Single-Particle Measurements Reveal the Origin of Low Solar-to-Hydrogen Efficiency of Rh-Doped SrTiO₃ Photocatalysts

Abstract

Solar-powered photochemical water splitting using suspensions of photocatalyst nanoparticles is an attractive route for economical production of green hydrogen. SrTiO₃-based photocatalysts have been intensely investigated due to their stability and recently demonstrated near-100% external quantum yield (EQY) for water splitting using wavelengths below 360 nm. To extend the optical absorption into the visible, SrTiO₃ nanoparticles have been doped with various transition metals. Here we demonstrate that doping SrTiO₃ nanoparticles with 1% Rh introduces midgap acceptor states which reduce the free electron concentration by 5 orders of magnitude, dramatically reducing built-in potentials which could otherwise separate electron-hole (e-h) pairs. Rhodium states also function as recombination centers, reducing the photocarrier lifetime by nearly 2 orders of magnitude and the maximum achievable EQY to 10%. Furthermore, the absence of built-in electric fields within Rh-doped SrTiO₃ nanoparticles suggests that modest e-h separation can be achieved by exploiting a difference in mobility between electrons and holes.