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

Abstract

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.

Review on strategies for improving the added value and expanding the scope of CO2 electroreduction products

“…4(a), the CO 2 electroreduction into formate comprises two primary steps: (1) the conversion of CO 2 molecules into *OCHO intermediate via a process involving the transfer of a proton–electron pair and (2) the subsequent conversion of *OCHO into *HCOOH intermediate through a proton-coupling electron transfer process, resulting in the generation of formate as the final product. 67 Furthermore, the formation of key reactive intermediates such as *OCHO and *HCOOH has been verified using in situ spectral characterization techniques during CO 2 RR 68,69 (Fig. 4(b)–(d)).…”

“…127 The Gemini surfactants, with their double quaternary ammonium cations and alkyl chains, serve the dual purpose of stabilizing the crucial intermediate HCOO* and facilitating the accessibility of CO 2 . Additionally, l -histidine, 68 polyethylene glycol, 124 vitamin C, 128 sulfur anions, and sodium cations 129 have also been reported for surface modification of Bi-based catalysts. However, currently, there is no research reported on whether these surface modifiers for Bi-based materials can effectively retain their presence on the catalyst surface during the long-time electrocatalytic CO 2 RR test process.…”

The Tandem Nitrate and CO2 Reduction for Urea Electrosynthesis: Role of Surface N‐Intermediates in CO2 Capture and Activation

“…Even at a low level of 15 %, the FE of urea reaches as high as 42.33 % that is already close to the optimal FE when using a flow cell. This result is intriguing, since the CO 2 level significantly affects the reaction rate of CO 2 RR [24] and thereby the surface coverage of CO 2 RR intermediates, if participant in CÀ N coupling is the CO 2 RR intermediates, it is apparently that the efficiency and selectivity of CÀ N coupling can be notably influence by CO 2 level. [25] Consequently, the limited influence of CO 2 concentration on urea FE would suggest the participant in CÀ N coupling being CO 2 itself.…”

Aqueous Zn–CO2 batteries: a route towards sustainable energy storage

“…An electrochemical CO 2 reduction reaction (CO 2 RR) has been recently demonstrated to be an effective strategy to use excess sustainable electricity for upgrading CO 2 into value-added chemicals (such as HCOOH or C 2 H 4 ). [4][5][6][7][8][9][10] Notably, compared with metal-ion or metal-air batteries, [11][12][13][14][15][16] metal-CO 2 batteries do not only reduce CO 2 into products of high value but also provide energy during the discharging process, which is regarded as an extra advantage compared to the individual electrochemical CO 2 conversion. 17,18 Therefore, metal-CO 2 batteries on a larger scale can become a powerful tool for both energy and raw material management.…”