Complex Photoconductivity Reveals How the Nonstoichiometric Sr/Ti Affects the Charge Dynamics of a SrTiO3 Photocatalyst.

Abstract

Strontium titanate (SrTiO3) is a perovskite that is important in water-splitting photocatalytic chemistry. Although excess Sr is known to improve the photocatalytic activity, its effect on charge dynamics remain largely unaddressed. Herein, we present a detailed analyses of gigahertz complex transient photoconductivity (Δσ) measured using time-resolved microwave conductivity (TRMC). We show that charge carrier trapping associated with the emergence of an anomalous positive imaginary part and the first-order rate constant of the normal positive real part of Δσ dramatically decreased with increasing Sr/Ti ratio. The second-order rate constant attributed to charge recombination simultaneously decreased, and these rate constants were well correlated with the improved hydrogen evolution rate of aqueous SrTiO3 suspensions with a Pt co-catalyst. These findings provide a fresh perspective on the stoichiometry-carrier dynamics relationship paramount for the optimization of composition-engineered photocatalysts and reveal the broad implications for mechanistic studies based on TRMC evaluation.