Design of Twisted Metal Intercalated Bilayer for Descriptor of Electrocatalytic Urea Synthesis

Metal intercalation and structural twisting are effective strategies for achieving precise control over the electronic properties, geometric configuration, and catalytic performance of layered materials. By regulating electron distribution and surface reactivity, these approaches facilitate reactant adsorption and subsequent activation, followed by coupling between surface species, thereby providing a versatile platform for the rational design of efficient and selective electrocatalysts. Based on this concept, we designed a twisted BC₄N-TM-BC₄N sandwich structure and systematically investigated its electrocatalytic performance for urea synthesis. After screening for stability and catalytic activity, 31 representative systems were identified and analyzed in terms of their electronic structures and catalytic behaviors. The results reveal that metal intercalation and twisting effectively modulate charge redistribution within the bilayer, enabling efficient electron transfer along the metal-B-N pathway and activating B sites to facilitate NO activation. This effect results in a marked decrease in reaction free energy, improves the adsorption process, and facilitates the coupling of NO and CO. Different metal systems exhibit optimal catalytic activity at specific twist angles, with most systems showing the best performance at 98.213°. Moreover, the majority of twisted systems demonstrate enhanced selectivity, indicating that this strategy improves both activity and selectivity simultaneously. Through SISSO-based machine learning, we derived a descriptor that quantitatively correlates catalytic activity to electronic properties as well as twist angle, exhibiting a robust linear relationship with U_max. This work delivers theoretical guidance for the rational construction of efficient and tunable urea electrocatalysts based on structural twisting and metal intercalation and offers valuable insights for the development of other multielectron coupling catalytic systems.