Screening copper-based single-atom alloy catalysts for electrochemical nitrogen reduction

Highly efficient and selective electrocatalyst exploration is crucial for advancing the green electrochemical technology of direct nitrogen-to-ammonia conversion through the electrocatalytic nitrogen reduction reaction (eNRR). In this study, we have systematically screened Cu based single-atom alloy (SAA) catalysts for electrochemical nitrogen reduction using density functional theory calculations and interpretable machine learning. We reveal that V-, Nb-, Mo-, Ta-, and W@Cu(100) SAAs exhibit exceptional eNRR performance. These candidates demonstrate robust structural stability, superior selectivity, and remarkably low limiting potentials (<i>U</i>_L > -0.30 V) that surpass those of conventional single-atom catalysts. By employing intrinsic physicochemical properties of SAA catalysts as feature descriptors, we have developed an adaptive boosting machine learning model that achieves accurate prediction of limiting potentials. SHapley Additive exPlanations analysis highlights the critical influence of two key parameters: the electron accumulation in adsorbed *N₂ species and the number of valence electrons of transition metals. Subsequent application of the sure independence screening and sparsifying operator algorithm further identifies an optimal combination of four essential features, corroborating the significance of ML-identified descriptors. This multiscale investigation establishes a robust framework for rational design of SAA catalysts, combining first-principles calculations with interpretable machine learning to accelerate the development of sustainable ammonia synthesis technologies.