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The present work brings together the concepts of defect chemistry and photoelectrochemistry in order to consider TiO2-based photosensitive oxide semiconductors as photocatalysts for water purification. This paper reports the most recent progress in the defect chemistry of TiO2 and its solid solutions with aliovalent ions forming donors and acceptors. The relationship between the defect-related properties, such as electrical and photocatalytic properties, are outlined. It is shown that reactivity, photoreactivity, and the related charge transfer of photocatalysts based on TiO2 are determined by defect disorder and the related chemical potential of electrons. Therefore, defect chemistry may be used as a framework for the processing of well-defined TiO2-based photocatalysts. The photoreactivity of TiO2 with water and its solutes is considered in terms of the effect of both collective and local properties. The effect of noble metals attached to TiO2 as a separate phase, such as platinum, on photoelectrochemical properties and the related photocatalytic performance of TiO2 is discussed. The key functional properties, which are responsible for the efficient conversion of solar energy into chemical energy (required for water purification), are outlined. The effect of TiO2 doping with aliovalent ions on properties is considered in terms of the doping mechanisms and the related semiconducting properties. It is argued that comparison of the experimental data reported in the literature on the photocatalytic properties of TiO2 dictates the need to establish standards for photocatalysts, which are well-defined. This paper reports the processing conditions of well-defined TiO2. It is argued that knowledge of the mass transport kinetic data, such as chemical and self-diffusion coefficients, is needed for selecting the optimal processing conditions.

The present work reports the electrical properties of high-purity single-crystal TiO(2) from measurements of the electrical conductivity in the temperature range 1073-1323 K and in gas phases of controlled oxygen activities in the range 10(-13) to 10(5) Pa. The effect of the oxygen activity on the electrical conductivity indicates that oxygen vacancies are the predominant defects in the studied ranges of temperature and oxygen activities. The electronic and ionic lattice charge compensations were revealed at low and high oxygen activities, respectively. The determined semiconducting quantities include: the activation energy of the electrical conductivity (E(sigma) = 125-205 kJ.mol(-1)), the activation energies of the electrical conductivity components associated with electrons (E(n) = 218 kJ.mol(-1)), electron holes (E(p) = 34 kJ.mol(-1)), and ions (E(i) = 227 kJ.mol(-1)), and the enthalpy of motion for electronic defects (DeltaH(m) = 4 kJ/mol). The electrical conductivity data are considered in terms of the components related to electrons, holes, and ions. The obtained data allow the determination of the n-p demarcation line in terms of temperature and oxygen activities. The band gap determined from the electronic component of the electrical conductivity is 3.1 eV.

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The present work derived defect disorder diagram representing the effect of oxygen activity on the concentration of both ionic and electronic defects for undoped TiO2. This diagram was determined using the equilibrium constants derived in the present work, including (i) the intrinsic electronic equilibrium constant, (ii) the equilibrium constant for the formation of oxygen vacancies, and (iii) equilibrium constant for the formation of titanium vacancies. These equilibrium constants are consistent with three properties determined independently, including: electrical conductivity, thermoelectric power and change of mass determined by thermogravimetry. The derived defect disorder diagram may be used for tailoring semiconducting properties of TiO2 that are desired for specific applications through the selection of optimized processing conditions.

Measurements of both electrical conductivity and thermoelectric power were used to monitor the equilibration kinetics of undoped single-crystal TiO(2) during prolonged oxidation at 1123 and 1323 K and p(O(2)) = 75 kPa. Two kinetics regimes were revealed: kinetics regime I (rapid kinetics), which is rate-controlled by the transport of oxygen vacancies, and kinetics regime II (slow kinetics), which is rate-controlled by the transport of titanium vacancies. The incorporation of titanium vacancies allows undoped p-type TiO(2) to be processed in a controlled manner. The kinetics data were used to determine the chemical diffusion coefficient (D(chem)) associated with the transport of titanium vacancies, which is equal to D(chem) = 8.9 x 10(-14) m(2) s(-1) and D(chem) = 9.3 x 10(-15) m(2) s(-1) at 1323 and 1123 K, respectively.

The semiconducting properties of single‐crystal TiO2 and their changes during prolonged oxidation at elevated temperatures and under controlled oxygen activity were monitored using measurements of electrical conductivity and thermo‐electric power. Two kinetic regimes were revealed: Regime I – rapid oxidation, associated with the transport of oxygen vacancies, and Regime II – prolonged oxidation, which corresponds to the transport of titanium vacancies. The present data represent the first documented evidence for the formation and transport of titanium vacancies in TiO2. This finding allows the processing of p‐type TiO2 without the incorporation of aliovalent foreign ions. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

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