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

WOS: 000260509000008

Brookite, the Least Known TiO2 Photocatalyst

Brookite is the least studied TiO2 photocatalyst due to the difficulties usually encountered in order to obtain it as a pure phase. In this review, a comprehensive survey of the different methods available for preparing brookite powders and films is reported. Attention has been paid both to the most traditional methods, such as hydrothermal processes at high temperatures and pressures, and to environmentally benign syntheses using water soluble compounds and water as the solvent. Papers reporting the photocatalytic activity of pure and brookite-based samples have been reviewed.

Junction Effect on the Photocatalytic Activity of Mixed-Phase TiO2 Nanoparticles

Active TiO2 photocatalysts were prepared under mild experimental conditions by thermohydrolysis of TiCl4 in pure water at 100 {degree sign}C. The preparation method is very simple and does not require the use of expensive thermal or hydrothermal treatments. Depending on the TiCl4/H2O ratio, pure rutile, binary mixtures of anatase and rutile or anatase and brookite, or ternary mixtures of anatase, brookite and rutile, can be obtained. 4-nitrophenol photodegradation was used to evaluate the photoactivity of the various powders. The high photocatalytic activity of the mixed samples was explained by the presence of junctions among different polymorphic TiO2 phases that allows an improved charge…

Preparation and photoactivity of nanocrystalline TiO2 powders obtained by thermohydrolysis of TiOSO4

Nanocrystalline TiO2 photocatalysts were synthesized in mild conditions by thermohydrolysis of TiOSO4 in water at 100 °C and post-calcination treatment at various temperatures. The TiO2 powders were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, specific surface area determinations, scanning electron microscopy and electron paramagnetic resonance measurements. The photoactivity of the samples was tested employing the photodegradation of 4-nitrophenol in liquid–solid regimen and the photooxidation of gaseous 2-propanol. The best results were obtained with the powder calcined at 600 °C for 10 h. Surprisingly, the not calcined sample was the most active for the abatement…

Photocatalytic and photoelectrocatalytic H2 evolution combined with valuable furfural production

In this work the photocatalytic (PC) and photoelectrocatalytic (PEC) reforming of furfuryl alcohol (FA) under environmental friendly conditions was investigated. Both H2 evolution and partial oxidation to furfuraldehyde were followed. For the first time TiO2 based photocatalysts were studied and the photocatalytic activity of home prepared photocatalysts was compared with that of commercial ones under both UVA and simulated solar irradiation. PEC tests were performed by using home prepared TiO2 nanotubes (TiO2 NTs) as photoanode and Pt free Ni foam as cathode to improve the Hydrogen Evolution Reaction (HER). Both the partial FA oxidation reaction rate and H2 evolution rate were normalized f…

Selective heterogeneous photocatalysis: examples of green photosyntheses

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…

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…

The role of different oxides as supports of an heteropolyacid in the catalytic and catalytic photo-assisted propene hydration

Photocatalytic partial oxidation of phenenthrene in green organic solvents

A Solar Photothermocatalytic approach for the CO2 conversion: Investigation of different synergisms on CoO-CuO/Brookite TiO2-CeO2 catalysts

Abstract The photoactive features of the least common polymorph of TiO2, i.e. brookite, were combined with the thermocatalytic redox ones of cerium oxide, focusing on the effects of the addition of small amounts of Co-Cu oxides for the solar CO2 conversion. By considering the characterization data, a surface segregation of the hosted metal oxides on the TiO2-CeO2 composite was evidenced, and their presence increased the amount of oxygen vacancies and improved the charge carriers separation. The bimetallic oxides-based sample was the most performing one in the photocatalytic carbon dioxide reduction at room temperature. The formation of carbon monoxide and methane was 5 and 0.5 μmol g−1h−1, …

Heterogeneous photocatalytic aqueous succinic acid formation from maleic acid reduction

This study reports the anaerobic reduction of maleic acid to succinic acid in aqueous dispersion of different TiO2 based photocatalysts. Some home prepared and commercial solids containing different polymorphic phases of TiO2 and loaded with Pt and Ru were compared at different acidic pHs. The aim of the work was to verify the feasibility of the process and to determine the best samples and the optimal experimental conditions of the reaction. The best selectivity towards succinic acid was 23.2 % at 70 % of maleic acid conversion. Fumaric acid was also formed as another high added value compound, and its quantity was related to the experimental conditions and the photocatalyst used.

