Environmentally Friendly Photocatalytic Oxidation of Aromatic Alcohol to Aldehyde in Aqueous Suspension of Brookite TiO(2)

WOS: 000260509000008

Photocatalytic oxidation of aromatic alcohols to aldehydes in aqueous suspension of home prepared titanium dioxide: 2. Intrinsic and surface features of catalysts

Some intrinsic electronic properties of home prepared (HP) TiO2 catalysts were investigated by diffuse reflectance spectroscopy and quasi-Fermi level measurements. These powders were used for carrying out the photocatalytic oxidation of benzyl alcohol to benzaldehyde and CO2 in water; the selectivity for aldehyde formation was enhanced by the addition of small amounts of ethanol, a typical hole trap. The values of band gap, valence band and conduction band edges are almost identical for all the HP samples in which anatase phase is predominant, whereas appreciable differences can be noticed for an HP sample containing high amount of rutile phase. A comparative ATR-FTIR study of the HP cataly…

Photocatalytic Selective Oxidation of 5-(Hydroxymethyl)-2-furaldehyde to 2,5-Furandicarbaldehyde in Water by Using Anatase, Rutile, and Brookite TiO2 Nanoparticles

5-(Hydroxymethyl)-2-furaldehyde (HMF) was selectively oxidized to 2,5-furandicarbaldehyde (FDC) in; aqueous medium by using home prepared (HP) anatase, rutile, and brookite TiO2 nanoparticles. HP samples were prepared via a sol-gel method by using TiCl4 as the TiO2 precursor. Commercial TiO2 catalysts were also used for, comparison. All samples were characterized by BET specific surface area, XRD, TGA, and SEM, and the reactivity results showed that HP catalysts are predominantly amorphous and give rise to selectivities toward FDC more than twice that of commercial and well crystallized catalysts.

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

WOS: 000256241700021

Polymer leaf of expanded material coated with titanium dioxide exhibiting photocatalytic activity, container and package for foodstuffs obtained from said polymer leaf

Waste-free electrochemical oxidation of alchools in water

We describe a new sol-gel molecular electrode made of a thin layer of organosilica doped with the nitroxyl radical TEMPO (2,2,6,6-tetrame-thylpiperidine-1-oxyl) electrodeposited on the surface of an ITO-coated glass and its employment as a selective and versatile oxidation catalyst in the electrochemical conversion of different alcohols to carbonyl compounds. Environmentally friendly water or a water/acetonitrile mixture buffered with bicarbonate is used as solvent. The electrode is highly stable and it can be reused for a prolonged period of time allowing easy separation from the products.

Alkaline treatment as a means to boost the activity of TiO(2)in selective photocatalytic processes

In this work, the activity enhancement of TiO(2)photocatalysts by alkaline treatment has been investigated. Commercial (BDH, U.K., anatase phase) TiO(2)samples, treated in alkaline solutions of NaOH at different concentrations and temperatures, were tested for the photocatalytic partial oxidation of 3-pyridinemethanol in water under UVA irradiation to form vitamin B-3. Photocatalyst characterization has been carried out by XRD, BET, TEM, TGA, photoluminescence, FTIR, Raman, DRS, EPR and photocurrent measurements. The alkaline-treated samples showed an increased activity of up to 7 times (by considering first order rate constant values) compared to untreated BDH and the superior performance …

Selective heterogeneous photocatalysis: examples of green photosyntheses

Photocatalytic selective oxidation of 4-methoxybenzyl alcohol to aldehyde in aqueous suspension of home-prepared TiO2 catalyst

The photocatalytic oxidation of 4-methoxy-benzyl alcohol to p-anisaldehyde (PAA) was performed in water with organic-free suspensions of home-prepared and commercial titanium dioxide (TiO2) catalysts. The nanostructured TiO2 samples were synthesised by boiling aqueous solutions of titanium tetrachloride (TiCl4), under mild conditions, for different times. The crystallinity increased with the boiling time. The 4-methoxybenzyl alcohol oxidation rate followed the same pattern but the highest yield (41.5 % mol) to PAA was found for the least crystalline sample, that showed a quantum efficiency of 0.116 %. A comparison with two commercial TiO2 samples showed that all the home-prepared catalysts …

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…

Halloysite Nanotube with Fluorinated Lumen: Non-Foaming Nanocontainer for Storage and Controlled Release of Oxygen in Aqueous Media

Halloysite clay nanotubes were selectivity modified by adsorbing perfluoroalkylated anionic surfactants at the inner surface. The modified nanotubes formed kinetically stable dispersions due to the enhanced electrostatic repulsions exercised between the particles. We proved that the modified nanotubes can be used as non-foaming oxygen nanocontainers in aqueous media. The gas release from supersaturated dispersions can be controlled by external stimuli and system composition. In conclusion, we managed to put forward an easy strategy to develop smart materials from natural nanoclays, which can endow important applications like the storage and delivery of gas.

Production of Aldehydes by Oxidation in Aqueous Medium with Selective Recovery of the Product by Means of Pervaporation

One-pot electrocatalytic oxidation of glycerol to DHA

Abstract One-pot, waste-free oxidation of glycerol to 1,3-dihydroxyacetone (DHA) was achieved by simply applying a small electric potential (1.1 V vs Ag/AgCl) to a glycerol solution in water buffered at pH 9.1 in the presence of 15 mol % TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl). Prolonging the reaction time affords comparable amounts of hydroxypyruvic acid.

