaded with Pt up to 1 wt% contained on the surface mainly Pt(2+) species, while those loaded with higher amounts contained Pt(0). Moreover, the samples were employed for a probe reaction, i.e. phenol photooxidation in aqueous suspension, and their photoactivity was compared with that of two TiO2 commercial samples, mainly in the anatase phase. All the Pt–WO3 sa…

Analytical control of photocatalytic treatments: degradation of a sulfonated azo dye

The degradation of Methyl Orange (C(14)H(14)N(3)SO(3)Na), chosen as a model sulfonated azo dye, was investigated in aqueous solutions containing suspended polycrystalline TiO(2) particles under irradiation with simulated sunlight. The dye disappearance and the formation of the mineralization end products were monitored; the formation of the main transient intermediates was also examined in detail. Particular attention was devoted to the identification and to the evolution of fragments retaining the chromophoric group. The comparison of data coming from various analytical techniques led to a possible reaction mechanism for the degradation process, giving insight into an aspect of the treatme…

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.

Selectivity of hydroxyl radical in the partial oxidation of aromatic compounds in heterogeneous photocatalysis

Abstract The photocatalytic oxidation of different benzene derivatives has been investigated in order to understand how the substituent group affects the selectivity to hydroxylated compounds. Experimental runs were performed by using TiO2 (Merck) aqueous suspensions at natural pH irradiated by near-UV light. The organic molecules used as substrate contained an electron withdrawing group (EWG) (nitrobenzene, cyanobenzene, benzoic acid, 1-phenylethanone), an electron donor one (EDG) (phenol, phenylamine, N-phenylacetamide) or both an EWG and an EDG (4-chlorophenol). The results clearly indicated that the primary photocatalytic oxidation of aromatic compounds containing an EDG gives rise main…

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…

Characterization of methyl orange and its photocatalytic degradation products by HPLC/UV–VIS diode array and atmospheric pressure ionization quadrupole ion trap mass spectrometry

Abstract HPLC/UV–VIS diode array and HPLC/MS techniques were successfully applied to the analysis of sulfonated molecules present in samples coming from the photocatalytic degradation of the azo dye indicator, methyl orange. The substrate was chosen as a simple model for the study of reactions involving the more complex commercial products used for the dyeing of textile fibers. Unexpected MS fragmentation path was observed, due to the very stable methyl orange molecular structure. The chromatographic information were combined with the obtained MS, MS/MS data and the UV–VIS diode array spectra and allowed to rationalize the molecular structures attributable to the various degradation product…

Paper Functionalized with Nanostructured TiO2/AgBr: Photocatalytic Degradation of 2–Propanol under Solar Light Irradiation and Antibacterial Activity

A facile method to produce paper&ndash

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…

Photocatalytic degradation of acid blue 80 in aqueous solutions containing TiO2 suspensions.

The photocatalytic degradation of the anthraquinonic dye Acid Blue 80 in aqueous solutions containing TiO2 dispersions has been investigated. The process has been monitored by following either the disappearance of the dye (via HPLC) and the formation of its end-products (via IC, GC, and TOC analysis). Although a relatively fast decolorization of the solutions has been observed, the mineralization is slower, and the presence of residual organic compounds was evidenced even after long term irradiation, confirming the relevant stability of anthraquinone derivatives. The identification of various unstable intermedi ates formed after low irradiation times was performed by HPLC-MS, allowing us to…

Photocatalytic activity of TiO2/SiO2 systems

Silica-supported TiO(2) powders were synthesized by a wet method under mild conditions. The aim of the work was the preparation of TiO(2)/SiO(2) additives for photocatalytic cements. Three types of commercial SiO(2) were used as supports: Cabot, Axim and Fly Ash. Cabot silica was ultra-pure whereas the other two silica contained different percentages of various oxides. The TiO(2)/SiO(2) samples, denoted TiO(2)/Cabot, TiO(2)/Axim and TiO(2)/Fly Ash, were prepared by boiling suspensions obtained by addition of silica to a solution of TiCl(4) in water (volume ratio 1:10). The photocatalytic activity was evaluated in a gas-solid system both in batch and in continuous reactors using 2-propanol a…

