Interfacing BiVO₄ with Reduced Graphene Oxide for Enhanced Photoactivity: A Tale of Facet Dependence of Electron Shuttling

Efficient interfacial charge transfer is essential in graphene-based semiconductors to realize their superior photoactivity. However, little is known about the factors (for example, semiconductor morphology) governing the charge interaction. Here, it is demonstrated that the electron transfer efficacy in reduced graphene oxide-bismuth oxide (RGO/BiVO₄) composite is improved as the relative exposure extent of {010}/{110} facets on BiVO₄ increases, indicated by the greater extent of photocurrent enhancement. The dependence of charge transfer ability on the exposure degree of {010} relative to {110} is revealed to arise due to the difference in electronic structures of the graphene/BiVO₄{010} and graphene/BiVO₄{110} interfaces, as evidenced by the density functional theory calculations. The former interface is found to be metallic with higher binding energy and smaller Schottky barrier than that of the latter semiconducting interface. The facet-dependent charge interaction elucidated in this study provides new aspect for design of graphene-based semiconductor photocatalyst useful in manifold applications.