Abstract
Bismuth vanadate (BiVO4) has been highlighted as the most efficient photoanode light absorber for the solar light-driven water oxidation reaction despite the lack of fundamental understanding of its poor performance. Though the BiVO4 performance has been significantly improved, the underlying reasons for this performance are not well understood. Here, anisotropically grown BiVO4 is designed to achieve band edge engineering induced by coupled crystal facets for hydrogen evolution reaction (HER), which is not possible with isotropic BiVO4 powder suspension. HER performances depending on the exposure area of the crystal facets in the anisotropic BiVO4 are investigated using electronic conduction and in situ X-ray absorption spectroscopy during HER. Our results reveal that the nature of the exposed area of the optimized coupled crystal facets in a BiVO4 photoelectrode critically dominates the surface charge density and conductivity, efficiently driving the HER. Sequentially, coupling between different crystal facets of BiVO4 photoelectrode led energy band edge to be upward. The results show that the energy band edge alignment tuned by coupled crystal facet can be applicable to other inorganic photocatalyst/photoelectrodes to promote efficient artificial photosynthetic reactions.
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