Co3O4 particles grown over nanocrystalline CeO2: influence of precipitation agents and calcination temperature on the catalytic activity for methane oxidation

Crystalline cobalt oxides were prepared by a precipitation method using three different precipitation agents, (NH4)(2)CO3, Na2CO3 and CO(NH2)(2). Cobalt oxide nanoparticles corresponding to a Co3O4 loading of 30 wt% were also deposited over high-surface area nanocrystalline ceria by the same precipitation agents. The effect of calcination temperature, 350 or 650 degrees C, on the morphological and structural properties was evaluated. Characterization by BET, XRD, SEM, TEM, Raman spectroscopy, H-2-TPR, XPS and NH3-TPD was performed and the catalytic properties were explored in the methane oxidation reaction. The nature of the precipitation agent strongly influenced the textural properties of…

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…

Preparation, Characterization, and Photoactivity of Polycrystalline Nanostructured TiO2 Catalysts.

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 samp…

Paper-TiO2 composite: An effective photocatalyst for 2-propanol degradation in gas phase

Two simple routes for the synthesis of a paper-TiO2 composite were tuned up and the efficiency of the resulting paper-TiO2 photocatalyst was investigated in the 2-propanol oxidation in gas phase. The first route involved the in-situ generation over the sheet of paper of a TiO2 layer starting from a solution of Ti (OBu)4 in tert-butanoliacetic acid, followed by hydrothermal treatment at 120 degrees C for 3 h. The sample was labelled as paper-TiO2 (H). The second approach was based on the adsorption on the paper of a ready-made suspension of titania nanoparticles (TiO2 sol), generated in autoclave at 140 degrees C and stable in acid medium at pH <3. The sample was labelled as paper-TiO2 (S). …

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 oxidation of cyanide in aqueous TiO2 suspensions irradiated by sunlight in mild and strong oxidant conditions

Abstract The photocatalytic oxidation of free cyanide ions was carried out in aqueous aerated suspensions containing polycrystalline TiO2 (anatase) irradiated by sunlight. The influence of the presence of an organic compound (phenol) or of a strong oxidant (H2O2) on the photoprocess was also studied. The dependence of cyanide photo-oxidation rate on the following parameters: (1) cyanide concentration; (2) catalyst amount; and (3) phenol concentration was investigated. At the used experimental conditions, the kinetics of cyanide photo-oxidation is independent of the initial cyanide concentration and of the catalyst amount while it is affected by the phenol concentration and by the presence o…

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&lt;sub&gt;2&lt;/sub&gt; 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.

Photocatalytic degradation of toluene in aqueous suspensions of polycrystalline TiO2 in the presence of the surfactant tetradecyldimethylamino-oxide

The heterogeneous photocatalytic method has been used for carrying out the toluene oxidation in synthetic aqueous solutions containing also a zwitterionic surfactant, i.e. tetradecyldimethylamino-oxide (C 14 DMAO). A batch photoreactor with immersed lamp and two kinds of polycrystalline TiO 2 catalysts were used. The results indicate a substantial increase of the toluene degradation rate in the presence of the surfactant; the complete photo- oxidation of toluene was achieved in a few hours of irradiation at the used experimental conditions; at higher irradiation times also C 14 DMAO was completely degraded. The main intermediates of toluene degradation were p-cresol (4-methyiphenol) and ben…

Photocatalytic Oxidation of Cyanides in Aqueous Titanium Dioxide Suspensions

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 p…

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 …

Citrate–nitrate auto-combustion synthesis of perovskite-type nanopowders: A systematic approach

