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The photocatalytic properties of bismuth-modified titania were studied by photobleaching of two aqueous azo dyes solutions (Reactive Black 5 and Acid Orange 7), and by photoinduced decomposition (PID) of acetaldehyde using in situ FTIR spectroscopy. Low bismuth doping concentrations up to 3 at.% is shown to lead to an increased photobleaching rate of both azo dyes solutions. Too high Bi dopant concentrations lead to less developed crystallite nanoparticles and exhibit weaker adsorption capacity. Bismuth doping altered the adsorption kinetics of acetaldehyde resulting in different surface products, and a modified photocatalytic reaction pathway was inferred. [ABSTRACT FROM AUTHOR]

Abstract: The structure and photocatalytic activity of Zr doped TiO2 nanocrystallites with a varying Zr content between 0 and 15wt% prepared by an efficient and environmentally benign method has been studied by vibrational spectroscopy, TEM and XRD. It is shown that the presence of Zr4+ ions stabilizes the anatase structure and delays phase transformation to rutile upon annealing as well as retarding grain coarsening. All TiO2 samples up to 13wt% Zr doping concentration show better or similar photoreactivity compared to P25 (Degussa) for decomposition of adsorbed 2-chloroethyl ethyl sulphide (CEES) and dimethyl methylphosphonate (DMMP) in synthetic air at room temperature. The most efficient sample for photodegradation of both CEES and DMMP is shown to be titania doped with 6.8wt% Zr. The photodegradation of CEES is faster than DMMP under the same experimental conditions. On the undoped TiO2 sample urea residues are detected spectroscopically. Much less is detected on the Zr doped samples. Mode resolved in situ FTIR surface spectroscopy enables distinction of CEES or DMMP, decomposition products as well as the influence of residues from the particle synthesis. This facilitates extraction of intra-comparable reaction rates. Possible explanations for the improved reactivity of the Zr doped titania are discussed. [Copyright &y& Elsevier]

We present a demonstration of online monitoring of gas-phase photocatalytic reactions. A cotton cloth impregnated with commercial titanium dioxide nanoparticles is used as a photocatalytic filter to clean air contaminated with a model pollutant. A fan forces air through the filter while it is irradiated by UV diodes. The concentration of the air pollutant is measured online by an inexpensive, commercially available semiconductor air quality sensor. The structural parts of the reactor were 3D printed in polylactide bioplastic. We provide all schematics, 3D printed model parts, hardware, firmware, and computer code of the reactor and control units. The device can be used for interactive learning of both gas phase photocatalysis and gas sensing, as well as in student laboratory classes for measuring air pollutants and their photodegradation. The experimental setup can also form the basis for a project work for chemical engineering university students, and it can be employed as a building block for development of other gas phase chemical reaction demonstrations. [ABSTRACT FROM AUTHOR]

The photocatalytic properties of bismuth-modified titania were studied by photobleaching of two aqueous azo dyes solutions (Reactive Black 5 and Acid Orange 7), and by photoinduced decomposition (PID) of acetaldehyde using in situ FTIR spectroscopy. Low bismuth doping concentrations up to 3 at.% is shown to lead to an increased photobleaching rate of both azo dyes solutions. Too high Bi dopant concentrations lead to less developed crystallite nanoparticles and exhibit weaker adsorption capacity. Bismuth doping altered the adsorption kinetics of acetaldehyde resulting in different surface products, and a modified photocatalytic reaction pathway was inferred. [ABSTRACT FROM AUTHOR]

Abstract: Pure titania and titania doped with Zn2+ were prepared by homogeneous hydrolysis in aqueous solution with urea and thioacetamide as precipitating agents. The materials were characterized by XRD, TEM, BET and BJH analysis, which show microporous, nanaocrytsalline anatase phase titania in the size range 4–5nm and specific surface area 200–500m2/g. Adsorption and photocatalytic decomposition of 2-chloroethyl ethyl sulfide (CEES) was measured on dry and water pre-covered titania surfaces, respectively. Illumination with UV light leads to rapid decomposition of CEES on all samples resulting in formation of surface bound ethoxy, chloro ethoxy, aldehydes, acetone and carboxylates. Volatile sulphur moieties (Socyanate (Ti-NCO) are observed which is related to the synthesis methods employed. A procedure for removing residual synthesis products from the particles was devised and the intrinsic photodegradation rate was determined on the purified samples and compared with the as prepared samples. The photodegradation rate is notable higher for the purified TiO2 nanoparticles prepared by the urea route with respect to the “as prepared”. In the case of the Zn doped TiO2 samples a diminution in photodegradation rate is observed after purification. The results are correlated with the amount of volatile residual synthesis products present on the different particles. All materials have comparable or higher photo-reactivity than P25 (Degussa). On a humidified surface, the effects from synthesis residues, in particular volatile sulphur moieties, are reduced due to reactions with water and improved photoreaction rates for all samples are observed. [Copyright &y& Elsevier]

• TiO 2 /ND nanocomposites were prepared by a low-temperature water-based method. • TiO 2 /ND were three times more efficient for degradation of soman than pure TiO 2. • in situ DRIFTS revealed improved (photo)decomposition of DMMP on TiO 2 /ND. • Kelvin probe measurements indicate charge transfer across TiO 2 /ND interfaces. We report on the synthesis and characterization of TiO 2 /Nanodiamond (ND) nanocomposites for rapid decontamination of chemical warfare agents (CWA) and toxic industrial compounds prepared by a simple water-based, low-temperature method using urea as a homogeneous precipitating agent. The excellent water-compatibility of NDs promoted their good dispersion within the TiO 2 matrix resulting in intergrown TiO 2 /ND nanostructures. NDs with an abundance of oxygen-containing surface moieties increased the porosity of the composites resulting in their three times more efficient spontaneous degradation of the CWA soman in solution compared to pure TiO 2. In situ DRIFT spectroscopy revealed the enhanced reactive adsorption and solar light photodecomposition of dimethyl methyl phosphonate vapor on TiO 2 /ND. The charge transfer across TiO 2 /ND interfaces that hinder recombination of photo-excited electron-hole pairs was inferred from surface potential measurements. The results indicate that well-dispersed NDs forming heterojunctions together with their high porosity contribute to the reactive properties of the nanocomposites. [ABSTRACT FROM AUTHOR]