Time-resolved microwave conductivity. Part 1.—TiO2 photoreactivity and size quantization

Abstract

Charge-carrier recombination dynamics after laser excitation are investigated by time-resolved microwave conductivity (TRMC) measurements of quantum-sized (Q-) TiO₂, Fe^III-doped Q-TiO₂, ZnO and CdS, and several commercial bulk-sized TiO₂ samples. After pulsed laser excitation of charge carriers, holes that escape recombination react with sorbed trans-decalin within ns while the measured conductivity signal is due to conduction-band electrons remaining in the semiconductor lattice. The charge-carrier recombination lifetime and the interfacial electron-transfer rate constant that are derived from the TRMC measurements correlate with the CW photo-oxidation quantum efficiency obtained for aqueous chloroform in the presence of TiO₂. The quantum efficiencies are 0. 4 % for Q-TiO₂, 1. 6 % for Degussa P25, and 2. 0 % for Fe^III-doped Q-TiO₂. The lower quantum efficiencies for Q-TiO₂ are consistent with the relative interfacial electron-transfer rates observed by TRMC for Q-TiO₂ and Degussa P25. The increased quantum efficiencies of Fe^III-doped Q-TiO₂ and the observed TRMC decays are consistent with a mechanism involving fast trapping of valence-band holes as Fe^IV and inhibition of charge-order recombination.