Abstract 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 par…

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

Preparation and characterization of Al2O3 supported TiO2 catalysts employed for 4-nitrophenol photodegradation in aqueous medium

Abstract In this paper the preparation and some bulk and surface characterizations of set of Al2O3 supported TiO2 photocatalysts are reported. The powders were home prepared by a wet impregnation method using titanium (IV) isopropylate. The impregnation was followed by thermal treatments and this procedure was repeated several times in order to obtain samples with different amounts of TiO2. The solids were characterized by X-ray diffraction, specific surface area determination, scanning electron microscopy coupled with an electron microprobe used in an energy-dispersive mode and diffuse reflectance spectroscopy. Moreover, all of them were tested as photocatalysts by using different kinds of…

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 …

Preparation and characterisation of TiO2 (anatase) supported on TiO2 (rutile) catalysts employed for 4-nitrophenol photodegradation in aqueous medium and comparison with TiO2 (anatase) supported on Al2O3

Abstract In this paper the preparation of two sets of polycrystalline photocatalysts prepared by supporting TiO2 (anatase) on TiO2 (rutile) or Al2O3 is reported. The powders were prepared by a wet impregnation method using titanium(IV) isopropylate. The impregnation was followed by thermal treatment and this procedure was repeated several times in order to obtain samples with progressively increasing amounts of TiO2 (anatase). The photocatalytic activity of all of the specimens was tested by carrying out the 4-nitrophenol photodegradation, used as a “probe” reaction, in aqueous medium and in different kinds of batch photoreactors. The solids were characterised by X-ray diffraction (XRD), sp…

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…

Photodegradation kinetics of aniline, 4-ethylaniline, and 4-chloroaniline in aqueous suspension of polycrystalline titanium dioxide

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. T…

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, …

Total oxidation of propene at low temperature over Co3O4–CeO2 mixed oxides: Role of surface oxygen vacancies and bulk oxygen mobility in the catalytic activity

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 …

Structural and morphological properties of Co-La catalysts supported on alumina/lanthana for hydrocarbons oxidation

Abstract 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 loadi…

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…

In search of layered antimony(III) materials: synthesis and characterization of oxo-antimony(III) catecholate and further studies on antimony(III) phosphate

Abstract A new layered oxo-antimony(III) catecholate, [Sb(C6H4O2)]2O, can be obtained by reacting senarmontite with aqueous catechol. The same reaction performed with valentinite, the other allotropic form of Sb2O3, shows an intermediate hydrate that loses water at about 100°C. Both compounds can be obtained from SbPO4 under appropriate experimental conditions. [Sb(C6H4O2)]2O and the hydrated form, which appear to be layered materials, have been characterized by X-ray diffraction, thermogravimetric/differential thermal analyses, and infrared techniques. Preliminary evidence of a reversible intercalation of pyridine into [Sb(C6H4O2)]2O was collected. Taking into consideration the possible us…

Preparation characterization and photocatalytic activity of polycrystalline ZnO/TiO2 systems. 1. Surface and bulk characterization

Polycrystalline ZnO/TiO2 solids have been prepared with four different methods using home prepared TiO2 (anatase) or TiO2 (rutile) as supports and Zn(NO3)2·6H2O or Zn(CH3COO)2·2H2O as precursors for ZnO. The bulk and surface properties of the samples were investigated by means of TG-DTA, XRD, TEM, SEM-EDAX, XPS, BET surface area determination, and porosity measurements. XRD and TEM results indicate that no significant defect structures exist in any of the samples. The ZnO crystallinity and its enrichment on the surface of TiO2 particles were dependent on the preparation method. The surface areas generally decrease by increasing the amount of ZnO except when ZnO from Zn(CH3COO)2·2H2O was sup…

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.

