A Facet‐Dependent Schottky‐Junction Electron Shuttle in a BiVO4010–Au–Cu2O Z‐Scheme Photocatalyst for Efficient Charge Separation

Abstract Interfacial charge separation and transfer are the main challenges of efficient semiconductor‐based Z‐scheme photocatalytic systems. Here, it is discovered that a Schottky junction at the interface between the BiVO 4 010 facet and Au is an efficient electron‐transfer route useful for constructing a high‐performance BiVO 4 010–Au–Cu 2 O Z‐scheme photocatalyst. Spectroscopic and computational studies reveal that hot electrons in BiVO 4 010 more easily cross the Schottky barrier to expedite the migration from BiVO 4 010 to Au and are subsequently captured by the excited holes in Cu 2 O. This crystal‐facet‐dependent electron shuttle allows the long‐lived holes and electrons to stay in the valence band of BiVO 4 and conduction band of Cu 2 O, respectively, contributing to improved light‐driven CO 2 reduction. This unique semiconductor crystal‐facet sandwich structure will provide an innovative strategy for rational design of advanced Z‐scheme photocatalysts.