Cooperative Atomic Palladium Site and Island-Distributed S-Scheme Heterostructure for Photocatalytic C<sub>2</sub>H<sub>6</sub> Production
Yan Wu, Zhujie Li, Qingqing Chen, Zaizhu Lou, Gang Wang, Junjie Mao
Abstract
The CO 2 reduction reaction (CO 2 RR) to produce C 2 products relies on the synergy between the C 1 generation site and the C–C coupling site within the photocatalytic system. However, yields are often limited by inadequate C 1 precursor production, inefficient multielectron transport, and weak C 1 adsorption at the C–C coupling site. In this study, we developed a highly efficient photocatalytic system that achieved remarkable conversion of CO 2 to C 2 H 6 by integrating Pd single atomic sites and island-distributed PdO nanoparticles onto phosphorus-modified BiOCl (PdO/BOCP-Pd 1 ). This system exhibited a prominent C 2 H 6 yield of 215.6 μmol g –1 h –1 and a selectivity of 97.5%, maintaining its performance with negligible decay over a minimum duration of 200 h, representing the top-level photocatalytic performance of reported photocatalysts. Both experimental and theoretical results confirm that the Pd 1 site in the PdO/BOCP-Pd 1 catalyst significantly enhances the availability of local CO. Its distinctive S-scheme charge transfer mode promotes the formation of electron-rich PdO sites. Thanks to the superior CO adsorption capacity of PdO, these electron-rich PdO sites can serve as efficient C–C coupling sites after adsorbing CO, ultimately leading to the highly efficient production of C 2 H 6 . This study provides insight into designing multisite cooperative photocatalysts for superior CO 2 RR to C 2 products.