Unveiling the Active Structure of Single Nickel Atom Catalysis: Critical Roles of Charge Capacity and Hydrogen...

A single nickel atom embedded in graphene is one of the most representative single-atom catalysts, and it has a high activity and selectivity for electrochemical CO₂ reduction (CO₂R) to CO. However, the catalytic origin, especially the coordination structure of Ni, remains highly puzzling, as previous density functional theory (DFT) calculations showed that all the possible structures should be inactive and/or nonselective. Here, using ab initio molecular dynamics (AIMD) and a "slow-growth" sampling approach to evaluate the reaction kinetic barriers, we show that the charge capacity (of the site) and hydrogen bonding (with the intermediates), which were neglected/oversimplified in previous DFT calculations, play crucial roles, and including their effects can resolve the catalytic origin. Particularly, a high charge capacity allows the catalytic site to carry more charges than required for the electrochemical step, lowering the electrochemical barrier, and hydrogen bonding promotes the reaction that produces polar intermediates by stabilizing the intermediates and facilitating the H transfer from water, explaining the high selectivity for CO₂R over the hydrogen evolution reaction. Consequently, we find that a hybrid coordination environment (with one nitrogen and three carbon atoms) for the Ni-atom is most active and selective for CO₂R. Our work not only explains a long-standing puzzle for an important catalyst but also highlights the crucial roles of charge capacity and hydrogen bonding, which can help elucidate the mechanisms of other heterogeneous electrocatalysts in aqueous solution and enable more effective catalyst design.