AbstractElectrocatalytic CO2 reduction (CO2RR) offers a promising avenue to address rising atmospheric CO2 levels by producing high‐value chemicals. However, the development of efficient, long‐lasting catalysts remains challenging. In this study, particle swarm optimization is employed to design a novel bimetallic boronene structure, thereby enhancing CO2RR activity through precise tuning of the metal‐substrate microenvironment. Through high‐throughput screening, seven CuMB4 (M = V, Zn, Nb, Ag, Cd, Ta, Au) monolayers are identified as promising CO2RR catalysts based on stability, conductivity, catalytic activity, and selectivity. These materials, characterized by hyper‐coordination and neighboring bimetallic effects, are proposed for synthesis via self‐assembled surface growth. Notably, CuZnB4 exhibited exceptional theoretical catalytic activity, characterized by remarkably low limiting potentials (UL) of −0.16 V for CH4 and −0.27 V for C2H4, as well as low kinetic barriers of 0.65 and 0.53 eV, respectively. The enhanced activity results from neighboring effects optimizing densely populated boron active sites and the ability to suppress hydrogen evolution reactions. Additionally, this study explored intrinsic properties influencing catalytic activity using volcano plots, descriptor analysis, and electron density evaluation. Unlike traditional catalysts prone to oxidation, CuMB4 varieties possess self‐activating properties, facilitating the conversion of *O/*OH to H2O and enhancing CO2 conversion. This research introduces robust CO2RR catalysts and provides insights into manipulating neighboring effects, thus guiding future catalyst design.
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