Enhanced Charge Separation in Nanoporous BiVO4 by External Electron Transport Layer Boosts Solar Water Splitting

The optimization of charge transport with electron-hole separation directed toward specific redox reactions is a crucial mission for artificial photosynthesis. Bismuth vanadate (BiVO₄ , BVO) is a popular photoanode material for solar water splitting, but it faces tricky challenges in poor charge separation due to its modest charge transport properties. Here, a concept of the external electron transport layer (ETL) is first proposed and demonstrated its effectiveness in suppressing the charge recombination both in bulk and at surface. Specifically, a conformal carbon capsulation applied on BVO enables a remarkable increase in the charge separation efficiency, thanks to its critical roles in passivating surface charge-trapping sites and building external conductance channels. Through decorated with an oxygen evolution catalyst to accelerate surface charge transfer, the carbon-encased BVO (BVO@C) photoanode manifests durable water splitting over 120 h with a high current density of 5.9 mA cm^-2 at 1.23 V versus the reversible hydrogen electrode (RHE) under 1 sun irradiation (100 mW cm^-2 , AM 1.5 G), which is an activity-stability trade-off record for single BVO light absorber. This work opens up a new avenue to steer charge separation via external ETL for solar fuel conversion.