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

Photocatalytic CO2 reduction into ideal hydrocarbon fuels, such as CH4, is a sluggish kinetic process involving adsorption of multiple intermediates and multi‐electron steps. Achieving high CH4 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 CO2 reduction. Herein, we construct La and Cu dual‐atom anchored carbon nitride (LaCu/CN), with La‐N4 and Cu‐N3 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 CO2 reduction on LaCu/CN demonstrate thermodynamically more favorable process for CH4 formation based on theoretical calculations. Eventually, LaCu/CN exhibits a high selectivity (91.6 %) for CH4 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. The asymmetric Cu−N−La species enables the establishment of an atomic‐level donor‐acceptor structure, facilitating the migration of electrons from La atoms to the reactive Cu atom sites. Intermediates adsorbed on Cu−N−La species in the CH4 production from CO2 form are more thermodynamically favorable. The photocatalyst exhibits outstanding CH4 selectivity (91.6 %) and high CH4 production rate (125.8 μmol g−1), over ten times of that for CN.