Surface atomic arrangement and coordination of photocatalysts highly exposed to different crystal facets significantly affect the photoreactivity. However, controversies on the true photoreactivity of a specific facet in heterogeneous photocatalysis still exits. Herein, we exemplified well-defined BiOBr nanosheets dominating with respective facets, (001) and (010), to track the reactivity of crystal facets for photocatalytic water splitting. The real photoreactivity of BiOBr-(001) were evidenced to be significantly higher than BiOBr-(010) for both hydrogen production and oxygen evolution reactions. Further in situ photochemical probing studies verified the distinct reactivity is not only owing to the highly exposed facets, but dominated by the co-exposing facets, leading to an efficient spatial separation of photogenerated charges and further making the oxidation and reduction reactions separately occur with different reaction rates, which ordains the fate of the true photoreactivity.

Plasmon-induced photocatalysts hold great promise for solar energy conversion owing to their strong light-harvesting ability and tunable optical properties. However, the complex process of interfacial extraction of hot carriers and the roles of metal/semiconductor interfaces in plasmonic photocatalysts are still not clearly understood. Herein, the manipulation of the interface between a plasmon metal (Au) and a semiconductor (rutile TiO₂) by introducing an interfacial metal oxide (Al₂O₃) is reported. The resulting Au/Al₂O₃/TiO₂ exhibits remarkable enhancement in photocatalytic water oxidation activity compared with Au/TiO₂, giving an apparent quantum efficiency exceeding 1.3% at 520 nm for photocatalytic water oxidation. Such an interfacial modulation approach significantly prolongs the lifetime of hot carriers in the Au/TiO₂ system, which conclusively improves the utilization of hot carriers for plasmon-induced water oxidation reaction upon irradiation. This work emphasizes the essential role of the interfacial structure in plasmonic devices and provides an alternative method for designing efficient plasmonic photocatalysts for solar energy conversion.