Abstract
Tuning the surroundings of single-atom catalysts (SACs) has been recognized as a successful approach to enhance their electrocatalytic efficiency. In this study, we utilized density functional theory (DFT) computations to systematically investigate how the coordination environment influences the catalytic performance of individual molybdenum atoms for the nitrogen reduction reaction (NRR) to NH(3). Upon comparing an extensive array of coordination combinations, Mo-based SACs were found to feature a distinctive N, P-dual coordination. Specifically, MoN(3)P(1)G demonstrates superior performance in the conversion of nitrogen into ammonia with an exceptionally low limiting potential (-0.64 V). This MoN(3)P(1)G catalyst preferably follows the distal pathway, with the initial hydrogenation step (*N(2) → *NNH) being the rate-determining step. Additionally, MoN(3)P(1)G exhibits the ability to suppress competing H(2) production, showcases high thermodynamic stability, and holds significant promise for experimental preparation. These findings not only contribute to diversifying the SAC family through localized coordination control but also present cost-effective strategies for enhancing sustainable NH(3) production.