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.

Structural insight on organosilica electrodes for waste-free alcohol oxidations

Organic modification of sol-gel catalytic glassy electrodes made of a thin layer of organosilica doped with nitroxyl radical TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) crucially enhances stability in the waste-free oxidation of alcohols to carbonyls in water. Structural comparison between analogous films made of organosilica and unmodified SiO2 shows that the origin of the pronounced stable activity of the ORMOSIL film lies in high hydrophobic and also in the pronounced low degree of hydrophilicity.

Ferulic Acid Oxidation Through Visible Light Induced TiO2 Photocatalysis

Kinetics of 4-Methoxybenzyl Alcohol Oxidation in Aqueous Solution in a Fixed Bed Photocatalytic Reactor

WOS: 000280384800004

Enhanced Mechanical Properties in Organofluorosilica Thin Films

Fluorinated hybrid organic-inorganic silicates (ORMOSIL) thin films display exceptional mechanical properties in terms of both hardness and elastic modulus that can be finely tuned by varying the angular velocity of the spin coating process. Hence, as traditional alkyl-modified silica xerogels generally show poor mechanical behavior, these materials offer a solution to a major limitation to applicability of ORMOSIL-based films.

Fabrication and Characterization of Dye-Sensitized Solar Cells

Among the next-generation solar cells, a predominant role is played by Dye sensitized solar cells (DSSC) based on ruthenium complexes as sensitizers. They take advantage of a photoelectrochemical system to transform solar radiation into electric energy. In fact, DSSCs represent a cost-effective alternative to traditional silicon-based photovoltaic devices and they do not require expensive and sophisticated apparatus for their fabrication. In this work, we have produced and tested ruthenium DSSCs. In particular, we have measured the main parameters of these cells, such as the electrical and power performances and the efficiency levels, at different irradiance levels and at different incident…

The chemical effects of molecular sol–gel entrapment

Chemical conversions within the cages of doped sol-gel porous oxides take place with unique advantages over reactions in solution as the glassy matrix has tremendous effects on the reactivity of the entrapped molecules. The chemical properties of sol-gel materials can be tailored in an immense range of values and chemists are increasingly achieving control on reactions taking place within these matrices, including crucially important photovoltaics. Highlighting recent major advancements, we show in this tutorial review how this is actually taking place.

Graphite-supported TiO2 for 4-nitrophenol degradation in a photoelectrocatalytic reactor

WOS: 000274769500044

A new class of heterogeneous Pd catalysts for synthetic organic chemistry

A new series of leach-proof nanostructured Pd(0) catalysts able to catalyze a number of fundamental organic transformations including C–C bond formation has been developed. Reactions in general proceed with high yield and often at completion, while the catalysts can be reused in further reaction runs. This establishes a new class of relevant solid catalysts for synthetic organic chemistry trademarked SiliaCat Pd0 Hydrogel.

Photocatalytic oxidation of nitrobenzene and phenylamine: Pathways and kinetics

WOS: 000245150800018

Selective photocatalytic oxidation of 4-substituted aromatic alcohols in water with rutile TiO2 prepared at room temperature

WOS: 000264978500012

Photochemically induced reactions on organic derivatives in the presence of titanium dioxide: a product study

A quantitative method of photoadsorption determination for irradiated catalyst in liquid–solid system

WOS: 000266963000002

Anatase photocatalyst with supported low crystalline TiO2: The influence of amorphous phase on the activity

Abstract In a previous study on commercial TiO2 nanoparticles (J. Soria et al.) we had shown that the superficial disordered layers influence their textural and reactivity features. In the present work we used well crystallized anatase particles (commercial TiO2, BDH) as support of different amounts of titania powders, prepared by TiCl4 hydrolysis and constituted by nanocrystals diluted into an amorphous matrix. The reactivity of these photocatalysts has been tested for the selective oxidation of 4-methoxybenzyl alcohol to aldehyde in aqueous suspension. The catalyst characteristics have been studied using adsorption-desorption isotherms, TEM, HRTEM, TGA, PL, DRIFT-IR, and 1H MAS-NMR spectr…

Synthesis of vanillin in water by TiO2 photocatalysis

Abstract The photoproduction of vanillin is studied in aqueous medium starting from trans-ferulic acid, isoeugenol, eugenol or vanillyl alcohol by using both commercial and home prepared TiO2 samples as photocatalysts and batch Pyrex photoreactors. The photo-oxidation at room temperature of these compounds produces vanillin with a selectivity ranging from 1.4 to 21 mol% with respect to the converted substrate. An investigation on the intermediates was performed in the case of trans-ferulic acid; for this substrate the most important intermediates were homovanillic acid, vanillyl mandelic acid, trans-caffeic acid, formic acid, acetic acid, and oxalic acid. The carbon mass balance, including …

Telloruro di Cadmio: Eldorado del fotovoltaico o insidia ambientale?

Influence of fluorine on the synthesis of anatase TiO2for photocatalytic partial oxidation: Are exposed facets the main actors?

