Spin engineering of single-site metal catalysts

Zichuang Li; Ruguang Ma; Qiangjian Ju; Qian Liu; Lijia Liu; Yufang Zhu; Minghui Yang; Jiacheng Wang

The Innovation (Jul 2022)

Affiliations

Zichuang Li: State Key Laboratory of High-Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, China; Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
Ruguang Ma: State Key Laboratory of High-Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, China; School of Materials Science and Engineering, Suzhou University of Science and Technology, 99 Xuefu Road, Suzhou 215009, China; Corresponding author
Qiangjian Ju: State Key Laboratory of High-Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, China; Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
Qian Liu: State Key Laboratory of High-Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, China; Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
Lijia Liu: Department of Chemistry, Western University, 1151 Richmond Street, London, ON N6A 5B7, Canada
Yufang Zhu: State Key Laboratory of High-Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, China; Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
Minghui Yang: Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, 1219 Zhongguan West Road, Ningbo 315201, China
Jiacheng Wang: State Key Laboratory of High-Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, China; Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China; Hebei Provincial Key Laboratory of Inorganic Nonmetallic Materials, College of Materials Science and Engineering, North China University of Science and Technology, Tangshan 063210, China; Corresponding author

Journal volume & issue: Vol. 3, no. 4
p. 100268

Abstract

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Single-site metal atoms (SMAs) on supports are attracting extensive interest as new catalytic systems because of maximized atom utilization and superior performance. However, rational design of configuration-optimized SMAs with high activity from the perspectives of fundamental electron spin is highly challenging. Herein, N-coordinated Fe single atoms are successfully distributed over axial carbon micropores to form dangling-FeN4 centers (d-FeN4). This unique d-FeN4 demonstrates much higher intrinsic activity toward oxygen reduction reaction (ORR) in HClO4 than FeN4 without micropore underneath and commercial Pt/C. Both theoretical calculation and electronic structure characterization imply that d-FeN4 endows central Fe with medium spin (t2g4 eg1), which provides a spin channel for electron transition compared with FeN4 with low spin. This leads to the facile formation of the singlet state of oxygen-containing species from triplet oxygen during the ORR, thus showing faster kinetics than FeN4. This work provides an in-depth understanding of spin tuning on SMAs for advanced energy catalysis.

Published in The Innovation

ISSN: 2666-6758 (Online)
Publisher: Elsevier
Country of publisher: United States
LCC subjects: Science: Science (General)
Website: https://www.cell.com/the-innovation

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