Enhancing Local CO2 Adsorption by L‐histidine Incorporation for Selective Formate Production Over the Wide Potential Window

Abstract Electrochemical carbon dioxide reduction reaction (CO 2 RR) to produce valuable chemicals is a promising pathway to alleviate the energy crisis and global warming issues. However, simultaneously achieving high Faradaic efficiency (FE) and current densities of CO 2 RR in a wide potential range remains as a huge challenge for practical implements. Herein, we demonstrate that incorporating bismuth‐based (BH) catalysts with L‐histidine, a common amino acid molecule of proteins, is an effective strategy to overcome the inherent trade‐off between the activity and selectivity. Benefiting from the significantly enhanced CO 2 adsorption capability and promoted electron‐rich nature by L‐histidine integrity, the BH catalyst exhibits excellent FE formate in the unprecedented wide potential windows (>90 % within −0.1–−1.8 V and >95 % within −0.2–−1.6 V versus reversible hydrogen electrode, RHE). Excellent CO 2 RR performance can still be achieved under the low‐concentration CO 2 feeding (e.g., 20 vol.%). Besides, an extremely low onset potential of −0.05 V RHE (close to the theoretical thermodynamic potential of −0.02 V RHE ) was detected by in situ ultraviolet‐visible (UV‐Vis) measurements, together with stable operation over 50 h with preserved FE formate of ≈95 % and high partial current density of 326.2 mA cm −2 at −1.0 V RHE .