Characterization of TiO2 thin films for photocatalytic applications

Photocatalysis in dimethyl carbonate green solvent: degradation and partial oxidation of phenanthrene on supported TiO2

Dimethyl carbonate (DMC) is here proposed – for the first time – as a green organic solvent for photocatalytic synthesis. In this work, the photocatalytic partial oxidation of phenanthrene in dimethyl carbonate (DMC) by using anatase TiO2 as the photocatalyst is described as paradigmatic example of a green synthetic process starting from polycyclic aromatic hydrocarbons (PAHs). For comparison, the same reaction carried out also in ethanol, 1-propanol or 2-propanol is reported. The use of DMC as the solvent allowed us to achieve 19% and 23% selectivity towards 9-fluorenone and 6H-benzo[c]chromen- 6-one, respectively. The proposed approach may represent both a new green synthetic process and …

Sintesi di Piperonale tramite fotocatalisi eterogenea in condizioni green

Preparation of N-doped TiO2: characterization and photocatalytic performance under UV and visibile light

Nanocrystalline N-doped TiO(2) samples were prepared by using TiCl(4) or TiOSO(4) as precursors. The powders were characterized by X-ray diffraction, BET specific surface area measurements, scanning electron microscopy, diffuse reflectance spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. The photocatalytic activity was tested using the photodegradation of 4-nitrophenol under UV and visible light.Some samples were more active than commercial Degussa P25. A shift of the absorption edge to a lower energy and a stronger absorption in the visible light region were observed in the samples obtained from TiCl(4). Two absorption edges were observed in the samples derived from T…

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…

Water Depollution by Advanced Oxidation Technologies

This chapter deals with water treatments by advanced oxidation processes (AOPs) based on chemical and photochemical reactions. The most used processes are described, and for each of them, the main reaction mechanisms, principles, advantages, drawbacks, performances and formation of by-products, coupled with technologies and their applications to waters and wastewater depollution, have been analysed, supporting the main results of studies published in the pertinent literature.

Synthesis of 9-fluorenone and 6H-benzo[c]chromen-6-one through photocatalytic oxidation of phenanthrene by TiO2 photocatalysis

Photocatalytic membranes based on TiO2 catalysts and fluorinated polymers for CO2 conversion

In this work, prepared TiO2–Nafion™-based membranes were used in a photocatalytic membrane reactor, operated in continuous mode, for converting CO2 to methanol.

Photocatalytic Properties of Nanostructured TiO2 Powders Obtained by Thermohydrolysis of TiOSO4

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…

Coupling of membrane and photocatalytic technologies for selective formation of high added value chemicals

Abstract This review presents a survey of some heterogeneous photocatalytic processes for the synthesis of high-value added compounds carried out in photocatalytic membrane reactors (PMRs). The two technologies can be easily integrated due to the similar conditions at which they usually operate. Furthermore, significant advantages derive from the coupling and in some cases also synergistic effects can be observed. These features have been highlighted for the photocatalytic syntheses reviewed along with engineering and design aspects investigated for some industrially relevant high-value added compounds. Notably, photocatalytic syntheses carried out in PMRs are still rare mainly because inte…

Photocatalytic CO2 reduction in gas-solid regime in the presence of bare or Cu-loaded TiO2 and water

Studies on Catalytic and catalytic photo-assisted propene hydration in the presence of H3PW12O40 supported on different oxides

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.

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

Sequential biological and photocatalysis based treatments for shipboard slop purification: A pilot plant investigation

This study investigated the treatment of a shipboard slop containing commercial gasoline in a pilot plant scale consisting of a membrane biological reactor (MBR) and photocatalytic reactor (PCR) acting in series. The MBR contributed for approximately 70% to the overall slop purification. More precisely, the biological process was able to remove approximately 40%, on average, of the organic pollution in the slop. Nevertheless, the membrane was capable to retain a large amount of organic molecules within the system, amounting for a further 30% of the influent total organic content removal. However, this affected the membrane fouling, thus resulting in the increase of the pore blocking mechani…

TiO2-induced photoisomerization of caffeic acid

CO2 conversion in a photocatalytic continuous membrane reactor

The reduction of CO2 with water by using photocatalysts is one of the most promising new methods for achieving CO2 conversion to valuable hydrocarbons such as methanol (MeOH). In this work, prepared TiO2-Nafion (TM)-based membranes were used in a photocatalytic membrane reactor, operated in continuous mode, for converting CO2 to methanol. By using the membrane with the best TiO2 distribution, a MeOH flow rate/TiO2 weight of 45 mu mol (g(catalyst) h)(-1) was measured when operating at 2 bar of feed pressure. This value is higher than those reported in most of the literature data to date. Moreover, methanol production is considered as a relevant advance over the existing literature results wh…

Semiconductor mixed oxides as innovative materials for the photocatalytic removal of organic pollutants

Abstract This work aims to provide a critical survey of the extensive literature concerning the potential applications of nanostructured mixed oxides for environmental remediation. In particular, our attention was focused on the feasibility to employ these materials as photocatalysts for the elimination of toxic organic pollutants contained in water and wastewater. The advantages and perspectives of the various nanocomposites are briefly discussed.