Anatase TiO2 samples were synthesized in the presence of different amounts of HF acid with the aim of understanding the effect of the presence of fluorine on the photocatalytic activity. It is well known that the presence of fluoride ions influences the photocatalytic performance by adsorption on the surface of TiO2 and that they are capping agents in the control of specific exposed facets. The samples were characterized by X-ray diffraction (XRD), Raman spectroscopy, nitrogen adsorption–desorption measurements, scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-vis spectrophotometry, and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity was eva…

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…

Hydroxilation of benzoic acid and phenol in the presence of TiO2 photocatalysts: selectivity and kinetics

Photocatalytic oxidation of aromatic alcohols to aldehydes in aqueous suspension of home-prepared titanium dioxide

Abstract Oxygenated aqueous suspensions of home-prepared (HP) and commercial TiO2 catalysts were used in a batch photoreactor for carrying out the oxidation of benzyl alcohol (BA) and 4-methoxybenzyl alcohol (MBA) under different operative conditions. HP catalysts were synthesized from TiCl4 and underwent a hydrolysis treatment of different times under mild conditions. The textural characterization of catalysts was carried out with XRD, SEM observations, BET surface area and porosity measurements. For both alcohols the main oxidation products were the corresponding aromatic aldehydes and CO2. The HP catalysts exhibited selectivity values towards the aldehyde production up to 28% (BA convers…

Clean by Light Irradiation: Practical applications of supported TiO2

The effect of the surface disordered layer on the photoreactivity of titania nanoparticles

It is well known that the surface of metal oxide catalysts presents, usually, non-crystalline species containing impurities and low coordinated cations, which are observed in HRTEM images as a disordered layer of amorphous phase. Despite of being these species more accessible and less stable than the crystalline catalysts components, they have been rarely considered when analysing the catalyst activity. In this work, we have studied the effect of a treatment with HCl solution at pH = 0 on the characteristics of the disordered layer in two commercial anatase TiO2 samples, using techniques such as TGA, 1H MAS-NMR and HRTEM, and by determining these sample photocatalytic activity for the 4-nit…

Preparation, characterization and photocatalytic activity of Phtalocyanine-doped TiO2/ORMOSIL thin films

Nanostructured anatase TiO2 densified at high pressure as advanced visible light photocatalysts

This study reports on characterization and photoactivity of nanostructured TiO2 samples, which have been permanently densified under high pressures, up to 2.1 GPa. Commercial Mirkat 211 anatase has been used as a benchmark sample, in order to investigate the effect of unidirectional high pressure on structural, optical and photocatalytic properties of TiO2. Vibrational Raman spectroscopy shows that the treatment does not cause transitions among the different crystalline phases of titanium dioxide. UV-vis diffuse reflectance spectra reveal that increasing pressure gives rise to a shift of the absorption onset towards higher wavelength enhancing the photoactivity under visible radiation. Samp…

TiO2 Nanomaterials Used as Photocatalysts for Selective Heterogeneous Syntheses of Alcohols to Aldehydes in Water

Highly stable defective TiO2-x with tuned exposed facets induced by fluorine: Impact of surface and bulk properties on selective UV/visible alcohol photo-oxidation

Abstract Titanium dioxide samples were prepared in the presence of different amounts of fluorine via hydrothermal method. It has been found that the presence of fluoride influenced the physico-chemical properties of TiO2 in various ways as polymorphic form stability, surface hydroxylation, generation of hydroxyl radicals under irradiation and formation of Ti3+ centers and oxygen vacancies. The generation rate of OH radicals was investigated by the photoluminescence technique in the presence of terephthalic acid. X-ray diffractometry indicated that fluorine stabilized the anatase TiO2. X-Ray photoelectron spectroscopy (XPS) revealed the presence of fluorine on the surface and the shift of th…

ORMOSIL thin films: Tuning mechanical properties via a nanochemistry approach

The mechanical properties (hardness and elastic modulus) of organically modified silicate thin films can be finely tuned by varying the degree of alkylation and thus the fraction of six- and four-membered siloxane rings in the organosilica matrix. This opens the way to large tunability of parameters that are of crucial practical importance for films that are finding increasing application in numerous fields ranging from microelectronics to chemical sensing.

Visible-light-induced oxidation of trans-ferulic acid by TiO2 photocatalysis

Abstract The oxidation of trans-ferulic acid (C10H10O4) in aqueous TiO2 dispersion occurs via the formation of a charge-transfer complex on the TiO2 surface that is able to absorb visible light (λ ⩾ 400 nm). The main product is CO2, whereas secondary oxidation products are organic species such as vanillin, caffeic acid, homovanillic acid, and vanillylmandelic acid. Oxidation through the formation of a charge-transfer complex occurs only in the presence of specific TiO2 samples. Experiments in the absence of oxygen, in the presence of bromate ions and by using a phosphate-modified TiO2, have been carried out for investigating the reaction mechanism. In order to study the interaction between …

Sintesi di Vanillina tramite Reazione di Ossidazione Fotocatalitica con TiO2 in Fase Acquosa

Photocatalytic synthesis of piperonal in aqueous TiO2 suspensions

Home-prepared anatase, rutile, and brookite TiO2 for selective photocatalytic oxidation of 4-methoxybenzyl alcohol in water: reactivity and ATR-FTIR study

5th European Meeting on Solar Chemistry and Photocatalysis -- OCT 04-08, 2008 -- Palermo, ITALY

Heterogeneous photocatalysis: guidelines on experimental setup, catalyst characterization, interpretation, and assessment of reactivity

