Boron‐Coordinated Carbon‐Nitrogen Monolayer Supported Transition Metal Catalysts for Efficient Electrochemical CO 2 RR

ABSTRACT Developing efficient electrocatalysts for the electrochemical reduction of CO 2 to valuable chemicals is crucial for reducing CO 2 concentration and achieving carbon neutrality. This study focuses on the nitrogen‐carbon monolayer (CN) and systematically investigates the electrocatalytic CO 2 reduction reaction (CO 2 RR) by introducing boron (B) as a central metal‐coordination atom. We constructed 26 TM@B‐CN catalysts and identified Ta@B‐CN as exhibiting superior CO 2 RR activity. Systematic studies revealed that Ta@B‐CN not only possesses higher Faradaic Efficiency (FE) but also exhibits lower potential limitations for CO 2 reduction to CO. Compared with the computational Hydrogen Electrode (CHE), the limiting potential for the CO 2 reduction to CO on Ta@B‐CN is only about −0.13 V. This research elucidates the intrinsic mechanisms of excellent catalysts through in‐depth computational and electronic structure analysis. The findings provide valuable guidance for designing more efficient CO 2 RR catalysts, holding significant implications for addressing climate change and advancing clean energy development.