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…

PREPARATION AND CHARACTERIZATION OF BROOKITE TiO2 PHOTOCATALYSTS FOR POLLUTANTS DEGRADATION AND ORGANIC SYNTHESIS

Front Cover: (Photo)electrocatalytic Versus Heterogeneous Photocatalytic Carbon Dioxide Reduction (ChemPhotoChem 9/2021)

Influence of crystallinity and OH surface density on the photocatalytic activity of TiO2 powders

Abstract The aim of the work was to study the influence of crystallinity and OH surface density on the photocatalytic activity of two commercial and two home-prepared TiO 2 powders. The samples were characterized by X-ray diffraction (XRD), thermogravimetric analysis (TG) and electron paramagnetic resonance (EPR) measurements. The photoactivity of the powders was tested employing the photodegradation of 4-nitrophenol (4-NP) and the selective oxidation of 4-methoxybenzyl alcohol (4-MBA) to 4-methoxybenzaldehyde ( p -anisaldehyde) under UV irradiation. An anti-correlation between oxidant power and selectivity of the various samples was found. A higher rate of 4-NP degradation was exhibited by…

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

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…

Highly Active Photocatalytic TiO2 Powders Obtained by Thermohydrolysis of TiCl4 in Water

Highly active photocatalytic TiO2 samples were synthesized by thermohydrolysis of TiCl4 in water at 100 °C. Rutile, binary mixtures of anatase and rutile or anatase and brookite or ternary mixtures of anatase, brookite, and rutile were obtained depending on the TiCl4/H2O ratio. Rietveld refinements were employed to evaluate the crystalline phases and composition of the mixtures. The effect of the aging time on the phase composition was also studied. The band gap values of the samples were obtained by the diffuse reflectance spectra. The position of the flat band potentials of anatase, brookite, and rutile was determined measuring the photovoltage as a function of the suspension pH. From the…

Determination of the crystallinity of TiO2 photocatalysts

Abstract This study reports a new simple method to determine the crystallinity of anatase and rutile TiO2 photocatalysts. The crystallinity degree of various anatase and rutile samples was estimated by XRD analysis from the ratio among the full width at half maximum intensities of the main diffraction peaks of anatase or rutile and the (111) peak of CaF2 as internal standard. The photocatalytic activity of selected powders was tested employing the photodegradation of 4-nitrophenol in aqueous solution as probe reaction. The results showed that the photoactivity of the investigated samples increased with increasing crystallinity and crystallite size.

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…

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…

Preparation of Sm-loaded brookite nanoparticles and thin films

Surface processes in selective photocatalytic oxidation of hydroxybenzyl alcohols by TiO2 P25

Aryl aldehydes and acids are important industrial intermediates, but their synthesis from the corresponding alcohols often requires the use of high temperatures and harmful solvents and oxidant agents. Heterogeneous photocatalysis represents an interesting option for the partial oxidation of alcohols to aldehydes at room temperature using water as solvent. In this work, the partial photocatalytic oxidation of 2-hydroxybenzyl alcohol (salicyl alcohol) and 4-hydroxybenzyl alcohol to the corresponding aldehydes and acids has been compared, under environmental-friendly conditions, employing TiO2 P25 as photocatalyst in water. The selectivity to the corresponding aldehydes and acids, under the s…

H2 and value added chemicals from photocatalytic conversion of glucose

Commercial and home prepared bare and Pt-supported TiO2 samples were used as the photocatalysts for the aqueous aerobic and anaerobic photo-conversion of glucose at ambient pressure and temperature. H2 and valuable chemicals were the obtained products. The home prepared samples resulted more active than the commercial ones

Photocatalytic H2 production over inverse opal TiO2 catalysts

Abstract The influence of BiVO4 and CuO on the chemico-physical properties of TiO2-based systems is reported. The performances of these systems were investigated in the photocatalytic H2 production both under UV and solar light irradiation. The characterization data pointed out that the obtained TiO2 samples have highly porous inverse opal structures with interconnected macropores. Inverse opal TiO2 exhibited higher activity in the H2 production than the commercial TiO2 due to the peculiar porosity that allows photons to enter inside the photocatalyst. A further improvement in terms of photoactivity was verified by addition of increasing amounts of BiVO4. On the contrary a small CuO content…

Ossidazione fotocatalitica del glucosio in presenza di TiO2

A facile way to synthesize noble metal free TiO2 based catalysts for glycerol photoreforming

In this work anaerobic heterogeneous photocatalytic solar/UV light reforming of glycerol in aqueous media was performed with Pt-photodeposition and noble metal free modified TiO2 photocatalysts prepared through ball milling, a very simple and cheap coupled catalyst preparation method. Different amounts of Cu2O or 3% CuO were loaded on TiO2 using ball milling and during each run glycerol conversion, hydrogen and CO2 formed in the gas phase and 1,3-dihydroxyacetone (DHA) and glyceraldehyde (GA) in the liquid phase were determined. The results were compared with the aim to verify the effectiveness of Cu2O in replacing Pt. Using noble metal free photocatalysts, 33% glycerol conversion, 10.3% an…

A solar photothermo-catalytic combined process for the VOCs combustion and the subsequent CO2 valorization using noble metal-free catalysts

We here investigated a solar photothermo-catalytic combined process where the toluene (as volatile organic compound model) was first oxidized to CO2 which was subsequently converted into solar fuels in a second reactor. For this aim two noble-metal free catalytic systems were used, namely MnOx-ZrO2, which gave the best results for the toluene removal, and brookite TiO2-CeO2 mixed oxides which were the most efficient in the subsequent CO2 conversion. This latter reaction was further improved by the addition of small amounts of copper-based materials on brookite-ceria, acting as co-catalysts. The key point for both the examined reactions was the synergism between the thermocatalytic and the p…