Soon after the publication of the first pioneering works on heterogeneous photocatalysis, the number of papers on this topic continuously increased. This intriguing field of research is very complex as it endows with an interdisciplinary overview that involves different aspects of chemistry, physics, material and environmental sciences. Even if photocatalytic applications in real processes are often difficult to be implemented and scaled-up, investigations at laboratory scale are easy to be performed, and in some cases they may give rise to misconceptions. For this reason, the present work aims to sum up most of the common experimental techniques and procedures generally used in heterogeneo…

Photocatalytic Oxidation of Aromatic Alcohols to Aldehydes in Aqueous Suspension of Home Prepared Titanium Dioxide. 1 Selectivity Enhancement by aliphatic alcohols

Oxygenated aqueous suspensions of home-prepared (HP) and commercial TiO2 catalysts were used in a batch photoreactor for carrying out the oxidation of benzyl alcohol (BA) and 4-methoxybenzyl alcohol (MBA) under different operative conditions. HP catalysts were synthesized from TiCl4 and underwent a hydrolysis treatment of different times under mild conditions. The textural characterization of catalysts was carried out with XRD, SEM observations, BET surface area and porosity measurements. For both alcohols the main oxidation products were the corresponding aromatic aldehydes and CO2. The HP catalysts exhibited selectivity values towards the aldehyde production up to 28% (BA conversion: 50%)…

CIGS PV Module Characteristic Curves Under Chemical Composition and Thickness Variations

This paper analyzes how the electrical characteristics of a CIGS photovoltaic module are affected by the chemical composition and by the thickness variations of the CIGS absorber. The electrical characteristics here considered are the short circuit current, the open circuit voltage, the efficiency and the power peak. The chemical composition is varied by tuning the ratio between gallium and indium. This analysis has been performed by means of the wxAMPS software, developed by the University of Illinois. The above variations have been taken into account on a PV module made of 72 cells. This analysis has been carried out employing a PV module mathematical model developed and implemented by th…

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

Heterogeneous photocatalysis and photoelectrocatalysis have been considered as oxidation technologies to abate unselectively noxious species. This article focuses instead on the utilization of these methods for selective syntheses of organic molecules. Some promising reactions have been reported in the presence of various TiO2 samples and the important role played by the amorphous phase has been discussed. The low solubility of most of the organic compounds in water limits the utilization of photocatalysis. Dimethyl carbonate has been proposed as an alternative green organic solvent. The recovery of the products by coupling photocatalysis with pervaporation membrane technology seems to be a…

Photocatalytic Selective Oxidation of 4-Methoxybenzyl Alcohol to Aldehyde in Aqueous Suspension of Home-Prepared Titanium Dioxide Catalyst

WOS: 000246040000026

Kinetics of photocatalytic degradation of pharmaceuticals in aqueous TiO2 suspension

(Photo)catalyst Characterization Techniques

Abstract This chapter reports on some characterization techniques that are commonly used for catalysts and photocatalysts. Brunauer–Emmett–Teller (BET), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), UV–visible (UV–Vis), photoluminescence (PL), and electrochemical characterization techniques are presented with experimental details and actual case studies from literature are discussed. The chapter starts with adsorption phenomena on (photo)catalysis and adsorption isotherms are presented. Then BET analysis technique and its applications in (photo)catalysis are explained. Morphological properties (SEM), functional groups, and the interaction of substrate (…

Photocatalytic oxidation of 4-methoxybenzyl alcohol to p-anisaldehyde in a fixed bed continuous reactor,

A reactor for photoelectrocatalytic oxidation of aromatic alcohols

Overview on oxidation mechanisms of organic compounds by TiO2 in heterogeneous photocatalysis

This review provides the reader with a general overview on heterogeneous photocatalytic oxidation mechanisms in the presence of TiO2, with a special address to conversion of aliphatic and aromatic organic species. The aim was to clarify the steps of the photo-oxidation of the various classes of compounds and to relate them with the properties of the catalysts and the experimental conditions used. Reactions carried out to perform complete degradation and photocatalytic partial oxidations have been deeply discussed. Recent isotopic studies highlighted new reaction pathways concerning partial oxidation of alcohols to aldehyde and oxidation of benzene while EPR investigations confirmed that not…

Enhancing Selectivity In Photocatalytic Formation Of P-Anisaldehyde In Aqueous Suspension Under Solar Light Irradiation Via Tio2 N-Doping

The photocatalytic partial oxidation of 4-methoxybenzyl alcohol to the corresponding aldehyde (p-anisaldehyde) was performed under simulated solar irradiation by using home prepared N-doped TiO2 catalysts. The photocatalysts were prepared by a sol–gel method, using TiCl4 as TiO2 precursor and NH4Cl, urea or NH4OH as N-doping sources. A commercial TiO2 (Degussa P25) was also used for comparison aims. The prepared catalysts were characterized by BET specific surface area, XRD, ESEM and UV-vis spectroscopy. The reactivity results show that (i) the doped catalysts are predominantly amorphous, and they show selectivity values far higher than those of the corresponding undoped ones and of well cr…

Photoadsorption determination for irradiated catalyst in liquid-solid system

Two-Dimensional Modeling of an Externally Irradiated Slurry Photoreactor

Abstract A batch cylindrical photocatalytic reactor, externally irradiated by 1–6 UV fluorescent lamps and containing a stirred slurry of polycrystalline TiO2, was modeled by coupling a modified Langmuir–Hinshelwood kinetics together with a two-dimensional light intensity field. The radiation field has been determined on the main assumptions of diffuse radiation, isotropic scattering and negligible backward reflected photon flow. The model has been applied to the photocatalytic oxidation of organic substrates which do not undergo homogeneous photochemical degradation. The model is characterized by the following four parameters: the kinetic constants of substrate adsorption, desorption and d…

