LAUSR

Abstract Carbon dioxide electrochemical reduction reaction (CO2RR) with proton-electron pair delineates an intriguing prospect for converting CO2 to useful chemicals. However, CO2RR is urgently required low-cost and high efficient electrocatalysts to overcome the sluggish reaction kinetic and ultralow selectivity. Here by means of first-principle computations, the geometric constructions, electronic structures, and CO2RR catalytic performance of boron- and nitrogen-doped graphdiyne anchoring a single Cu atom (Cu@N-doped GDY and Cu@B-doped GDY) were systematically investigated. These eight Cu@doped GDY complexes possess excellent stability. The adsorption free energies showed that the eight Cu@doped GDY could spontaneously capture CO2 molecules. The Cu@N-doped GDY monolayers exhibit a more efficient catalytic performance for CO2 reduction compared to Cu@B-doped GDY because of the differences in adsorption energies and charge transfer. The calculations further indicated that the Cu@Nb-doped GDY complex possesses excellent catalytic character toward CO2RR with the same limiting potentials of −0.65 V for production of HCOOH, CO, OCH2, CH3OH, and CH4. Charge analysis indicated that the *OCHO and *COOH species gain more electrons from Cu@N-doped GDY than from Cu@B-doped GDY complexes due to different electronegativity of coordinated element. Our findings highlighted the electronegativity of coordinated elements for the design of atomic metal catalysts.