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

Electrochemical carbon dioxide reduction reaction (CO2RR) 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 CO2RR 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 CO2 adsorption capability and promoted electron-rich nature by L-histidine integrity, the BH catalyst exhibits excellent FEformate 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 CO2RR performance can still be achieved under the low-concentration CO2 feeding (e.g., 20 vol.%). Besides, an extremely low onset potential of -0.05 VRHE (close to the theoretical thermodynamic potential of -0.02 VRHE) is detected by in situ ultraviolet measurements, together with stable operation over 50 h with preserved FEformate of ~ 95% and a high partial current density of 326.2 mA cm-2 at -1.0 VRHE.