The decisive role of adsorbed OH* in low‐potential CO electro‐oxidation on single‐atom catalytic sites
Yang Li,
Xian Wang,
Ying Wang,
Zhaoping Shi,
Yuqi Yang,
Tuo Zhao,
Zheng Jiang,
Changpeng Liu,
Wei Xing,
Junjie Ge
Affiliations
Yang Li
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
Xian Wang
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
Ying Wang
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry Chinese Academy of Sciences Changchun China
Zhaoping Shi
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
Yuqi Yang
Shanghai Institute of Applied Physics Chinese Academy of Sciences Shanghai China
Tuo Zhao
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
Zheng Jiang
Shanghai Institute of Applied Physics Chinese Academy of Sciences Shanghai China
Changpeng Liu
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
Wei Xing
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
Junjie Ge
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
Abstract 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 RhN4 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.