Performance of a Continuousfixed Bed Photocatalytic Reactor for Selective Oxidation of 4-Methoxybenzyl Alcohol to Aldehyde in Organic-free Water

Photocatalytic oxidation of aromatic alcohols to aldehydes in aqueous suspension of home prepared titanium dioxide

In this paper some intrinsic electronic properties of home prepared (HP) TiO2 catalysts were investigated by diffuse reflectance spectroscopy and quasi-Fermi level measurements. These powders were used for carrying out the photocatalytic oxidation of benzyl alcohol to benzaldehyde and CO2 in water; the selectivity for aldehyde formation was enhanced by the addition of small amounts of ethanol, a typical hole trap. The values of band gap, valence band and conduction band edges are almost identical for all the HP samples in which anatase phase is predominant, whereas appreciable differences can be noticed for an HP sample containing high amount of rutile phase. A comparative ATR-FTIR study of…

Parametrical study of multilayer structures for CIGS solar cells

In this paper, a numerical analysis of relevant electrical parameters of multilayer structures for CIGS-based solar cells was carried out, employing the simulation software wxAMPS. In particular, we have focused on thin film cells having a ZnO:Al/ZnO/CdS/CIGS structure with a Molybdenum back contact. The aim of this work is to establish good theoretical reference values for an ongoing experimental activity, where our technology of choice is the single-step electrodeposition. In detail, we have analyzed how the main electrical properties change with the bang gap and the thickness of the absorber layer, for such a type of solar cell structure. Our results show that both efficiency and fill fa…

Determination of Photoadsorption Capacity of Polychrystalline TiO2 Catalyst in Irradiated Slurry

WOS: 000322711800002

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.

Nanochemistry Aspects of Titania in Dye Sensitized Solar Cells

We analyze the main nanochemistry factors affecting photovoltaic performance in TiO2 employed as wide bandgap semiconductor in dye-sensitized solar cells (DSCs). What is the best morphology of the oxide? Which processes yield the required structures? Finally, putting the discussion in the context of the rapid evolution of photovoltaic technologies, we argue that new titania nanostructures will form the basic component of second-generation solar modules based on dye solar cells.

Validation of a two-dimensional modeling of an externally irradiated slurry photoreactor

Abstract A two-dimensional model describing the behavior of a batch cylindrical photoreactor has been validated through a series of photocatalytic reactivity runs. The light intensity radiation field produced by 1–6 external UV fluorescent lamps was modeled together with Langmuir–Hinshelwood kinetics and 4-nitrophenol (NP) and Degussa P25 TiO 2 were used as the probe molecule and the catalyst, respectively. The experiments were carried out under different conditions of light intensity, photocatalyst amount and substrate concentration. The model parameters were the kinetic constant of substrate adsorption, desorption and degradation and the exponent of the power law expressing the kinetics d…

Combination of ozonation and photocatalysis for purification of aqueous effluents containing formic acid as probe pollutant and bromide ion

The treatment by advanced oxidation processes (AOPs) of waters contaminated by organic pollutants and containing also innocuous bromide ions may generate bromate ions as a co-product. In the present work heterogeneous photocatalysis and ozonation have individually been applied and in combination (integrated process) to degrade the organic compounds in water containing also bromide anions. The results show that: i) the sole photocatalysis does not produce bromate ions and in the case of its presence, it is able to reduce bromate to innocuous bromide ions; ii) the integration of photocatalysis and ozonation synergistically enhances the oxidation capabilities; and iii) in the integrated proces…

Photocatalytic process intensification by coupling with pervaporation

The integration of photocatalysis with a membrane separation process, in particular pervaporation, permits the recovery of valuable intermediate compounds (aromatic aldehydes) while they are produced avoiding their further degradation in the reactive ambient. In this way the yield and the conversion are enhanced. The coupling of the two processes is straightforward and the integration is complete even maintaining pervaporation and photocatalysis in two separate apparatuses provided that the process stream is continuously recycled at a sufficiently high flow rate. Additional advantages are: higher degree of purification of the aldehyde in the powder-free product stream, semicontinuous produc…

TiO2/ORMOSIL Thin Films Doped with Phthalocyanine Dyes:  New Photocatalytic Devices Activated by Solar Light

WOS: 000253222200065

Modelling of a recirculating photocatalytic microreactor implementing mesoporous N-TiO2 modified with graphene

Abstract The use of microreactors in (photo)catalytic processes offers new possibilities for studying and optimizing many mass and photon transfer limited reactions. In this study, we propose a scalable computational fluid dynamics (CFD) model for the prediction of photocatalytic degradation of a model pollutant (4-nitrophenol) using immobilized N-doped TiO2 grown over reduced graphene oxide (N-TiO2/rGO) in a photocatalytic microreactor working in continuous flow-recirculation mode. The mode of operation used in this study allows the reduction of mass transfer limitations inherent to heterogeneous photocatalytic reactions taking place on immobilized catalysts. A CFD model was developed for …

Sol-gel entrapped visible light photocatalysts for selective conversions

A general method to heterogenize, stabilize and significantly enhance the activity of selective visible light photocatalysts for aerobic oxidation of glycerol is devised. The new method makes use of the sol-gel encapsulation of photocatalytic species in silica-based matrices to afford leach-proof catalysts capable to afford valued products at low cost with little or no waste generation. In particular, the photocatalytic selective conversion of glycerol is performed in water solvent under ambient conditions with molecular oxygen as oxidant and visible light as the driving energy source, thereby meeting all requirements for a green chemical process. Entrapment of the semiconductor-based photo…

Preparation, thermal analysis and photoactivity of TiO2 samples

TiO2 Heterogeneous Photocatalysis as a Selective Tool for Organic Green Syhtneses

Influence of the Substituent on Selective Photocatalytic Oxidation of Aromatic Compounds in Aqueous TiO2 Suspensions.

