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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.

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