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Title: Engineering Single-Atom Cobalt Catalysts toward Improved Electrocatalysis

Abstract

In this paper, the development of cost-effective catalysts to replace noble metal is attracting increasing interests in many fields of catalysis and energy, and intensive efforts are focused on the integration of transition-metal sites in carbon as noble-metal-free candidates. Recently, the discovery of single-atom dispersed catalyst (SAC) provides a new frontier in heterogeneous catalysis. However, the electrocatalytic application of SAC is still subject to several theoretical and experimental limitations. Further advances depend on a better design of SAC through optimizing its interaction with adsorbates during catalysis. Here, distinctive from previous studies, favorable 3d electronic occupation and enhanced metal-adsorbates interactions in single-atom centers via the construction of nonplanar coordination is achieved, which is confirmed by advanced X-ray spectroscopic and electrochemical studies. The as-designed atomically dispersed cobalt sites within nonplanar coordination show significantly improved catalytic activity and selectivity toward the oxygen reduction reaction, approaching the benchmark Pt-based catalysts. More importantly, the illustration of the active sites in SAC indicates metal-natured catalytic sites and a media-dependent catalytic pathway. Achieving structural and electronic engineering on SAC that promotes its catalytic performances provides a paradigm to bridge the gap between single-atom catalysts design and electrocatalytic applications.

Authors:
 [1];  [2];  [2];  [3];  [3];  [3];  [2];  [1];  [1];  [4];  [5]; ORCiD logo [2]
  1. Chinese Academy of Sciences, Shanghai (People's Republic of China); Univ. of Chinese Academy of Sciences, Beijing (People's Republic of China)
  2. Chinese Academy of Sciences, Shanghai (People's Republic of China)
  3. Argonne National Lab. (ANL), Lemont, IL (United States)
  4. Illinois Institute of Technology, Chicago, IL (United States)
  5. Argonne National Lab. (ANL), Lemont, IL (United States); Northern Illinois Univ., DeKalb, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Key Basic Research Program of China; USDOE
OSTI Identifier:
1474147
Alternate Identifier(s):
OSTI ID: 1423700
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Small
Additional Journal Information:
Journal Volume: 14; Journal Issue: 15; Journal ID: ISSN 1613-6810
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; electrocatalysis; media-dependence; metal-adsorbate interactions; selectivity; single-atom dispersed catalysts

Citation Formats

Wan, Gang, Yu, Pengfei, Chen, Hangrong, Wen, Jianguo, Sun, Cheng-jun, Zhou, Hua, Zhang, Nian, Li, Qianru, Zhao, Wanpeng, Xie, Bing, Li, Tao, and Shi, Jianlin. Engineering Single-Atom Cobalt Catalysts toward Improved Electrocatalysis. United States: N. p., 2018. Web. doi:10.1002/smll.201704319.
Wan, Gang, Yu, Pengfei, Chen, Hangrong, Wen, Jianguo, Sun, Cheng-jun, Zhou, Hua, Zhang, Nian, Li, Qianru, Zhao, Wanpeng, Xie, Bing, Li, Tao, & Shi, Jianlin. Engineering Single-Atom Cobalt Catalysts toward Improved Electrocatalysis. United States. doi:10.1002/smll.201704319.
Wan, Gang, Yu, Pengfei, Chen, Hangrong, Wen, Jianguo, Sun, Cheng-jun, Zhou, Hua, Zhang, Nian, Li, Qianru, Zhao, Wanpeng, Xie, Bing, Li, Tao, and Shi, Jianlin. Mon . "Engineering Single-Atom Cobalt Catalysts toward Improved Electrocatalysis". United States. doi:10.1002/smll.201704319. https://www.osti.gov/servlets/purl/1474147.
@article{osti_1474147,
title = {Engineering Single-Atom Cobalt Catalysts toward Improved Electrocatalysis},
author = {Wan, Gang and Yu, Pengfei and Chen, Hangrong and Wen, Jianguo and Sun, Cheng-jun and Zhou, Hua and Zhang, Nian and Li, Qianru and Zhao, Wanpeng and Xie, Bing and Li, Tao and Shi, Jianlin},
abstractNote = {In this paper, the development of cost-effective catalysts to replace noble metal is attracting increasing interests in many fields of catalysis and energy, and intensive efforts are focused on the integration of transition-metal sites in carbon as noble-metal-free candidates. Recently, the discovery of single-atom dispersed catalyst (SAC) provides a new frontier in heterogeneous catalysis. However, the electrocatalytic application of SAC is still subject to several theoretical and experimental limitations. Further advances depend on a better design of SAC through optimizing its interaction with adsorbates during catalysis. Here, distinctive from previous studies, favorable 3d electronic occupation and enhanced metal-adsorbates interactions in single-atom centers via the construction of nonplanar coordination is achieved, which is confirmed by advanced X-ray spectroscopic and electrochemical studies. The as-designed atomically dispersed cobalt sites within nonplanar coordination show significantly improved catalytic activity and selectivity toward the oxygen reduction reaction, approaching the benchmark Pt-based catalysts. More importantly, the illustration of the active sites in SAC indicates metal-natured catalytic sites and a media-dependent catalytic pathway. Achieving structural and electronic engineering on SAC that promotes its catalytic performances provides a paradigm to bridge the gap between single-atom catalysts design and electrocatalytic applications.},
doi = {10.1002/smll.201704319},
journal = {Small},
number = 15,
volume = 14,
place = {United States},
year = {2018},
month = {3}
}

Journal Article:
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Cited by: 9 works
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Figures / Tables:

Figure 1 Figure 1: Synthesis and composition of the SAC (a) Schematic illustration of the supportassisted pyrolysis synthesis approach for catalyst CoNC700. (b) The Co K-edge X-ray absorption near edge structure (XANES) of catalyst CoNC700, cobalt phthalocyanine (CoPC), and cobalt tetramethoxyphenylporphyrin (CoTMPP), and Co foil; (c) Fitting of the Co-N/O bonding inmore » Fourier transforms of Co K-edge extended X-ray absorption fine structure (EXAFS) data; Bright-field scanning transmission electron microscopy (STEM) images (d) and high-angle annular dark-field (HAADF)-STEM images (e) of catalyst CoNC700.« less

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