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

Partial photocatalytic oxidation of glycerol in TiO2 water suspensions

2nd European Conference on Environmental Applications of Advanced Oxidation Processes -- SEP 09-11, 2009 -- Nicosia, CYPRUS

Self-assembled titania-silica-sepiolite based nanocomposites for water decontamination

WOS: 000264524200020

Oxidacíon fotocatalítica de alcoholes aromáticos. Influencia de la adicíon de atrapadores de huecos en la selectividad a aldehídos

Selective Heterogeneous Photocatalysis: Achievements and Challenges

Photodegradation of pharmaceutical drugs in aqueous TiO2 suspensions: mechanism and kinetics

WOS: 000251165800003

Photocatalytic green synthesis of piperonal in aqueous TiO2 suspension

Abstract Piperonal (heliotropine or 3,4-methylenedioxybenzaldehyde) has been synthesized by oxidizing piperonyl alcohol in aqueous UV-irradiated TiO2 suspensions. This compound was identified by GC–MS chromatography, 1H NMR and melting point determination. The other products of the photoprocess were 1,3-bis(3,4-(methylenedioxy)benzyl) ether (found in traces) and CO2, derived from the parallel pathway of photo-mineralization. Commercial and home-prepared TiO2 samples have been tested and the best selectivity (ca. 35%) was obtained by using the home-prepared ones. The reported green process allows to obtain an added value product (piperonal), upon partial oxidation of a cheap reagent.

Photocatalytic ozonation under visible light for the remediation of water effluents and its integration with an electro-membrane bioreactor

Abstract Photocatalysis and photocatalytic ozonation under visible light have been applied for the purification of a complex aqueous matrix such as the grey water of Masdar City (UAE), by using N-doped brookite-rutile catalysts. Preliminary runs on 4-nitrophenol (4-NP) solutions allowed to test the reaction system in the presence of a model pollutant and to afford the relevant kinetic parameters of the process. Subsequently, the remediation of grey water effluent has been evaluated in terms of the reduction of total organic carbon (TOC) and bacterial counts. The concentration of the most abundant inorganic ionic species in the effluent has been also monitored during reaction. Photocatalytic…

Selective Photocatalytic Oxidation of 4-Methoxybenzyl Alcohol to p-Anisaldehyde in Organic-Free Water in a Continuous Annular Fixed Bed Reactor

Photocatalytic oxidation of 4-methoxybenzyl alcohol to p-anisaldehyde was performed in water organic-free solutions by using a fixed bed continuous photoreactor containing Pyrex beads on which a TiO2 home prepared photocatalyst was supported. The influence of liquid flow rate, inlet alcohol concentration and catalyst amount on the photoprocess was studied. The highest selectivity to p-anisaldehyde was about 47% being CO2, the other main oxidation product; traces of 4-methoxybenzoic acid were also detected. The radiation field inside the photoreactor has been modelled by applying the Monte Carlo method thus allowing the determination of the local volumetric rate of photon absorption (LVRPA).…

Ossidazione selettiva di alcoli aromatici ad aldeidi in sospensioni acquose di TiO2 anatasio e rutilo

Influenza del Sostituente sulla Ossidazione Fotocatalitica Selettiva di Composti Aromatici

A PERVAPORATION PHOTOCATALYTIC REACTOR FOR THE GREEN SYNTHESIS OF VANILLIN

Abstract Pervaporation is the ideal membrane separation process to be coupled with photocatalysis for the green synthesis of vanillin from ferulic acid. In fact the operative conditions of the two processes are absolutely congruent and the integration is straightforward even operating with separate equipments. The utilization of a highly selective membrane allows the continuous recovery of vanillin by pervaporation from the reacting solution, so that its oxidative degradation is largely avoided and the yield is substantially enhanced. The effects of the main parameters are analyzed resorting to a mathematical model, which is validated by a comparison with the experimental data. In particula…

Visible Light Induced Oxidation of Ferulic Acid by TiO2 Photocatalysis

Oxidation of ferulic acid (C10H10O4) in aqueous medium occurs by using both commercial and home prepared TiO2 samples under visible light irradiation. Among the oxidation products vanillin was found with a selectivity ranging from 1 to 2% with respect to the converted substrate. By considering that TiO2 is unable to absorb visible light and ferulic acid does not react in the absence of TiO2, the observed photoactivity may be explained by the formation of a charge-transfer complex between ferulic acid and TiO2, being the complex able to absorb visible light. Among all the tested semiconductor oxides, only Merck anatase TiO2 does not perform the oxidation of ferulic acid under visible light i…

Nanomateriali a base di TiO2 come fotocatalizzatori per sintesi selettive di alcoli ad aldeidi in fase acquosa

Green Production of Aldehydes from Alcohols by Heterogeneous Photocatalysis

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.

