Silver-modified octahedral anatase particles as plasmonic photocatalyst.

Octahedral anatase particles (OAPs) were modified with silver nanoparticles (NPs) by photodeposition method. The properties of OAPs influenced the properties of silver deposits, and thus the photocatalytic activity of the obtained silver-modified OAPs. Photocatalytic activities were tested under UV and vis irradiation for oxidative decomposition of acetic acid and oxidation of 2-propanol, respectively. The properties of silver-modified OAPs were investigated by XRD, STEM, DRS, XPS and time-resolved microwave conductivity (TRMC) method. It was found that electron traps (ETs) worked as nucleation sites for silver, resulting in formation of smaller silver NPs on smaller OAPs with larger content of ETs. The modification with silver resulted in enhanced photocatalytic activity under both UV and vis irradiation. It was found that larger crystallite size of silver NPs, and thus larger polydispersity of silver deposits resulted in broad and intense plasmon resonance peak causing enhanced visible activity. The correlation between photocatalytic activity and TRMC data, e.g., slower decay of TRMC signal for more active samples, allowed discussion on property-governed photocatalytic activities of silver-modified titania.

Role of Cr(III) deposition during the photocatalytic transformation of hexavalent chromium and citric acid over commercial TiO2 samples.

Removal of Cr(VI) and citric acid (Cit) by heterogeneous photocatalytic Cr(VI) transformation under UV light over two commercial TiO2 samples (1 g L(-1)), Evonik P25 and Hombikat UV100, was studied at pH 2 and Cr(VI) concentrations between 0.2 and 3 mM, with a fixed [Cit]0/[Cr(VI)]0 molar ratio (MR) of 2.5. In both cases, up to complete Cr(VI) removal, the temporal profiles of Cr(VI) and Cit were well adjusted to a pseudo-first order rate law with the same rate constant, evidencing that Cr(VI) removal controls the kinetics of the system. Once Cr(VI) is fully removed, Cit degradation continues with a Langmuir-Hinshelwood behaviour. In all cases, the rate constants decreased with increasing [Cr(VI)]0, and time resolved microwave conductivity (TRMC) measurements revealed that this was due to an increasing retention of Cr(III) on the surface of the photocatalysts, which reduces the lifetime of the electrons. Both kinetic experiments and TRMC measurements confirm that UV100 is not only more efficient than P25 for Cr(VI) and Cit removal, but it is also less influenced by the poisoning of the surface, consistent with its larger specific area. The use of Cit as the sacrificial agent improves the rate and efficiency of the photocatalytic Cr(VI) removal, and also the stability of the photocatalyst by preventing Cr(III) deposition, due to the formation of soluble Cr(III)-complexes, envisaged as a general result of the presence of oligocarboxylic acids in the photocatalytic Cr(VI) system.

A comparative study of photo-assisted deposition of silver nanoparticles on TiO2.

Noble metals deposited on TiO2 act as electron traps facilitating electron-hole separation and promoting the interfacial electron transfer process. In particular, silver nanoparticles have the ability to absorb visible light due to localized surface plasmon resonance. Here we report a photochemical and photocatalytic method for depositing Ag nanoparticles (2-20 nm) on TiO2 by using UV light at room temperature. UV-Vis diffuse reflectance spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and time-resolved microwave conductivity were used as characterization techniques. The photocatalytic activity was investigated by measuring the decomposition of rhodamine B under UV and visible light irradiation. The fastest bleaching of RhB under visible-light irradiation has been obtained by Ag/TiO2 plasmonic photocatalyst prepared by the photocatalytic route. These results were explained in terms of the more efficient photon absorption due to the presence of the surface plasmon resonance.

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).