Reaction mechanism and kinetics for CO2 reduction on nickel single atom catalysts from quantum mechanics.

Experiments have shown that graphene-supported Ni-single atom catalysts (Ni-SACs) provide a promising strategy for the electrochemical reduction of CO2 to CO, but the nature of the Ni sites (Ni-N2C2, Ni-N3C1, Ni-N4) in Ni-SACs has not been determined experimentally. Here, we apply the recently developed grand canonical potential kinetics (GCP-K) formulation of quantum mechanics to predict the kinetics as a function of applied potential (U) to determine faradic efficiency, turn over frequency, and Tafel slope for CO and H2 production for all three sites. We predict an onset potential (at 10 mA cm-2) Uonset = -0.84 V (vs. RHE) for Ni-N2C2 site and Uonset = -0.92 V for Ni-N3C1 site in agreement with experiments, and Uonset = -1.03 V for Ni-N4. We predict that the highest current is for Ni-N4, leading to 700 mA cm-2 at U = -1.12 V. To help determine the actual sites in the experiments, we predict the XPS binding energy shift and CO vibrational frequency for each site.