A comparison between photocatalytic and catalytic oxidation of 2-Propanol over Au/TiO2-CeO2 catalysts

Abstract Photocatalytic and catalytic oxidation of 2-propanol, representative of volatile organic compounds (VOC’s), were compared over mixed TiO 2 –CeO 2 -based catalysts. The effect of different amounts of CeO 2 and the presence of gold (1 wt%) on TiO 2 was investigated. In the photocatalytic oxidation CeO 2 had a negative effect on the performance towards the alcohol conversion of both TiO 2 –CeO 2 and Au/TiO 2 –CeO 2 catalysts, being Au/TiO 2 the most active system. On the contrary mixed TiO 2 –CeO 2 and Au/TiO 2 –CeO 2 samples showed a higher catalytic oxidation efficiency for 2-propanol conversion compared to the single oxides. In this case Au/CeO 2 catalyst had the best performance. …

Photocatalytic synthesis of piperonal in aqueous TiO2 suspensions

TiO2 photocatalysts prepared by thermohydrolysis of TiCl4 in aqueous solutions

Abstract Nanostructured TiO 2 photocatalysts were synthesized by thermohydrolysis of TiCl 4 at 100 °C in various aqueous solutions. Anatase or rutile, binary mixtures of anatase and rutile or anatase and brookite, and ternary mixtures of anatase, brookite and rutile were obtained depending on the hydrolysis solution. The most efficient catalysts consisted of ternary mixtures of the three polymorphic TiO 2 phases.

Photocatalytic behaviour of metal-loaded TiO2 aqueous dispersions and films

Abstract Titanium dioxide nanoparticles loaded with Ce, Co, Eu, Sm, W and Yb species were prepared by coprecipitation in mild conditions using TiCl 4 as precursor with the aim to enhance the photocatalytic activity, especially under visible light irradiation. The photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), specific surface area (SSA) determination and UV–Vis diffuse reflectance spectroscopy. The photocatalytic activity of the powders of pure and loaded TiO 2 was investigated by employing the photodegradation of 4-nitrophenol as probe reaction in a liquid–solid system. Loading with suitable amounts of W, Co and Sm resulted in a significan…

Photocatalytic and photothermocatalytic applications of cerium oxide-based materials

Abstract Cerium dioxide (CeO2) presents unique properties as the special electronic and optical properties of the 4f electrons, the capacity to form nonstoichiometric oxygen-deficient CeO2 − x oxides, the high oxygen mobility, and the reversible transformation between Ce4 + and Ce3 + that make it interesting for photocatalytic applications. CeO2 is a wide bandgap semiconductor (3.0–3.4 eV), but different approaches as combination with oxides, deposition of noble metals, doping with metal and nonmetal species, and the formation of surface defects have been adopted to extend its absorption towards the visible region with the aim to improve its photocatalytic performance. Cerium oxide-based ma…

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

Photocatalytic conversion of glucose was carried out in aqueous suspensions in the presence of dfifferent commercial and home prepared TiO2 samples functionalized with a commercial heteropolyacid. Different reaction extents and distribution of intermediate oxidation products were observed depending on the photocatalyst.

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

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

Sintesi e caratterizzazione di polveri e film di TiO2

(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 (…

Nanocrystalline TiO2 Photocatalysts Obtained by Thermohydrolysis of TiCl4 in Aqueous Solutions

Photocatalytic Solar Light H 2 Production by Aqueous Glucose Reforming

Formation of high added value chemicals by photocatalytic treatment of biomass

The depletion of fossil fuel requires the search for alternative renewable feedstock and environmentally friendly methods for the production of high value-added compounds and fuels. In this context, the efficient use of biomass has emerged as a significant research field as it represents an alternative green and renewable carbon source. Various technologies have been explored for this purpose and heterogeneous photocatalysis represents a valid alternative to the catalytic methods since it can be carried out under mild experimental conditions without the addition of harmful oxidizing agents. Different biomass components have been used as the starting materials, and many valuable chemicals h…

Green Organic Reactions by TiO2 Photocatalysis

This contribution 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.

Preparazione e fotoattività di rutilo e brookite ottenuti per termoidrolisi di TiCl4

Synthetic Green Chemistry through Heterogeneous Photocatalysis

This contribution deals with a short review of some application of TiO2 to green organic synthesis. In particular to selective oxidation of aromatic alcohols under mild conditions.

Catalytic applications of TiO2

Abstract The use of TiO2 as heterogeneous catalyst and/or active support for metals or other oxides is here reported. Many reactions of industrial relevance involve, in fact, titania-based catalysts, among them, NOx abatement, Fischer–Tropsch and water–gas shift, Deacon and Claus processes, hydrodesulfurizations and hydrogenations, selective reductions and selective oxidations. This chapter aims to discuss the main applications of TiO2, in its different forms, as effective support or catalyst for thermocatalytic and photo-thermocatalytic reactions, focusing on the role of its structural and physicochemical properties on the catalytic performance (activity, selectivity, stability).

