0000000000541467
AUTHOR
Sedat Yurdakal
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
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 …
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…
The influence of the anatase nanoparticles boundaries on the titania activity performance
Metal oxides structures, formed by ordered self-assembling of crystalline nanoparticles aggregates, are attracting growing attention in fields such as catalysis or solar cells. The properties of these structures are influenced not only by their morphology and nanoparticles composition but also by the assembled particles boundaries. In order to determine the influence of these boundaries on the structures properties, the present investigation has been devoted to study the characteristics of anatase nanoparticles boundaries in titania aggregates prepared by TiCl4 hydrolysis at low temperature. Proton magic angle spinning nuclear magnetic resonance and high resolution transmission electron mic…
Kinetics of 4-Methoxybenzyl Alcohol Oxidation in Aqueous Solution in a Fixed Bed Photocatalytic Reactor
WOS: 000280384800004
Graphite-supported TiO2 for 4-nitrophenol degradation in a photoelectrocatalytic reactor
WOS: 000274769500044
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
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…
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…
Preparation of Catalysts and Photocatalysts Used for Similar Processes
Abstract This chapter reports the main techniques used to synthesize powders and films of heterogeneous catalysts and photocatalysts, often used for similar processes. Traditional preparation processes of bulky (photo)catalysts including precipitation, sol–gel technique, hydrothermal or solvothermal method, solid-state reactions, and flame syntheses were briefly described. The sonochemical method and microwave irradiation technique were also considered. The syntheses of supported catalysts by different techniques, including deposition–precipitation, impregnation, and wet coating technologies were also described. Moreover, a survey is reported of methods to deposit thin films of catalysts on…
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…
Removal of Intermediate Compounds in a Photocatalytic Process
6th European Meeting on Solar Chemistry and Photocatalysis: Environmental Applications (SPEA6) -- JUN 13-16, 2010 -- Prague, CZECH REPUBLIC
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 from fundamentals to possible applications
This special issue of Catalysis Today Journal, is dedicated to the career of Prof. Vincenzo Augugliaro, University of Palermo, Italy, in the occasion of his retirement in 2015. Prof. Vincenzo Augugliaro was Full Professor of Transport Phenomena at the University of Palermo (Italy) since 1994. He contributed to the fol- lowing research fields: chemical absorption kinetics, biochemical reactor modelling, diffusional kinetics in metallizing alloys and heterogeneous photocatalysis; in this last field he investigated on chemical kinetics of heterogeneous photocatalytic systems, modelling of heterogeneous photoreactors, radiation field in absorbing-reacting media and application of heterogeneous …
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…
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
Glycerol Partial Oxidation in Aqueous Solution by Home Prepared TiO2 Photocatalyst
6th European Meeting on Solar Chemistry and Photocatalysis: Environmental Applications (SPEA6) -- JUN 13-16, 2010 -- Prague, CZECH REPUBLIC
(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 (…
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…
Anatase nanoparticles boundaries resulting from titanium tetrachloride hydrolysis
An important factor that governs solar energy transformation into electrical or chemical energy, when using nanoparticles-based devices, is the spatial location of traps limiting electron transport. Evidences have been presented indicating that the electron diffusion is strongly influenced by nanoparticle boundaries, whose characteristics depend on the particles preparation. In the present work we have studied the role of hydrated excess proton structures in the formation of anatase nanoparticles boundaries in samples prepared by TiCl4 hydrolysis at low temperature and strong acidic conditions. The samples, constituted by anatase nanocrystals but, mainly, by amorphous titania, are studied b…
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…
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.
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…
Economical aspects, toxicity, and environmental fate of cerium oxide
Abstract The present chapter reports some economical aspects of the cerium oxide market. Porter’s and PESTEL analyses have been used to evidence the strengths and weaknesses of the ceria market, along with the potentiality and opportunities within the years to come. The wide use of CeO2 nanoparticles in many applications requires to consider also issues related to their toxicity and environmental fate. In this regard, some contradictory reports in the relevant literature have been surveyed, thus highlighting the need for further and detailed investigation on these topics in order to propose effective strategies of risk assessment and environmental remediation.
TiO2/ORMOSIL Thin Films Doped with Phthalocyanine Dyes: New Photocatalytic Devices Activated by Solar Light
WOS: 000253222200065
Synthesis and characterization of titanium dioxide and titanium dioxide–based materials
Abstract The aim of the chapter is to describe some different preparation methods and characterization techniques for bare, supported, and coupled TiO2 samples used in different fields. Particular attention has been paid both to the fundamental aspects of the different TiO2 preparation and characterization methods and the practical applications that the results obtained can have. Various examples have been reported from the literature to demonstrate the usefulness that students and scientists working with TiO2-based materials in different research areas can derive from various characterizations.
