Operando formation of highly efficient electrocatalysts induced by heteroatom leaching

Cong Liu; Bingbao Mei; Zhaoping Shi; Zheng Jiang; Junjie Ge; Wei Xing; Ping Song; Weilin Xu

doi:10.1038/s41467-023-44480-9

Operando formation of highly efficient electrocatalysts induced by heteroatom leaching

Nat Commun. 2024 Jan 4;15(1):242. doi: 10.1038/s41467-023-44480-9.

Authors

Cong Liu^{1

2}, Bingbao Mei³, Zhaoping Shi^{1

2}, Zheng Jiang^{2

3}, Junjie Ge¹, Wei Xing^{1

2}, Ping Song⁴, Weilin Xu^{5

6}

Affiliations

¹ State Key Laboratory of Electroanalytical Chemistry, & Jilin Province Key Laboratory of Low Carbon Chemical Power, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, China.
² School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei, 230026, China.
³ Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201204, China.
⁴ State Key Laboratory of Electroanalytical Chemistry, & Jilin Province Key Laboratory of Low Carbon Chemical Power, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, China. songping@ciac.ac.cn.
⁵ State Key Laboratory of Electroanalytical Chemistry, & Jilin Province Key Laboratory of Low Carbon Chemical Power, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, China. weilinxu@ciac.ac.cn.
⁶ School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei, 230026, China. weilinxu@ciac.ac.cn.

Abstract

Heterogeneous nano-electrocatalysts doped with nonmetal atoms have been studied extensively based on the so-called dopant-based active sites, while little attention has been paid to the stability of these dopants under working conditions. In this work, we reveal significantly, when the redox working potential is too low negatively or too high positively, the active sites based on these dopants actually tend to collapse. It means that some previously observed "remarkable catalytic performance" actually originated from some unknown active sites formed in situ. Take the Bi-F for the CO₂RR as an example, results show that the observed remarkable activity and stability were not directly from F-based active sites, but the defective Bi sites formed in situ after the dopant leaching. Such a fact is unveiled from several heteroatom-doped nanocatalysts for four typical reactions (CO₂RR, HER, ORR, and OER). This work provides insight into the role of dopants in electrocatalysis.