Polaron-Mediated Transport in BiVO₄ Photoanodes for Solar Water Oxidation

Hydrogen dopants and oxygen vacancies (OVs) play crucial roles in BiVO 4 photoanodes. However, the decisive factor determining the charge transport of the hydrogenated BiVO 4, particularly with electron small polaron formation, remains elusive. Here we show a decreased charge transport barrier upon mildly hydrogenating the nanoporous BiVO 4 photoanode, as evidenced by the thermally activating photocurrent responses. Monochromatic light photoelectrochemical performance, temperature-dependent conductivity, proton nuclear magnetic resonance, and density functional theory calculation disclose that the external hydrogen atoms occupy the intrinsic OVs in the BiVO 4, reducing the hopping activation energy and facilitating electron small polaron transport. The resulting BiVO 4 photoanode with NiFeO x cocatalyst achieves an applied-bias photon-to-current efficiency of 1.91% at 0.58 V vs RHE with front-illumination. This study extends the common understanding of the beneficial role in conventional donor density/surface chemisorption mediations of hydrogen doping to now include small polaron hopping.