Engineering Molecular Heterostructured Catalyst for Oxygen Reduction Reaction

Chang Chen; Yifan Li; Aijian Huang; Xuerui Liu; Jiazhan Li; Yu Zhang; Zhiqiang Chen; Zewen Zhuang; Yue Wu; Weng-Chon Cheong; Xin Tan; Kaian Sun; Zhiyuan Xu; Di Liu; Zhiguo Wang; Kebin Zhou; Chen Chen

doi:10.1021/jacs.3c05371

Engineering Molecular Heterostructured Catalyst for Oxygen Reduction Reaction

J Am Chem Soc. 2023 Oct 4;145(39):21273-21283. doi: 10.1021/jacs.3c05371. Epub 2023 Sep 20.

Authors

Chang Chen^{1

2}, Yifan Li^{2

3}, Aijian Huang^{1

4}, Xuerui Liu⁵, Jiazhan Li¹, Yu Zhang¹, Zhiqiang Chen⁶, Zewen Zhuang⁷, Yue Wu⁷, Weng-Chon Cheong⁸, Xin Tan¹, Kaian Sun¹, Zhiyuan Xu¹, Di Liu¹, Zhiguo Wang⁴, Kebin Zhou², Chen Chen¹

Affiliations

¹ Engineering Research Center of Advanced Rare Earth Materials, Department of Chemistry, Tsinghua University, Beijing 100084, China.
² School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China.
³ Department of Chemical and Materials Engineering, University of Alberta, Edmonton, AB T6G1H9, Canada.
⁴ School of Electronics Science and Engineering, University of Electronic Science and Technology of China, Chengdu 610054, China.
⁵ Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China.
⁶ Beijing Key Laboratory of Research and Application for Aerospace Green Propellants, Beijing Institute of Aerospace Testing Technology, Beijing 100048, China.
⁷ College of Materials Science and Engineering, Fuzhou University, Fuzhou 350108, China.
⁸ Macao Institute of Materials Science and Engineering (MIMSE), Faculty of Innovation Engineering, Macau University of Science and Technology, Taipa, Macao SAR 999078, China.

PMID: 37729633
DOI: 10.1021/jacs.3c05371

Abstract

Introducing a second metal species into atomically dispersed metal-nitrogen-carbon (M-N-C) catalysts to construct diatomic sites (DASs) is an effective strategy to elevate their activities and stabilities. However, the common pyrolysis-based method usually leads to substantial uncertainty for the formation of DASs, and the precise identification of the resulting DASs is also rather difficult. In this regard, we developed a two-step specific-adsorption strategy (pyrolysis-free) and constructed a DAS catalyst featuring FeCo "molecular heterostructures" (FeCo-MHs). In order to rule out the possibility of the two apparently neighboring (in the electron microscopy image) Fe/Co atoms being dispersed respectively on the top/bottom surfaces of the carbon support and thus forming "false" MHs, we conducted in situ rotation (by 8°, far above the critical angle of 5.3°) and directly identified the individual FeCo-MHs. The formation of FeCo-MHs could modulate the magnetic moments of the metal centers and increase the ratio of low-spin Fe(II)-N₄ moiety; thus the intrinsic activity could be optimized at the apex of the volcano-plot (a relationship as a function of magnetic moments of metal-phthalocyanine complexes and catalytic activities). The FeCo-MHs catalyst displays an exceptional ORR activity (E_1/2 = 0.95 V) and could be used to construct high-performance cathodes for hydroxide exchange membrane fuel cells and zinc-air batteries.