The decisive role of adsorbed OH^(*)in low‐potential CO electro‐oxidation on single‐atom catalytic sites  

作　　者：Yang Li Xian Wang Ying Wang Zhaoping Shi Yuqi Yang Tuo Zhao Zheng Jiang Changpeng Liu Wei Xing Junjie Ge 

机构地区：[1]State Key Laboratory of Electroanalytic Chemistry,Jilin Province Key Laboratory of Low Carbon Chemistry Power,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun,China [2]School of Applied Chemistry and Engineering,University of Science and Technology of China,Hefei,China [3]State Key Laboratory of Rare Earth Resource Utilization,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun,China [4]Shanghai Institute of Applied Physics,Chinese Academy of Sciences,Shanghai,China [5]Shanghai Synchrotron Radiation Facility,Zhangjiang National Laboratory,Shanghai Advanced Research Institute,Chinese Academy of Sciences,Shanghai,China [6]University of Chinese Academy of Sciences,Beijing,China [7]Dalian National Laboratory for Clean Energy,Dalian,China

出　　处：《Carbon Energy》2023年第9期63-73,共11页碳能源（英文）

基　　金：Jilin Province Science and Technology Development Program,Grant/Award Numbers:20180101030JC,20190201270JC,20200201001JC;National Natural Science Foundation of China,Grant/Award Numbers:21633008,21673221,21875243,U1601211;Research Innovation Fund,Grant/Award Number:DNL202010;Special Funds for Guiding Local Scientific and Technological Development by the Central Government,Grant/Award Number:2020JH6/10500021。

摘　　要：CO impurity-induced catalyst deactivation has long been one of the biggest challenges in proton-exchange membrane fuel cells,with the poisoning phenomenon mainly attributed to the overly strong adsorption on the catalytic site.Here,we present a mechanistic study that overturns this understanding by using Rh-based single-atom catalysis centers as model catalysts.We precisely modulated the chelation structure of the Rh catalyst by coordinating Rh with C or N atoms,and probed the reaction mechanism by surface-enhanced Raman spectroscopy.Direct spectroscopic evidence for intermediates indicates that the reactivity of adsorbed OH^(*),rather than the adsorption strength of CO^(*),dictates the CO electrocatalytic oxidation behavior.The RhN_(4)sites,which adsorb the OH^(*)intermediate more weakly than RhC4 sites,showed prominent CO oxidation activity that not only far exceeded the traditional Pt/C but also the RhC4 sites with similar CO adsorption strength.From this study,it is clear that a paradigm shift in future research should be considered to rationally design high-performance CO electro-oxidation reaction catalysts by sufficiently considering the water-related reaction intermediate during catalysis.

关 键 词：adsorbed CO^(*)and OH^(*) carbon‐based Rh single‐atom catalysts CO electro‐oxidation reaction electron interaction MNx moiety 

分 类 号：O64[理学—物理化学]