Lead-free inorganic halide perovskites have triggered appealing interests in various energy-related applications including solar cells and photocatalysis. However, why perovskite-structured materials exhibit excellent photoelectric properties and how the unique crystalline structures affect the charge behaviors are still not well elucidated but essentially desired. Herein, taking inorganic halide perovskite Cs₃Bi₂Br₉ as a prototype, the significant derivation process of silver atoms incorporation to induce the structural transformation from Cs₃Bi₂Br₉ to Cs₂AgBiBr₆, which brings about dramatic differences in photoelectric properties is unraveled. It is demonstrated that the silver incorporation results in the co-operated orbitals hybridization, which makes the electronic distributions in conduction and valence bands of Cs₂AgBiBr₆ more dispersible, eliminating the strong localization of electron–hole pairs. As consequences of the electronic structures derivation, exhilarating changes in photoelectric properties like band structure, exciton binding energy, and charge carrier dynamics are verified experimentally and theoretically. Using photocatalytic hydrogen evolution activity under visible light as a typical evaluation, such crystalline structure transformation contributes to a more than 100-fold enhancement in photocatalytic performances compared with pristine Cs₃Bi₂Br₉, verifying the significant effect of structural derivations on the exhibited performances. The findings will provide evidences for understanding the origin of photoelectric properties for perovskites semiconductors in solar energy conversion.

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.