Nanostructured rutile TiO2 for selective photocatalytic oxidation of aromatic alcohols to aldehydes in water

WOS: 000253100100022

Selective photocatalytic oxidation of 3-pyridinemethanol on platinized acid/base modified TiO2

TiO2 catalysts, modified with acidic or alkaline solutions and then platinized, were used for the partial photocatalytic oxidation of 3-pyridinemethanol to 3-pyridinemethanal and vitamin B-3 under environmentally friendly conditions. The reaction took place in water under UVA light and air oxygen. Catalysts were characterized by TEM, photoluminescence, DRIFT-IR, Raman, DRS, XPS, and photocurrent measurements. The photocatalytic activity results show that Pt loading of untreated samples leads to a significant activity improvement (hence product yield) as much as acid and alkaline treatments do. Moreover, the alkaline treated TiO2 samples exhibit a further increase in activity after loading w…

Photocatalysis: Applications

Heterogeneous photocatalysis is a sustainable technology mainly employed for water and air cleaning purposes. However, in the last two decades a lot of attention has been given to photocatalysis as an alternative route to be used in place of traditional industrial processes. The sustainability of photocatalysis mainly comes from the exploitation of renewable sources, such as solar light, and the possibility to avoid unsafe reagents/solvents and severe temperatures and pressures. In this chapter we give a critical presentation of some case studies concerning the use of heterogeneous photocatalysts, such as modified and bare TiO2, ZnO, ZnS, WO3, titanium silicalite, V2O5, polyoxometalates, Cd…

Influence of the Preparation Temperature on the Photocatalytic Activity of 3D-Ordered Macroporous Anatase Formed with an Opal Polymer Template

Even if many aspects of three-dimensionally ordered macroporous (3DOM) titania have been extensively studied, the interplay between the amorphous and crystalline components of their skeleton wall has not attracted too much attention, although it should strongly influence the properties of these materials. In order to gain new insight on this interplay, we have studied in detail the wall structure of three 3DOM titania samples prepared by heating the 3DOM titania precursor at 673, 773, and 873 K by X-ray diffraction, thermogravimetric analysis, differential thermal analysis, N2 adsorption/desorption, pore-size distribution, high-resolution transmission electron microscopy, and IHmagic-angle-…

Photocatalytic Active Polymer Expanded Materials Coated with TiO2 Used as Package for Foodstuffs

Proprietà ottiche e determinazione della resa quantica per sospensioni fotocatalitiche

Heterogeneous Photocatalysis: a Promising Tool for Green Organic Syntheses

The present work deals with a short review of some applications of photocatalysis to green organic synthesis of valuable products in mild experimental conditions and in the presence of water as solvent.

Selective photooxidation of ortho-substituted benzyl alcohols and the catalytic role of ortho-methoxybenzaldehyde

It has been recently reported by Palmisano et al. (2015) [1] that the oxidation of 2-methoxybenzyl alcohol (2-MBA) to 2-methoxybenzaldehyde (2-MBAD) proceeds in water under near-UV light with an unexpected catalytic effect of 2-MBAD. In order to investigate the catalytic role of aldehyde in photolytic oxidation of ortho-substituted benzyl alcohols (OSBAs), reactivity runs were carried out with 2-methylbenzyl alcohol (2-MeBA), 2-nitrobenzyl alcohol (2-NBA), 2-hydroxybenzyl alcohol (2-HBA) and 2-chlorobenzyl alcohol (2-CIBA) in the absence and in the presence of their corresponding aldehyde. None of those alcohols showed a measurable oxidation rate even in the presence of their aldehydes but …

Photocatalysis: a promising route for 21st century organic chemistry

One of the main goals of 21st century chemistry is to replace environmentally hazardous processes with energy efficient routes allowing to totally avoid the use and production of harmful chemicals and to maximise the quantity of raw material that ends up in the final product. Selective photocatalytic conversions will play a major role in this evolution and this account shows how photocatalysis is offering an alternative green route for the production of organics.

TiO2 Nanocristalline samples used to photo-oxidize aromatic alcohols to aldehydes

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 …

Optical properties of TiO2 suspensions: Influence of pH and powder concentration on mean particle size

WOS: 000250584100025

A preliminary investigation of total organic carbon variation in influent and effluent of Isfahan (Iran) water treatment plant, urban network and Fellman wells

In this work a series of total organic carbon (TOC) analyses were carried out to analyse the influent and the effluent of a water treatment plant providing Isfahan city in Iran. Other analyses were focused on the determination of TOC in the urban network and Fellman wells (in Isfahan and Dehaghan cities), in order to compare the water quality soon after the treatment with that of circulating water in the city network. Since it supplies water treatment plant, TOC content of Zayandehrood River was also compared with the treated water. The obtained results revealed that there were significant differences between TOC content of effluent of water treatment plant and that of the urban network (ma…

Visible-light driven oxidation of gaseous aliphatic alcohols to the corresponding carbonyls via TiO2 sensitized by a perylene derivative