Selective Photocatalytic Production of Aldehydes

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…

Preparation and photoactivity of nanostructured anatase, rutile and brookite TiO2 thin films

Photoactive films consisting of pure anatase, brookite or rutile TiO2 were prepared by dip coating from water dispersions obtained by using TiCl4 as the precursor under similar mild experimental conditions

Inorganic gels as precursors of TiO2 photocatalysts prepared by low temperature microwave or thermal treatment

Abstract A simple procedure for preparing active TiO2 photocatalysts is presented. The starting materials were unusual TiO2 gels formed from TiCl4. The use of microwaves for a very short time enhanced the TiO2 crystallinity preventing an increase of particle size and minimizing the decrease of specific surface area. This result makes this preparation very attractive. The formation of the gels was monitored through measurements of viscosity. All the samples were characterized by means of X-ray diffraction, diffuse reflectance spectroscopy and BET specific surface area measurements. The photoactivity of the samples was evaluated using the photodegradation of 4-nitrophenol in liquid–solid regi…

Photoactivity under visible light of metal loaded TiO2 catalysts prepared by low frequency ultrasound treatment

Abstract Visible-light responsive bare and metal loaded (Pt, Ag, Rh, Pd) TiO 2 photocatalysts were prepared by using a simple ultrasound treatment. This method induced bulk oxygen deficiency resulting in a narrowing bandgap (from 3.18 to 3.04 eV) and in visible light absorption. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), BET specific surface area (SSA) and pore size distribution (PSD), UV–vis diffuse reflectance spectroscopy (DRS), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity of the samples was evaluated by using the 4-nitrophenol oxidation reaction and the photocatalytic oxidation of glucose w…

Preparazione, Caratterizzazione e Fotoattività di Film di TiO2

Electron and Energy Transfer Mechanisms: The Double Nature of TiO2 Heterogeneous Photocatalysis

Photocatalytic chemical transformations in the presence of irradiated TiO2 are generally considered in terms of interfacial electron transfer. However, more elusive energy-transfer-driven reactions have been also hypothesized to occur, mainly on the basis of the indirect evidence of detected reaction products whose existence could not be justified simply by electron transfer. Unlike in homogeneous and colloidal systems, where energy transfer mechanisms have been investigated deeply for several organic syntheses, understanding of similar processes in heterogeneous systems is at only a nascent level. However, this gap of knowledge can be filled by considering the important achievements of syn…

Preparation of photocatalytic brookite thin films

Pure brookite films were deposited from a brookite dispersion obtained by peptizing a mixture brookite–rutile prepared by thermolysis of TiCl4 in a HCl solution. The films were characterised by X-ray diffraction and Raman spectroscopy. The photoactivity of the samples was tested by using the photo-oxidation of 2-propanol in gas–solid regime as a probe reaction. The brookite films efficiently degraded 2-propanol under UV illumination.

Preparazione e caratterizzazione di fotocatalizzatori a base di TiO2

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…

Photocatalytic oxidation in green organic solvent: the case study of water-insoluble phenanthrene

PHOTOCATALYTIC ACTIVITY OF TIO2 IN ITS POLYMORPHIC FORMS ANATASE, BROOKITE AND RUTILE

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…

(Photo)electrocatalytic Versus Heterogeneous Photocatalytic Carbon Dioxide Reduction

The present review summarizes some of the main results achieved in electrochemical, photocatalytic, and (photo)-electrocatalytic systems for the reduction of carbon dioxide. After a preliminary survey of the electrocatalytic and photocatalytic systems in terms of materials used, efficiencies, operating conditions, and product distribution, it is shown how the combination of the two approaches affords often higher efficiency than the single technologies and allows better control of the product distribution. In fact, the peculiar energetic distribution at the interface of irradiated semiconductors under opportune electrical bias enables enhancement of the spatial separation of the photogenera…

Effect of the addition of different doping agents on visible light activity of porous TiO2 photocatalysts

Abstract The influence of the addition of different doping agents (N, W and Hf) on the macroporous TiO2 photoactivity toward the Rhodamine B degradation and ethanol photo-oxidation was evaluated. The samples were characterized by XRD, XPS, SEM, TEM, N2 adsorption-desorption, UV–vis Diffuse Reflectance and Photoluminescence spectroscopies to study also the changes in the physico-chemical properties due to the presence of dopants. The photonic effect and the high ordered porous structure of the macroporous TiO2 that lead to increase the path length of the light, were the key factors that allow to enhance the catalytic activity towards the dye and VOC degradation under visible and solar light …

Characterisation and photoactivity of nanostructured TiO2 obtained by hydrolysis of TiCl4

N-TiO2 Photocatalysts highly active under visible irradiation for NOX abatement and 2-propanol oxidation

N-doped TiO2 powders were prepared by two different sol-gel methods. Samples were characterised by X-ray diffraction (XRD), BET specific surface area measurements (SSA), scanning electron microscopy (SEM), diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS) and Electron Paramagnetic Resonance (EPR). XPS measurements revealed a signal at 400 eV assignable to nitrogen in the form of Ti-N-O. EPR signals are attributed to molecular NO trapped with cavities/defects possibly interacting with oxygen vacancies. The photocatalytic activity under UV and visible light was determined following the abatement of NOx and the photodegradation of 2-propanol in gas-solid systems. N…

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.

