Revealing the activity and selectivity of atomically dispersed Ni in Zn3In2S6 for benzyl alcohol photoreforming

Photoreforming enables simultaneous H2 production and organic synthesis in a one-pot system. In this study, a single-step synthesis approach was employed to fabricate atomically dispersed Ni in Zn3In2S6 (NixZIS) for benzyl alcohol photoreforming. While neat ZIS exhibits high selectivity toward hydrobenzoin via C-H activation and C-C coupling, its H2 evolution rate remains below feasible levels. Incorporating Ni single atoms significantly enhances ZIS activity by improving the carrier dynamics, resulting in an optimal H2 evolution rate of 9.13 mmol g-1 h−1 on Ni4ZIS, over five times higher than neat ZIS. The presence of Ni single atoms also alters selectivity, suppressing C-C coupling products and promoting benzaldehyde generation. The Ni single atoms induce facile O-H activation following the C-H activation of benzyl alcohol on ZIS, inhibiting the desorption of carbon radicals and causing consecutive oxidation to benzaldehyde. This study elucidates the role of Ni single atoms in driving activity and selectivity during organic photoreforming.