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
Photodegradation of pharmaceutical drugs in aqueous TiO2 suspensions: mechanism and kinetics
WOS: 000251165800003
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).…
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.
Influence of Amorphous TiO2-x on Titania Nanoparticle Growth and Anatase-to-Rutile Transformation
Amorphous TiO2-x formed together with precursors and anatase nuclei, during TiCl4 hydrolysis at soft conditions, influences both crystal growth and phase stability. The highly defective nanoparticles of anatase grow by reaction of their basic hydroxyls with acidic ones of TiO2 precursor species. The growth of anatase crystals, however, is affected by their interactions with simultaneously formed amorphous TiO2-x which increasingly covers the particles hindering the anatase-precursor contact. The interactions among anatase and amorphous and precursor components have been studied by H-1-MAS (magic angle spinning) NMR spectroscopy. The interaction between acid and basic hydroxyls favors the fo…
Nanostructured rutile TiO2 for selective photocatalytic oxidation of aromatic alcohols to aldehydes in water
WOS: 000253100100022
Photoelectrocatalytic oxidation of 3-pyridinemethanol to 3-pyridinemethanal and vitamin B3 by TiO2 nanotubes
In this paper, the first photoelectrocatalytic (PEC) 3-pyridinemethanol oxidation to 3-pyridinemethanal and vitamin B-3 was investigated. To meet this aim, efficient nanotube structured TiO2 on a Ti plate as a photoanode was prepared by an anodic oxidation method in ethylene glycol and characterized by XRD, SEM, and photocurrent techniques. The effect of nanotube morphology, applied potential, Na2SO4 concentration, stirring speed of solution, and pH on the reaction activity and product selectivities were investigated. The TiO2 phase of all of the anodes was mainly the anatase one. The PEC activity, the intensity of the XRD peak and the photocurrent increased by increasing the nanotube lengt…
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…
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-…
Partial oxidation of aromatic alcohols via TiO2 photocatalysis: the influence of substituent groups on the activity and selectivity
Aromatic alcohols with substituent groups in different positions have been partially oxidised to the corresponding aldehydes in a photocatalytic system in order to investigate the influence of the substituents on reactivity and selectivity to aldehyde. To this aim benzyl alcohol, 2-methoxybenzyl alcohol, 3-methoxybenzyl alcohol, 4-methoxybenzyl alcohol, 2,4-dimethoxybenzyl alcohol, 4-hydroxybenzyl alcohol and 4-hydroxy-3-methoxybenzyl alcohol have been photocatalytically oxidised to their corresponding aldehydes in aqueous TiO2 suspensions under near-UV irradiation. Home-made and commercial rutile TiO2 samples were used as photocatalysts. The catalysts were characterized by XRD, BET, SEM, T…
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 …
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
Partial photoelectrocatalytic oxidation of 3-pyridinemethanol by Pt, Au and Pd loaded TiO2 nanotubes on Ti plate
Abstract The photoelectrocatalytic (PEC) oxidation of 3-pyridinemethanol to 3-pyridinemethanal and vitamin B3 was investigated by using Pt, Au and Pd loaded (as single or bimetallic) nanotube structured TiO2 on Ti plate in water under UVA irradiation. Nanotube structured TiO2 on Ti plate samples were prepared as anode by anodic oxidation method in ethylene glycol solution in different times, and then they were calcined at 500 °C to be obtained in crystalline form. The anodes were loaded with noble metals by electrochemical reduction method and characterized by XRD, XPS, SEM, and photocurrent techniques. The TiO2 on the plates was in the anatase phase. The loaded metals were in metallic form…
Aqueous selective photocatalytic oxidation of salicyl alcohol by TiO2 catalysts: Influence of some physico-chemical features
Abstract Partial photocatalytic oxidation of salicyl alcohol (2-hydroxybenzyl alcohol) to salicylaldehyde in water was investigated under environmental friendly conditions in the presence of home-prepared and commercial TiO2 (Merck and Aeroxide P25) samples under UVA irradiation. The photocatalysts were characterized by using BET, XRD, SEM and/or TEM techniques. The effects of crystallinity degree, pH (3–11) and presence of a hole trap (ethanol) on the photocatalytic activity and product selectivity were investigated. 4-Hydroxybenzyl alcohol was also used to study the influence of the position of the substituent group in the aromatic ring. High alcohols conversion and product selectivity va…
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…
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…
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…