d‐Electron Asymmetry‐Driven CN Coupling on Heteronuclear Dual‐Atom Catalysts for Sustainable Urea Electrosynthesis

Abstract The transition toward carbon‐neutral chemical manufacturing calls for innovative strategies to produce nitrogen‐based compounds with minimal environmental impact. Urea, a key nitrogen‐rich chemical, is currently synthesized via the energy‐intensive Bosch‐Meiser process, which relies heavily on fossil fuel‐derived ammonia. As a sustainable alternative, electrochemical urea synthesis (ECUS) enables the direct coupling of nitrogenous and carbonaceous precursors under ambient conditions, yet remains hampered by sluggish kinetics and poor selectivity—particularly in the critical C─N bond formation step. Here, density functional theory (DFT) calculations is integrated with data‐driven machine learning to systematically explore the activity landscape of nitrogen‐doped graphene‐supported dual‐metal‐atom catalysts (M′M@NC) for C─N coupling. A comprehensive reaction network is evaluated across 45 M′M@NC configurations, revealing three heteronuclear catalysts—VNi@NC, CoNi@NC and CoCu@NC—with consistently favorable thermodynamic and kinetic performance. Electronic structure analysis indicates that heteronuclear coordination promotes *CO activation and optimizes *NH x adsorption, facilitating C─N coupling. Leveraging symbolic regression via the sure independence screening and sparsifying operator (SISSO) algorithm, interpretable descriptors linking C─N coupling energy to atomic‐level electronic properties is established, highlighting the critical role of d‐electron asymmetry. This results uncover fundamental design principles for dual‐atom catalysts and provide a predictive framework for guiding the development of next‐generation electrocatalysts for sustainable urea synthesis.