Abstract

Carbon dioxide (CO2) capture and utilization have garnered significant interest across various industrial fields due to both challenges and opportunities. This study presents a comprehensive theoretical screening of 18 transition metal-doped defective porous boron nitride (TM@p-BNVB and TM@p-BNVN) catalysts using density functional theory (DFT) to assess their potential for CO2 reduction reaction (CO2RR). Among these, 11 TM@p-BNVB candidates exhibited excellent thermodynamic and electrochemical stability, effective CO2 activation and high selectivity for CO2RR. Transition metals such as V, Fe, Ni, Cu, and Pd anchored on p-BNVB emerged as top performers, demonstrating outstanding activity and selectivity toward C1 products while effectively surpassing the competing hydrogen evolution reaction (HER). Specifically, V@p-BNVB and Fe@p-BNVB exhibited remarkable electrocatalytic activity for HCOOH and CH3OH production, achieving exceptionally low limiting potentials of-0.16V and-0.12V for V@p-BNVB, and-0.05V and-0.20V for Fe@p-BNVB, respectively. Notable, V@p-BNVB displayed the lowest limiting potential for CH3OH production, while Fe@p-BNVB showed superior activity for HCOOH generation, underscoring their exceptional activity and selectivity among the screened materials. Furthermore, this study introduces an innovative descriptor that quantitatively elucidates structure-Activity relationships for C1 product formation. Derived from fundamental properties such as d-electron count and the electronegativity of the metal, along with the generalized electronegativity of substrate atoms and key intermediates, the descriptor φ provides a straightforward yet effective framework for predicting catalytic performance. These findings offer valuable insights and establish a robust foundation for the rational design and screening of highly active and selective CO2RR catalysts.