文献类型：期刊文献

英文题名：Boosting Electrochemical CO2 Reduction via Surface Hydroxylation over Cu-Based Electrocatalysts

作者：Li, Congcong[1];Guo, Zhongyuan[3,4];Liu, Zhongliang[1];Zhang, Tingting[1];Shi, Haojun[2];Cui, Jialin[1];Zhu, Minghui[1];Zhang, Ling[2];Li, Hao[3];Li, Huihui[1];Li, Chunzhong[1,2]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, Key Lab Ultrafine Mat, Minist Educ, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Shanghai Engn Res Ctr Hierarch Nanomat, Sch Mat Sci & Engn, Shanghai 200237, Peoples R China;[3]Tohoku Univ, Adv Inst Mat Res WPI AIMR, Sendai 9808577, Japan;[4]Zhejiang Univ, Coll Environm & Resource Sci, Hangzhou 310058, Peoples R China

年份：2023

卷号：13

期号：24

起止页码：16114

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20235015222244);WOS:【SCI-EXPANDED(收录号:WOS:001142912700001)】；

基金：This work was supported by the National Natural Science Foundation of China (grants 21838003, 21771170, and 22008069), the Shanghai Municipal Science and Technology Major Project, Shanghai Rising-Star Program (20QA1402700), the Shanghai Sailing Program (20YF1410200), the JSPS KAKENHI (JP23K13703), and the Iwatani Naoji Foundation. The authors thank the Shanghai synchrotron Radiation Facility (14W1, SSRF). H.L. acknowledges the Center for Computational Materials Science, Institute for Materials Research, Tohoku University for the use of MASAMUNE-IMR (project no. 202212-SCKXX-0204) and the Institute for Solid State Physics (ISSP) at the University of Tokyo for the use of their supercomputers.

语种：英文

外文关键词：electrochemical CO2 reduction; surface hydroxylation; C-C coupling; multicarbon products; Cu-based catalysts

摘要：Electrochemical CO2 reduction (CO2R) to valuable multicarbon (C2+) products is an attractive means for upgrading waste CO2. One of the intensively studied strategies is to apply concentrated KOH solution to extensively proceed with CO2R to C2+ products; however, the undesired carbonate formation at the cathode consumes majority of the input CO2. Therefore, it is crucial to seek a new strategy to improve the local environment at the electrode and thus eliminate or reduce dependence of the selectivity of CO2R on bulk OH- concentration. However, tailoring a stable surface hydroxylation reaction microenvironment near the catalyst surface throughout the extended CO2R operation process is still a challenge. Here, we implement the concept of molecular surface modification experimentally by applying a hydroxyl-functionalized surface strategy (i.e., capping hydroxyl-rich molecules over a set of Cu2O catalysts) to enhance the formation of C2+ products. Electrochemical experiments and operando characterizations confirm the stable presence of hydroxyl species near the catalyst surface during the CO2R operation and its advantage in converting absorbed *CO into C2+ products. As a result, the Faradaic efficiency of C2+ products of 81.5% and the cathodic energy efficiency of 43.1% were achieved with a partial current density of 285 mA cm(-2) in a flow cell. Using a cation-exchange membrane electrode assembly device, we demonstrated the stable production of ethylene over 100 h at an average current density of 151 mA cm(-2). Theoretical analyses also show that hydroxyl-rich molecules such as gluconic acid can lead to the electron loss of the Cu sites, which is beneficial for *CO adsorption and thus the formation of C2+ products. Our results reveal the significance of tailoring a stable local reaction microenvironment over the catalyst surface in an electrochemical system.