Efficient BiVO₄ Photoanode with an Excellent Hole Transport Layer of CuSCN for Solar Water Oxidation

Abstract Bismuth vanadate (BiVO₄) is reported as a key material in photoelectrocatalysis owing to high theoretical efficiency, relatively narrow band gap of 2.4 eV, and favorable conduction band edge position for hydrogen evolution. However, the sluggish hole transport dynamics lead to slow photogenerated charge separation and transport efficiencies, which result in charge recombination due to aggregation. Herein, a novel hole transport layer of copper(I) thiocyanate (CuSCN) with the aim of significantly enhancing the efficiency of charge transport and stability of BiVO₄ photoanodes is reported. The introduction of the hole transport layer could provide an appropriate intermediate energy level for photogenerated hole transfer and avoid charge recombination and trapping. After a photoassisted electrodeposition process of NiCoFe‐B_i catalysis, the obtained photoanode achieves a photocurrent density of 5.6 mA cm⁻² at 1.23 V versus reversible hydrogen electrode under AM 1.5 G simulated solar radiation, and an applied bias photon to current efficiency of 2.31%. With the CuSCN layer, BiVO₄ photoanode presented impressive stable photocurrent during 50 h continuous illumination. Meanwhile, the unbiased tandem device of the NiCoFe‐B_i/CuSCN/BiVO₄ photoanode and the Si solar cell exhibit a solar‐to‐hydrogen efficiency of 5.75% and excellent stability for 14 h.