Asymmetric Cu−N−La Species Enabling Atomic‐Level Donor‐Acceptor Structure and Favored Reaction Thermodynamics for Selective CO2 Photoreduction to CH4

Abstract Photocatalytic CO 2 reduction into ideal hydrocarbon fuels, such as CH 4 , is a sluggish kinetic process involving adsorption of multiple intermediates and multi‐electron steps. Achieving high CH 4 activity and selectivity therefore remains a great challenge, which largely depends on the efficiency of photogenerated charge separation and transfer as well as the intermediate energy levels in CO 2 reduction. Herein, we construct La and Cu dual‐atom anchored carbon nitride (LaCu/CN), with La‐N 4 and Cu‐N 3 coordination bonds connected by Cu−N−La bridges. The asymmetric Cu−N−La species enables the establishment of an atomic‐level donor‐acceptor structure, which allows the migration of electrons from La atoms to the reactive Cu atom sites. Simultaneously, intermediates during CO 2 reduction on LaCu/CN demonstrate thermodynamically more favorable process for CH 4 formation based on theoretical calculations. Eventually, LaCu/CN exhibits a high selectivity (91.6 %) for CH 4 formation with a yield of 125.8 μmol g −1 , over ten times of that for pristine CN. This work presents a strategy for designing multi‐functional dual‐atom based photocatalysts.