Nanoporous BiVO ₄ Photoanodes with Dual-Layer Oxygen Evolution Catalysts for Solar Water Splitting

Bismuth vanadate (BiVO4) has a band structure that is well-suited for potential use as a photoanode in solar water splitting, but it suffers from poor electron-hole separation. Here, we demonstrate that a nanoporous morphology (specific surface area of 31.8 square meters per gram) effectively suppresses bulk carrier recombination without additional doping, manifesting an electron-hole separation yield of 0.90 at 1.23 volts (V) versus the reversible hydrogen electrode (RHE). We enhanced the propensity for surface-reaching holes to instigate water-splitting chemistry by serially applying two different oxygen evolution catalyst (OEC) layers, FeOOH and NiOOH, which reduces interface recombination at the BiVO4/OEC junction while creating a more favorable Helmholtz layer potential drop at the OEC/electrolyte junction. The resulting BiVO4/FeOOH/NiOOH photoanode achieves a photocurrent density of 2.73 milliamps per square centimenter at a potential as low as 0.6 V versus RHE.