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L R Sheppard

Publications and source records attributed to L R Sheppard.

3 recordsLinked to original sources

Electrical properties of niobium-doped titanium dioxide. 1. Defect disorder.

The present work reports the electrical conductivity and thermoelectric power for Nb-doped TiO(2) at elevated temperatures (1073-1298 K) in the gas phase of controlled oxygen activity, 10(-14) Pa < p(O(2)) < 75 kPa. It is shown that in reduced conditions the Nb-doped TiO(2) exhibits metallic-type conductivity. This finding paves the way for the development of high-performance photoelectrodes with substantially reduced internal energy losses during charge transport. The present work also determined the equilibrium constant for the formation of oxygen vacancies and titanium vacancies for Nb-doped TiO(2).

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Electrical properties of niobium-doped titanium dioxide. 2. Equilibration kinetics.

The present work reports isothermal gas/solid equilibration kinetics for Nb-doped TiO(2) (0.65 atom %) at elevated temperatures (1073-1298 K) within narrow ranges of oxygen activity spanning between 10(-13) Pa and 75 kPa. The equilibration kinetics were monitored using electrical conductivity measurements. The kinetic data were used to determine the chemical diffusion coefficient (D(chem)). D(chem) as a function of p(O(2)) exhibits a complex dependence, which is considered in terms of defect disorder and the related concentrations of electronic charge carriers. The activation energy of D(chem) in the p(O(2)) range 10 Pa < p(O(2)) < 75 kPa varies in the range 88.0-98.2 kJ/mol. It is important to note that the chemical diffusion coefficient in strongly reduced conditions [p(O(2)) = 10(-9) Pa] exhibits a negative temperature dependence of D(chem) (-67.2 kJ/mol). This finding indicates that under these conditions transport in a chemical potential gradient is consistent with metallic charge transport.

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TiO2 surface active sites for water splitting.

The mechanism of photoreactivity between the TiO(2) surface and H(2)O, and the related charge transfer, is considered in terms of both collective and local properties. It is shown that the effective charge transfer between TiO(2) and water requires the presence of surface active sites that are able to provide electron holes to adsorbed water molecules. Titanium vacancies located at or near the surface are identified as the active sites for water adsorption leading to the formation of an active complex and resulting, in consequence, in water splitting. A model of the photoreactivity between the TiO(2) surface and water is proposed. This model indicates that the photoreactivity of the TiO(2)-based photoelectrode may be enhanced through imposition of the surface active sites (Ti vacancies) in a controlled manner by surface engineering.

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