Twist Engineering of M₂CO/BCN Heterostructures for Descriptor of Urea Electrocatalysis

Electrocatalytic urea production through C-N coupling offers a sustainable alternative to traditional energy-intensive processes; however, its practical implementation is still limited by thermodynamically unfavorable pathways and slow C-N coupling kinetics. We design systematically a series of twisted two-dimensional heterostructures composed of BCN and MXenes, denoted as M₂CO/BCN (M = Ti, V, Cr), with six representative rotation angles (0°, 10.89°, 49.11°, 60°, 70.89°, and 109.11°). Density functional theory calculations reveal that interfacial twisting effectively modulates charge redistribution and electronic coupling, thereby promoting CO and NO activation. Thermodynamic analyses combined with constrained ab initio molecular dynamics simulations demonstrate that twisting markedly reduces both the free energy variation and the kinetic barriers associated with the C-N coupling step. As a result, V₂CO/BCN-109.11° exhibits the lowest reaction potential of -0.23 V. Our findings establish interfacial twisting as an effective strategy for simultaneously optimizing thermodynamics and kinetics in electrocatalytic urea synthesis. Finally, we apply the Sure Independence Screening and Sparsifying Operator (SISSO) approach to identify a physically interpretable descriptor that quantitatively correlates twist-induced structural factors with catalytic performance, providing a key insight into the structure-activity relationship.