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…

Preparation, thermal analysis and photoactivity of TiO2 samples

TIO2 brookite: Properties, synthesis and applications

Brookite is one of the less studied polymorphic phases of titanium dioxide. Indeed, synthetic procedures affording brookite as a pure phase were not straightforward and have been only recently optimized. For this reason, brookite has received particular attention in the last years, especially as a promising photocatalytic material for environmental remediation and for the synthesis of valuable organic products. The present chapter will review the main synthetic methods reported in literature to produce brookite as a pure phase or mixed with rutile and/or anatase. Morphological, structural and electronic properties both of pure or variously modified brookite will be presented. The particular…

TiO2 Heterogeneous Photocatalysis as a Selective Tool for Organic Green Syhtneses

Photocatalytic Isomerization of Caffeic Acid and its Cyclization to Esculetin

tThe photoisomerization of trans-caffeic acid to cis-caffeic acid has been studied in the presence of N2in homogeneous aqueous solutions and in suspensions of various TiO2catalysts. The results supportedthe hypothesis of an energy transfer process from TiO2 to the substrate due to the recombination of the photogenerated electron–hole pairs.

Exploring the photothermo-catalytic performance of brookite tio2-ceo2 composites

The thermocatalytic, photocatalytic and photothermo-catalytic oxidation of some volatile organic compounds (VOCs), 2-propanol, ethanol and toluene, was investigated over brookite TiO2-CeO2 composites. The multi-catalytic approach based on the synergistic effect between solar photocatalysis and thermocatalysis led to the considerable decrease in the conversion temperatures of the organic compounds. In particular, in the photothermo-catalytic runs, for the most active samples (TiO2-3 wt% CeO2 and TiO2-5 wt% CeO2), the temperature at which 90% of VOC conversion occurred was about 60 &deg

Photocatalytic properties of TiO2 doped with metal and non metal species

Photocatalytic abatement of organic compounds using home prepared TiO2 as photocatalysts

Efficient H2 production by photocatalytic water splitting under UV or solar light over variously modified TiO2-based catalysts

Abstract This paper focused for the first time on the comparison between three different approach to modify the chemico-physical properties of TiO2-based photocatalysts and their effect in the H2 production by photocatalytic water splitting both under UV and solar light irradiation, under the same experimental conditions. The application of pulsed laser irradiation to aqueous TiO2 suspensions (first approach) induced structural transformations both on the bulk and on the surface of TiO2, boosting the H2 production, under UV light irradiation, of almost three times (20.9 mmol/gcat·h) compared to bare TiO2 (7.7 mmol/gcat·h). The second strategy was based on a templating method to obtain TiO2 …

Confronto tra attività catalitica e fotocatalitica dell’eteropoliacido di Keggin H3PW12O40 supportato su ossidi o su nanotubi di carbonio

Catalytic and catalytic photo-assisted dehydration of 2-propanol to form propene in gas-solid regime at atmospheric pressure and 80°C was carried out by using a Keggin heteropolyacid H3PW12O40 (PW12) supported on different oxides. Binary materials have been prepared by impregnation of PW12 on different commercial and home prepared supports (TiO2, SiO2 or carbon nanotubes). The supported Keggin PW12 species played a key role both for the catalytic and the photo-assisted catalytic reactions, due to their strong acidity and ability to form strong oxidant species under UV irradiation, respectively. The contemporary presence of heat and UV light improved the activity of almost all POM supported …

Photocatalytic oxidation of trans-ferulic acid to vanillin on TiO2 and WO3-loaded TiO2 catalysts

Abstract The photocatalytic oxidation of trans-ferulic acid to vanillin in water has been studied by using various TiO2 and WO3-loaded TiO2 samples as catalysts. Different values of selectivity were obtained depending on the physico-chemical properties of the single samples and a vanillin selectivity of 10% was reached in the presence of the commercial TiO2 Merck. Higher selectivity values were obtained by impregnation of TiO2 with H2WO4 followed by calcination. The increased production of vanillin exhibited by the obtained WO3-loaded TiO2 powders was attributed to a reduced further oxidation of the aldehyde caused by the presence of the practically inactive tungsten trioxide hydrate on the…

Highly active photocatalytic TiO2 powdwers obtained by thermohydrolysis of TiCl4 in water

Highly active photocatalytic TiO2 samples were synthesized by thermohydrolysis of TiCl4 in water at 100 °C. Rutile, binary mixtures of anatase and rutile or anatase and brookite, or ternary mixtures of anatase, brookite and rutile were obtained depending on the TiCl4/H2O ratio. Rietveld refinements were employed to evaluate the crystalline phases and composition of the mixtures. The effect of the aging time on the phase composition was also studied. The band gap values of the samples were obtained by the diffuse reflectance spectra. The position of the flat band potentials of anatase, brookite and rutile was determined measuring the photovoltage as a function of the suspension pH. From thes…

Selective Heterogeneous Photocatalysis: Achievements and Challenges

Catalytic and photothermo-catalytic applications of TiO2-CoOx composites

Objective: The necessity to have green and sustainable industrial processes has promoted new technologies for air and water purification together with the research of new energy sources. In this contest, the TiO2-based photocatalysis can be considered a promising route for both environmental applications aIn this work, we have investigated the photocatalytic performance of TiO2-CoOx composites on both photooxidation and photoreduction reactions. Specifically, we have compared the performance of the composites in the thermo-catalytic, photo-catalytic and photothermal-catalytic oxidation of ethanol chosen as model volatile organic compound (VOC) and in the photocatalytic hydrogen production …

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.