Preparation of Sm-loaded brookite TiO2 photocatalysts

Abstract Pure and Sm-loaded brookite nanoparticles and thin films were prepared using TiCl4 as precursor of TiO2. The samples were characterized by X-ray diffraction (XRD), specific surface area (SSA) determination, diffuse reflectance spectroscopy (DRS) and photoluminescence (PL) measurements. The photocatalytic activity of the powders was investigated by employing the photodegradation of 4-nitrophenol in a liquid–solid system whilst the photoreactivity of the films was tested by evaluating the rate of degradation of 2-propanol in a gas–solid system. Loading with Sm resulted in a significant improvement of the photoreactivity of brookite and the beneficial effect was attributed to an incre…

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 …

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…

Preface

Preface of the book "Heterogeneous Photocatalysis Relationships with Heterogeneous Catalysis and Perspectives"

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.

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…

Local structure of the supported Keggin and Wells-Dawson heteropolyacids and its consequence on their (photo)catalytic activity

An Investigation into the Stability of Graphitic C 3 N 4 as a Photocatalyst for CO 2 Reduction

The increasing CO 2 concentration in the atmosphere exerts a significant influence on global warming and climate change. The capture and utilization of CO 2 by conversion to useful products is an area of active research. In this work, the photodriven reduction of CO 2 was investigated using graphitic carbon nitride (g-C 3 N 4 ) as a potential photocatalyst. The photocatalytic reduction of CO 2 was investigated with g-C 3 N 4 powder immobilized on a glass support in a batch gas-phase photoreactor. The experiments were carried out under UV-vis irradiation at 70 °C and an initial pressure of 2.5 bar. The only gas-phase product detected during the irradiation of the g-C 3 N 4 in the presence of…

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…

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.

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 …

Photocatalytic activity of transition-metal-loaded titanium(IV) oxide powders suspended in aqueous solutions: Correlation with electron–hole recombination kinetics

Photocatalytic reactions by transition-metal (V, Cr, Fe, Co, Cu, Mo, or W) loaded TiO2 (M-TiO2) powders suspended in aqueous solutions of methanol, (S)-lysine (Lys), or acetic acid were investigated. The photoactivities of various samples were compared with the rate constant (kr) of recombination of photoexcited electrons and positive holes determined by femtosecond pump–probe diffuse reflection spectroscopy (PP-DRS). As a general trend, increased loading decreased the rate of formation of the main products (H2 , pipecolinic acid (PCA), and CO2) under UV (>300 nm) irradiation, and the effect became more intense on increasing the loading. In PP-DRS, these M-TiO2 gave similar decays of absorp…

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…

Sustainable Recycling of Insoluble Rust Waste for the Synthesis of Iron-Containing Perovskite-Type Catalysts

Insoluble rust waste from the scraping of rusted iron-containing materials represents a cheap, eco-friendly, and available source of iron. LaFeO3 perovskite-type powders were successfully prepared by solution combustion synthesis using rust waste from an electricity transmission tower manufacturer. Solution combustion synthesis enabled introduction of this insoluble iron precursor directly into the final product, bypassing complex extraction procedures. Catalytic activity in the propylene oxidation of the waste-derived LaFeO3 with stoichiometric Fe/La ratio was almost identical to the commercial iron nitrate-derived LaFeO3 , thus demonstrating the viability of this recycling solution. The a…

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…

The role of water in the photocatalytic degradation of acetonitrile and toluene in gas-solid and liquid-solid regimes

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 …

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…

Extruded Expanded Polystyrene Sheets Coated by TiO2 as New Photocatalitic Materials for Foodstuffs Packaging

Nanostructured, photoactive anatase TiO2 sol prepared under very mild conditions using titanium tetraisopropoxide as the precursor is used to functionalise extruded expanded polystyrene (XPS) sheets by spray-coating resulting in stable and active materials functionalised by TiO2 nanoparticles. Photocatalytic tests of these sheets performed in a batch reactor in gas-solid system under UV irradiation show their successful activity in degrading probe molecules (2-propanol, trimethylamine and ethene). Raman spectra ensure the deposition of TiO2 as crystalline anatase phase on the polymer surface. The presence of TiO2 with respect to polymer surface can be observed in SEM images coupled to EDAX …

