Angulated Edge Intrinsic Defect in Carbon as Bridge‐Adsorption Site of CO for Highly Efficient CO2 Electroreduction.

Pervasive intrinsic defects have a significant impact on the electrocatalytic activity of carbon materials, but previous research has focused on the effects of topological structures exclusively. Herein, a compelling demonstration of the pivotal role played by the positions and spatial arrangement of intrinsic defects in determining their efficacy for electrochemical CO2 reduction (ECR) is presented. Theoretical calculations reveal a substantial reduction in energy barriers for *COOH formation at intrinsic defects positioned along the edges while hindering the transformation of *COOH to *CO in the ECR process. To address this issue, a sea urchin‐like nanocarbon (F1100) is designed, which provides adjacent intrinsic defects located in V‐type arranged carbon nanorods. The angulated edge intrinsic defects facilitate the bridge adsorption of carbon monoxide (CO), as confirmed by in situ attenuated total reflection surface‐enhanced infrared absorption spectroscopy, thereby enhancing the specific activity of ECR on intrinsic carbon defects. In a 0.1 m potassium bicarbonate (KHCO3) solution, F1100 achieves a FECO of 95.0%, while in an ionic liquids‐based electrolyte, a current density of 90.0 mA cm−2 is obtained with nearly complete conversion of CO2 to CO in an H‐type cell. [ABSTRACT FROM AUTHOR]