C(sp3)–H Bond Activation by Perovskite Solar Photocatalyst Cell

Inspired by efficient perovskite solar cells, we developed a three-component hybrid perovskite-based solar photocatalyst cell, NiOx/FAPbBr3/TiO2, for C(sp3)–H bond activation with high selectivity (∼90%) and high conversion rates (3800 μmol g–1 h–1) under ambient conditions. Time-resolved spectroscopy on our photocatalytic cell reveals efficient exciton dissociation and charge separation, where TiO2 and NiOx serve as the electron- and hole-transporting layers, respectively. The photogenerated charge carriers injected into TiO2 and NiOx drive the challenging C–H activation reaction via the synergetic effects of their band alignment relative to FAPbBr3. The reaction pathway is investigated by controlling the free-radical formation, and we find that C–H activation is mainly triggered by hole oxidation. Besides aromatic alkanes, also the C(sp3)–H bond in cycloalkanes can be oxidized selectively. This work demonstrates a generic strategy for engineering high-performance photocatalysts based on the perovskite s...