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…

Preparation of polycrystalline TiO2 photocatalysts impregnated with various transition metal ions : characterization and photocatalytic activity for the degradation of 4-nitrophenol

A set of polycrystalline TiO2 photocatalysts loaded with various ions of transition metals (Co, Cr, Cu, Fe, Mo, V, and W) were prepared by using the wet impregnation method. The samples were characterized by using some bulk and surface techniques, namely X-ray diffraction, BET specific surface area determination, scanning electron microscopy, point of zero charge determination, and femtosecond pump-probe diffuse reflectance spectroscopy (PP-DRS). The samples were employed as catalysts for 4-nitrophenol photodegradation in aqueous suspension, used as a probe reaction. The characterization results have confirmed the difficulty to find a straightforward correlation between photoactivity and si…

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…

Structural and morphological investigation of a cobalt catalyst supported on alumina-baria: effects of redox treatments on the activity in the NO reduction by CO

Abstract 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…

Genotoxicity of citrus wastewater in prokaryotic and eukaryotic cells and efficiency of heterogeneous photocatalysis by TiO(2).

Abstract The presence of (±)α-pinene, (+)β-pinene, (+)3-carene, and R-(+)limonene terpenes in wastewater of a citrus transformation factory was detected and analyzed, in a previous study, by using Solid Phase Micro-extraction (SPME) followed by GC analyses. Purpose of that research was to compare the genotoxic responses of mixtures of terpenes with the genotoxicity of the individual compounds, and the biological effects of actual wastewater. Genotoxicity was evaluated in the Salmonella reversion assay (Ames test) and in V79 cells by Comet assay. Ames tests indicated that the four single terpenes did not induce an increase of revertants frequency. On the contrary, the mixtures of terpenes ca…

Different approaches for the solar photocatalytic removal of micro-contaminants from aqueous environment: Titania vs. hybrid magnetic iron oxides

Abstract This work reports on the light-induced heterogeneous photodegradation of four micro-contaminants (MCs): Carbamazepine (C), Flumequine (F), Ibuprofen (I), and Sulfamethoxazole (S), using two different heterogeneous advanced oxidation processes. The first one is the semiconductor photocatalysis, run in the presence of the suspension of a home prepared TiO2 (TiO2 HP); the second one is an heterogeneous photo-Fenton process run in the presence of a hybrid magnetic nanomaterial (MB3) with an iron oxides core and an organic shell made of bio-based substances (BBS) isolated from urban biowaste. The two materials work upon two different mechanisms and were already tested (and the action me…

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…

Preparation characterization and photocatalytic activity of polycrystalline ZnO/TiO2 systems. 2. Surface, bulk characterization, and 4-nitrophenol photodegradation in liquid-solid regime

Electron spin resonance spectroscopy (ESR), Fourier transform infrared spectroscopy (FTIR), and monitoring of pyridine (py) and boric acid trimethyl ester (BATE) adsorption for determining surface acidity and basicity, respectively, were used to carry out further characterization of mixed ZnO/TiO2 polycrystalline solids prepared by different methods. Moreover, the powders were tested in a batch photoreactor for a probe reaction, i.e., 4-nitrophenol photodegradation in aqueous medium. ESR results indicated the presence of signals attributable to Zn+ species in ZnO/TiO2 (anatase) solids, while in ZnO/TiO2 (rutile) samples the presence of zinc induced only the formation of signals probably due…

Tungstophosphoric acid supported on polycrystalline TiO2 for the photodegradation of 4-nitrophenol in aqueous solution and propan-2-ol in vapour phase

Abstract 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…

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.

Synthesis of high-surface area CeO2 through silica xerogel template: influence of cerium salt precursor”;

Abstract 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 …

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…