Marianna Bellardita

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 as probe molecule. SEM-EDX analysis revealed that titanium dioxide was quantitatively deposited on silica. TiO(2)/Axim and TiO(2)/Fly Ash were scarcely active whereas a good photoactivity was exhibited by the TiO(2)/Cabot sample both in the batch and in the continuous system. Consequently only the last sample was tested for both NO(x) abatement and for 4-nitrophenol photodegradation in a liquid-solid system.

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.

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 °C 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 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 materials. All materials were characterized by X-ray diffraction (XRD), scanning electron microscopy observations (SEM), diffuse reflectance spectroscopy (DRS), determination of the conduction and valence band energy by photovoltage measurements, Fourier transform infrared spectroscopy (FTIR), NH3-TPD experiments and time resolved microwave conductivity (TRMC).

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 an environmentally friendly route to degradation of PAHs.

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) H3PW12O40 (PW12) or with a hydrothermally home prepared K7PW11O39 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 isomerization to form fructose was also observed and in some runs traces of glucaric acid and glyceraldehyde were also found. The carbon mass balance was accomplished in the presence of the commercial Evonik P25 TiO2 powder and the composites where TiO2 was present, whereas the presence of the solvothermically prepared TiO2 gave rise to a carbon unbalance, due to strong adsorption of the products on the photocatalyst surface. No reactivity was observed in the presence of PW12 alone while PW11 induced only isomerization of the glucose.

Photocatalytic processes in membrane reactors

Conversion and degradation processes of various substrates in various types of matrices using both artificial and solar light are today very attractive by considering the scarcity and the expensiveness of the conventional energy sources. Coupling of membrane with light has shown to be very powerful and promising hybrid process, especially because a synergistic effect has often been observed.

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 used to study the surface acidity of the solids. Photodegradation of 4-nitrophenol and gemfibrozil (5-(2,5-dimethylphenoxy)-2,2-dimethyl-pentanoic acid) was used as probe reactions to evaluate the photoactivity and the obtained results showed that the home prepared samples are effective to degrade both substrates. The photoreactivity results were compared to those obtained using commercial photocatalysts.

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 improved the formaldehyde yield obtained with the bare HP1 by one order of magnitude. Differently, the presence of Cu or SiO2 in the HP2 samples markedly reduced the production of methane.

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™-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 μmol (gcatalyst 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 which mostly propose CH4 as the reaction product.

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.