Visible light photocatalytic activity of macro-mesoporous TiO2-CeO2inverse opals

Macro-mesoporous TiO2 inverse opal materials were synthesized and they were tested as photocatalysts under visible light irradiation. The influence of cerium oxide addition towards the Rhodamine B (RhB) photodegradation activity was evaluated. Structural, textural, spectral and surface properties of the TiO2-CeO2 inverse opal nanocomposites were studied by XRD, XPS, SEM, TEM, N2 adsorption-desorption, Diffuse Reflectance UV–vis and Photoluminescence spectroscopies. Compared to commercial TiO2 anatase, the macro-mesoporous TiO2 inverse opal exhibited six times higher kinetic rate constant in the RhB degradation under visible light irradiation. The good photocatalytic activity was related to …

Reduced grey brookite for noble metal free photocatalytic H2evolution

Herein we introduce for the first time a reduced “grey” brookite TiO2 photocatalyst, produced by thermal hydrogenation of brookite nanoparticles, that shows a remarkable noble metal free photocatalytic H2 evolution. Its activity is substantially higher than that of other TiO2 polymorphs, i.e. anatase or rutile, comparably sized and activated by hydrogenation under optimized conditions. Along with brookite powders, an oriented brookite single crystal was investigated as a defined surface to confirm the effects of the hydrogenation treatment. By a combination of electron paramagnetic resonance (EPR), electron and X-ray characterization techniques applied to the powders and single crystal, we …

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…

Brookite, the least known TiO2 photocatalyst, Catalysts

Brookite is the least studied TiO2 photocatalyst due to the difficulties usually encountered in order to obtain it as a pure phase. In this review, a comprehensive survey of the different methods available for preparing brookite powders and films is reported. Attention has been paid both to the most traditional methods, such as hydrothermal processes at high temperatures and pressures, and to environmentally benign syntheses using water soluble compounds and water as the solvent. Papers reporting the photocatalytic activity of pure and brookite-based samples have been reviewed.

Selective (photo)catalytic formation of 2-propanol from propene by using an heteropolyacid supported on different oxides

Selective aqueous oxidation of aromatic alcohols under solar light in the presence of TiO2 modified with different metal species

AbstractA set of metals modified TiO2 photocatalysts were prepared starting from titanium tetraisopropoxyde and different metal precursors to study the influence of the addition of the various foreign agents on the physico-chemical and photocatalytic properties of the catalysts. The powders were characterized by X-ray diffraction, Raman spectroscopy, specific surface area measurements, scanning electron microscopy, energy dispersive X-ray spectroscopy, UV–Vis diffuse reflectance spectroscopy, photoluminescence, temperature programmed desorption after CO2 adsorption. The photocatalytic activity was evaluated using as probe reactions the partial oxidation of three aromatic alcohols: benzyl al…

Photochemical and photocatalytic isomerization of trans -caffeic acid and cyclization of cis -caffeic acid to esculetin

Abstract The photoisomerization of trans-caffeic acid to cis-caffeic acid has been studied in the presence of N2 in homogeneous aqueous solutions and in suspensions of various TiO2 catalysts. The results supported the hypothesis of an energy transfer process from TiO2 to the substrate due to the recombination of the photogenerated electron–hole pairs. The differences among the measured photostationary [cis]/[trans] ratios have been attributed to the different physico-chemical properties of the catalysts. In particular, the lowest ratio measured in the presence of Merck TiO2 was ascribed to the very low adsorption of trans-caffeic acid onto the surface of this sample. In the presence of O2 a…

Preparazione di fotocatalizzatori a base di TiO2 brookite drogati con samario

TiO2 photocatalysts prepared by thermohydrolysis of TiCl4 solutions

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

Preparation and photoactivity of samarium loaded anatase, brookite and rutile catalysts

Abstract Pure and samarium loaded anatase, brookite and rutile nanopowders were synthesized by thermohydrolysis of TiCl 4 . The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), specific surface area (SSA) determination, UV–vis diffuse reflectance spectroscopy (DRS), atomic force microscopy (AFM), contact angle (CA) measurements and photoluminescence (PL) spectroscopy. The photocatalytic activity of pure and Sm-loaded TiO 2 polymorphs was investigated by employing the photodegradation of 4-nitrophenol as probe reaction in a liquid-solid system. Loading with Sm resulted in an improvement of the photoreactivity of the three TiO 2 polymorphs. The benefi…

Green Production of Aldehydes from Alcohols by Heterogeneous Photocatalysis

Synthesis and Characterization of TiO2 Deposited on Silica

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.