Sensitized P25 TiO2 was prepared by wet impregnation with a home-prepared perylene dye, i.e., N,N?-bis(2-(1- piperazino)ethyl)-3,4,9,10-perylene-tetracarboxylic acid diimide dichloride (PZPER). Energy levels of PZPER were found to be compatible with those of TiO2 allowing fast electron transfer. The obtained catalyst has been characterized and used in the gas-phase partial oxidation of aliphatic primary and secondary alcohols, i.e., methanol, ethanol, and 2- propanol. The reaction was carried out under cut-off (?> 400 nm) simulated solar radiation in O2 atmosphere. The perylene derivative allowed a good absorbance of visible radiation thanks to its low optical energy gap (2.6 eV) which was …

NanoMORALs: Metal Nanoparticles Doped with Organic Molecules

A new class of nanosized metal–organic alloys (MORALs) has been synthesized for the first time. Silver nanoparticles doped with Cu(II) and Fe(III) phthalocyanines were thus synthesized in the presence of sodium dodecyl sulfate (SDS). The resulting materials were characterized by means of XRD, SEM, TEM coupled to energy dispersive X-ray analysis, and thermogravimetric analysis. No leaching of the photoactive dopant species was observed in water or in common organic solvents.

Selective oxidation of phenol and benzoic acid in water via home-prepared TiO2 photocatalysts: Distribution of hydroxylation products

Abstract The hydroxylation of phenol (a substrate containing an electron donor group) and of benzoic acid (a substrate containing an electron withdrawing group) has been carried out by the photocatalytic method in aqueous suspensions containing commercial or home prepared TiO2 samples. The aim of the work was to study the distribution of hydroxylation products when different photocatalysts were used and to correlate the selectivity to some physico-chemical features of the powders. The samples were characterized by X-ray diffraction, thermogravimetry, determination of crystalline phase percentage, specific surface area and zero charge point. The photoreactivity results indicate that the prod…

Tuning The Selectivity To Aldehyde Via Ph Regulation In The Photocatalytic Oxidation Of 4-Methoxybenzyl Alcohol And Vanillyl Alcohol By Tio2 Catalysts

Abstract The influence of pH on the photocatalytic partial oxidation of 4-methoxybenzyl alcohol (MBA) and vanillyl alcohol (VA) to their corresponding aldehydes in aqueous suspension under UVA irradiation was investigated by using poorly crystalline home-prepared and crystalline commercial TiO2 (BDH, Merck and Degussa P25) photocatalysts. The results clearly show as tuning pH can strongly impart selectivity and activity to photocatalytic processes which are often quite unselective in aqueous suspensions. It was found that pH effect on reaction rate and product selectivity strongly depended on TiO2 crystallinity and substrate type. In the case of MBA oxidation, photoreactivity and selectivit…

N-Doped Anatase/Rutile Photocatalysts for the Synthesis of Aromatic Aldehydes Under Ultraviolet and Solar Irradiation

N-doped anatase/rutile photocatalysts were prepared by a sol-gel method, using TiCl4 as TiO2 precursor and urea as N-dopant source. The catalysts required a thermal treatment at temperature higher than 300 degrees C to achieve actual nitrogen doping; this treatment also allowed obtaining crystalline and hydrophobic samples. Moreover, nitrogen doping modified the surface of samples by increasing the anatase to rutile phase ratio and hydrophilicity. The catalysts were characterized by BET specific surface area, XRD, ESEM, TGA, FT-IR, DRS and XPS measurements, with particular attention to the assessment of the N-doping effect. It was found that XPS analysis should be used together with DRS and…

Home-prepared anatase, rutile, and brookite TiO2 catalysts for selective photocatalytic oxidation of p-methoxybenzyl alcohol in water: reactivity and ATR-FTIR study

Photoelectrocatalytic selective oxidation of 4-methoxybenzyl alcohol in water by TiO2 supported on titanium anodes

The photoelectrocatalytic partial oxidation of 4-methoxybenzyl alcohol in aqueous solution irradiated by near-UV light was carried out in a three-electrode batch reactor. TiO2 films were either deposited by dip-coating of a TiO2 sol onto a Ti foil and subsequent calcination or generated on Ti plates by thermal oxidation in air at 400-700 degrees C. The effects of the anode preparation method and bias potential values on conversion and selectivity to the corresponding aldehyde were investigated. The photoelectrocatalytic results were compared with the photocatalytic and electrocatalytic ones. The results indicated that no reaction occurred during the electrocatalytic experiments, whereas the…

Heterogeneous Photocatalysis and Catalysis

Abstract General definitions of heterogeneous catalysis and photocatalysis are reported together with parameters to assess the catalytic and photocatalytic performances. Some features of catalytic and photocatalytic reactions, the importance of amorphous and crystalline phases of the solid photocatalysts, and reactors and photoreactors with the most important kinetic aspects are presented.

Unexpectedly ambivalent O-2 role in the autocatalytic photooxidation of 2-methoxybenzyl alcohol in water

An unusual autocatalytic photooxidation of 2-methoxybenzyl alcohol has been observed under UV irradiation in aqueous medium. The homogeneous oxidation is catalyzed by the corresponding aldehyde that is also the main oxidation product. The trend of alcohol disappearance rate matches the typical shape of an autocatalytic process, where a crucial and ambivalent role is played by the presence of molecular oxygen. Low oxygen concentrations give rise to a zero-order reaction since the beginning of irradiation, while higher amounts of oxygen reduce the alcohol oxidation rate until the aldehyde reaches a concentration high enough to speed up the alcohol's conversion. Experiments performed by varyin…