Ingenious p‐d orbital hybridization induced by atomic Yb doping for CO 2 reduction to CO

Abstract Orbital hybridization plays a crucial role in catalytic processes, yet elucidating its mechanism remains a significant challenge. Here, we have developed a strategy for the formation of Yb‐C bond by unconventional p‐d orbital hybridization, which induced carbon nitride modified by rare‐earth metal element Yb. The optimal sample exhibits catalytic performance 11.2 times greater than that of g‐C 3 N 4 with N vacancies (NvCN). Yb‐C bond and N vacancies reduced the energy barrier and optimized the rate‐determining step (*COO + *H → *CO + *OH). Additionally, the intense Yb‐C interaction created a specific electrons bridge, which accelerated the transfer rate of electrons on the photocatalytic surface. Next, the CO 2 conversion reaction mechanism was studied by in situ infrared spectroscopy and theoretical calculations, and the unconventional p‐d orbital hybridization contributed to the generation of vital intermediate *CO. This study provides a theoretical basis for designing single‐atom photocatalysts for the reduction of CO 2 .