Rational Linker Design for Enhanced Performance of MOF‐Derived Catalysts in Electrochemical Urea Synthesis

Abstract 2D metal–organic frameworks (2D MOFs) offer promising electrocatalytic potential for urea synthesis, yet the underlying reaction mechanisms and structure‐activity relationships remain unclear. Using Cu‐BDC as a model, density functional theory (DFT) calculations to elucidate these aspects are conducted. The results reveal a novel coupling mechanism involving *NO─CO and *NO─*ONCO, emphasizing the impact of linker modifications on Cu spin states and charge distribution. Notably, Cu‐BDC‐NH₂ and Cu─BDC─OH emerge as promising catalysts. Additionally, structure‐activity relationships through descriptors like d‐band center, IE ratio, and L(Cu─O), providing insights for rational catalyst design is established. These findings pave the way for optimized catalysts and sustainable urea production, opening avenues for future research and technological advancements.