Sintesi di TiO2 anatasio in presenza di HF: studio delle proprietà strutturali e fotocatalitiche

In questo lavoro viene riportata la sintesi di TiO2 anatasio in presenza di soluzioni contenenti quantità diverse di HF allo scopo di ottenere campioni con proprietà strutturali diverse e la valutazione dell’attività fotocatalitica in reazioni liquido-solido e gas-solido.

The influence of the catalyst on the photacatalytic synthesis of vanillin

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

H3PW12O40 SUPPORTED ON DIFFERENT OXIDES: INFLUENCE OF THE SUPPORT ON THE CATALYTIC AND CATALYTIC PHOTO-ASSISTED PROPENE HYDRATION

Photocatalytic activity of nanocrystalline TiO2 (brookite, rutile and brookite-based) powders prepared by thermohydrolysis of TiCl4 in aqueous chloride solutions

Abstract Nanocrystalline TiO2 powders were synthesized by thermohydrolysis of TiCl4 in HCl or NaCl aqueous solutions. Rutile, mixtures of brookite and rutile or mixtures of anatase, brookite and rutile were obtained depending on the acidity of the medium. Crystalline phases and composition of the mixtures were identified by using XRD analysis. Pure brookite nanoparticles, separated from the mixtures of brookite and rutile by simple peptization with water, were stable against transformation to rutile up to 750 °C. The prepared TiO2 powders were characterized by thermal analysis, diffuse reflectance spectroscopy and BET surface area determinations. The band gap of bulky brookite was estimated…

Hyperactive TiO2 Photocatalyst Obtained by Microwave Treatment

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

Commercial and home prepared TiO2 samples were functionalized with a commercial Keggin heteropolyacid (HPA) H 3PW12O 40 (PW12) or with a hydrothermally home prepared K 7PW11O 39 salt (PW11). All the materials were characterized by specific surface area measurements (BET), XRD analyses, Raman, DRS along with SEM observations and they have been used for glucose photocatalytic conversion in an aqueous suspension. Different reaction extents and distribution of intermediate oxidation products were observed depending on the photocatalyst. Gluconic acid, arabinose, erythrose and formic acid were observed as oxidation products when bare TiO2 or HPA/TiO2 composite materials were used. Glucose isomer…

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

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

Inverse opal TiO2 as visible-light driven photocatalysts

Semiconductor photocatalysts have attracted a great deal of attention due to their potential application in environmental remediation. Titanium dioxide has been extensively investigated as the most promising photocatalyst. To improve the optical response of TiO2 in the visible region, Inverse Opal TiO2 has been recognized as an efficient photocatalyst due to its unique properties in terms of uniformly ordered and interconnected macroporous architecture.

TiO2-CeO2 based catalysts for photocatalytic oxidation of VOC and water splitting reactions

Photocatalysis with TiO2 is one of the most promising green process for the decomposition of organic pollutants and the hydrogen production . Photo-oxidation of 2-propanol, representative of volatile organic compounds (VOC) and photo-catalytic water splitting for H2 production were investigated over TiO2 catalysts doped with a metal (Au and Ag at 1wt. %) and/or ceria (10 wt.%).

Studio delle proprietà acido-base superficiali e fotoattività di catalizzatori nanostrutturati costituiti da TiO2

Preparation of photocatalytic nanostructured TiO2 thin films

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…

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…

Fotocatalizzatori Ottenuti per Termoidrolisi di TiCl4

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…

Photocatalytic activity of nanocrystalline TiO2 (brookite, rutile and brookite-based) powders

RIDUZIONE FOTOCATALITICA DI CO2 IN SISTEMI GAS-SOLIDO IN PRESENZA DI TiO2 PURO E DROGATO CON RAME

Absolute crystallinity and photocatalytic activity of brookite TiO2 samples

Abstract This study reports a method to determine the absolute crystallinity of partly crystalline brookite TiO2 photocatalysts. A natural, a commercial and various home-prepared brookite powders were characterized by X-ray diffraction analysis, Raman spectroscopy, scanning electron microscopy, UV–vis diffuse reflectance spectroscopy and nitrogen adsorption measurements. The absolute crystallinity was calculated from the ratio between the full width at half maximum intensity of the (121) X-ray diffraction peaks of the brookite samples and the (111) peak of CaF2 as internal standard. The photocatalytic activity of the powders was tested employing the photodegradation of 4-nitrophenol as well…

Au/TiO2-CeO2 Catalysts for Photocatalytic Water Splitting and VOCs Oxidation Reactions

Photocatalytic water splitting for H2 production and photocatalytic oxidation of 2-propanol, an example of volatile organic compounds, were investigated over TiO2 catalysts loaded with gold and/or ceria. In the water splitting reaction the presence of gold only slightly affected the performance of TiO2 whereas the presence of CeO2 had a more remarkable positive effect. In the 2-propanol oxidation Au/TiO2 was the most active sample in terms of alcohol conversion whereas Au/TiO2-CeO2 exhibited the highest CO2 yield. On the basis of characterization experiments (X-Ray Diffraction (XRD), Energy Dispersive X-ray Analysis EDX, surface area measurements, Diffuse Reflectance Spectroscopy (DRS) and …