Chinese Journal of Catalysis ›› 2022, Vol. 43 ›› Issue (11): 2772-2791.DOI: 10.1016/S1872-2067(22)64095-6

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Fundamental aspects in CO2 electroreduction reaction and solutions from in situ vibrational spectroscopies

Hong Lia, Kun Jiangb, Shou-Zhong Zouc,#(), Wen-Bin Caia,*()   

  1. aShanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, Fudan University, Shanghai 200438, China
    bSchool of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
    cDepartment of Chemistry, American University, Washington, District of Columbia 20016, United States
  • Received:2022-04-30 Accepted:2022-07-27 Online:2022-11-18 Published:2022-10-20
  • Contact: Shou-Zhong Zou, Wen-Bin Cai
  • About author:Shouzhong Zou (Department of Chemistry, American University) earned his B.S. in Chemistry in 1991 and completed his MS studies in 1994 from Xiamen University under the guidance of Prof. Zhong-Qun Tian. He received his Ph.D. in Chemistry from Purdue University in 1999 under the direction of Prof. Michael J. Weaver. He then did postdoctoral work at Caltech with Profs. Fred C Anson and Ahmed H. Zewail. He started his independent research as an assistant professor in 2002 at Miami University (Oxford, Ohio), and was promoted to associate professor in 2008. He joined American University in the summer of 2015 as a full professor and chair. His research interests include developing catalysts for low temperature fuel cells, CO2 reduction and gas sensing, and advancing spectroscopic and microscopic techniques for the characterization of surfaces and interfaces.
    Wen-Bin Cai (Department of Chemistry, Fudan University) received his B.A. degree and M.S. degree from Shanghai University of Science and Technology in 1989 and 1992, respectively, under the guidance of Prof. Xun-Nan Deng and Ph.D. degree from Fudan University in 1995 under the guidance of Prof. Wei-Fang Zhou. From 1995 to 2002, he did postdoctoral research work consecutively at Xiamen University (with Prof. Zhong-Qun Tian), Hokkaido University (with Prof. Masatoshi Osawa), and Case Western Reserve University (with Profs. Daniel Scherson and James Burgess). Since July 2002, he has been a professor at Fudan University. His research interests cover interfacial spectroelectrochemistry and electrocatalysis, including but not limited to methodological development and application of electrochemical ATR-SEIRAS, mechanistic understanding and catalyst development towards electrocatalysis of small organic molecule oxidation, oxygen reduction and carbon dioxide reduction.
  • Supported by:
    National Natural Science Foundation of China(21733004);National Natural Science Foundation of China(22002088);International Cooperation Program of Shanghai Science and Technology Committee(17520711200);Shanghai Sailing Program(20YF1420500)


Using renewable energy to drive carbon dioxide reduction reaction (CO2RR) electrochemically into chemicals with high energy density is an efficient way to achieve carbon neutrality, where the effective utilization of CO2 and the storage of renewable energy are realized. The reactivity and selectivity of CO2RR depend on the structure and composition of the catalyst, applied potential, electrolyte, and pH of the solution. Besides, multiple electron and proton transfer steps are involved in CO2RR, making the reaction pathways even more complicated. In pursuit of molecular-level insights into the CO2RR processes, in situ vibrational methods including infrared, Raman and sum frequency generation spectroscopies have been deployed to monitor the dynamic evolution of catalyst structure, to identify reactive intermediates as well as to investigate the effect of local reaction environment on CO2RR performance. This review summarizes key findings from recent electrochemical vibrational spectrosopic studies of CO2RR in addressing the following issues: the CO2RR mechanisms of different pathways, the role of surface-bound CO species, the compositional and structural effects of catalysts and electrolytes on CO2RR activity and selectivity. Our perspectives on developing high sensitivity wide-frequency infrared spectroscopy, coupling different spectroelectrochemical methods and implementing operando vibrational spectroscopies to tackle the CO2RR process in pilot reactors are offered at the end.

Key words: Carbon dioxide electroreduction reaction, Electrocatalytic mechanism, Vibrational spectroscopy, Intermediate, Structure-performance relation, Electrolyte effect