High-Throughput Screening of Nitrogen-Coordinated Bimetal Catalysts for Multielectron Reduction of CO₂ to CH₄ with High Selectivity and Low Limiting Potential

Significant challenges remain for developing efficient catalysts in an electrochemical multielectron CO₂ reduction reaction (CO₂RR), which usually suffers from poor activity and selectivity. Motivated by the recent experimental progress in fabricating dual-metal atom catalysts (DMACs) in N-doped graphene materials (graphene-N6V4; N: nitrogen and V: vacancy), we sampled eight types of homonuclear (N6V4-M₂, M = Cr, Mn, Fe, Co, Ni, Cu, Pd, and Ag) catalysts and 28 types of heteronuclear (N6V4-M1M2) catalysts to study CO₂RR activity via first-principles high-throughput screening. Using stability, activity, and selectivity as indicators along with the broken conventional scaling relationship, N6V4-AgCr was selected as a promising candidate for deep CO₂ reduction to methane with a low overpotential of 0.55 V after two screening rounds. Further analysis showed that a frustrated Lewis pair, formed between metal and the para-N, owing to the difference in the electronic arrangement of the d orbitals of various transition metals, caused a difference in the spin polarization of the systems and affected the catalytic performance of each DMAC. Our work not only provides a solid strategy for screening potential catalysts but also demonstrates that their CO₂ reduction activities originate from the various atomic and electronic structures of DMACs.