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

摘要

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.