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Title: Anion-Regulated Selective Generation of Cobalt Sites in Carbon: Toward Superior Bifunctional Electrocatalysis

Abstract

We report the introduction of active transition metal sites (TMSs) in carbon enables the synthesis of noble-metal-free electrocatalysts for clean energy conversion applications, however, there are often multiple existing forms of TMSs, which are of different natures and catalytic models. Regulating the evolution of distinctive TMSs is highly desirable but remains challenging to date. Anions, as essential elements involved in the synthesis, have been totally neglected previously in the construction of TMSs. Herein, the effects of anions on the creation of different types of TMSs is investigated for the first time. It is found that the active cobalt-nitrogen sites tend to be selectively constructed on the surface of N-doped carbon by using chloride, while metallic cobalt nanoparticles encased in protective graphite layers are the dominant forms of cobalt species with nitrate ions. The obtained catalysts demonstrate cobalt-sites-dependent activity for ORR and HER in acidic media. And the remarkably enhanced catalytic activities approaching that of benchmark Pt/C in acidic medium has been obtained on the catalyst dominated with cobalt-nitrogen sites, confirmed by the advanced spectroscopic . In conclusion, our finding demonstrates a general paradigm of anion-regulated evolution of distinctive TMSs, providing a new pathway for enhancing performances of various targeted reactionsmore » related with TMSs.« less

Authors:
 [1];  [2];  [1];  [1];  [1];  [2];  [2];  [3]; ORCiD logo [3]
  1. Chinese Academy of Sciences, Shanghai (China); University of Chinese Academy of Sciences, Beijing (China)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
  3. Chinese Academy of Sciences, Shanghai (China)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE; National Key Basic Research Program of China
OSTI Identifier:
1416001
Alternate Identifier(s):
OSTI ID: 1407824
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 47; Journal ID: ISSN 0935-9648
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; anions; cobalt-sites-dependent activities; electrocatalysis; selective generation; transition metal sites

Citation Formats

Wan, Gang, Yang, Ce, Zhao, Wanpeng, Li, Qianru, Wang, Ning, Li, Tao, Zhou, Hua, Chen, Hangrong, and Shi, Jianlin. Anion-Regulated Selective Generation of Cobalt Sites in Carbon: Toward Superior Bifunctional Electrocatalysis. United States: N. p., 2017. Web. doi:10.1002/adma.201703436.
Wan, Gang, Yang, Ce, Zhao, Wanpeng, Li, Qianru, Wang, Ning, Li, Tao, Zhou, Hua, Chen, Hangrong, & Shi, Jianlin. Anion-Regulated Selective Generation of Cobalt Sites in Carbon: Toward Superior Bifunctional Electrocatalysis. United States. doi:10.1002/adma.201703436.
Wan, Gang, Yang, Ce, Zhao, Wanpeng, Li, Qianru, Wang, Ning, Li, Tao, Zhou, Hua, Chen, Hangrong, and Shi, Jianlin. Mon . "Anion-Regulated Selective Generation of Cobalt Sites in Carbon: Toward Superior Bifunctional Electrocatalysis". United States. doi:10.1002/adma.201703436. https://www.osti.gov/servlets/purl/1416001.
@article{osti_1416001,
title = {Anion-Regulated Selective Generation of Cobalt Sites in Carbon: Toward Superior Bifunctional Electrocatalysis},
author = {Wan, Gang and Yang, Ce and Zhao, Wanpeng and Li, Qianru and Wang, Ning and Li, Tao and Zhou, Hua and Chen, Hangrong and Shi, Jianlin},
abstractNote = {We report the introduction of active transition metal sites (TMSs) in carbon enables the synthesis of noble-metal-free electrocatalysts for clean energy conversion applications, however, there are often multiple existing forms of TMSs, which are of different natures and catalytic models. Regulating the evolution of distinctive TMSs is highly desirable but remains challenging to date. Anions, as essential elements involved in the synthesis, have been totally neglected previously in the construction of TMSs. Herein, the effects of anions on the creation of different types of TMSs is investigated for the first time. It is found that the active cobalt-nitrogen sites tend to be selectively constructed on the surface of N-doped carbon by using chloride, while metallic cobalt nanoparticles encased in protective graphite layers are the dominant forms of cobalt species with nitrate ions. The obtained catalysts demonstrate cobalt-sites-dependent activity for ORR and HER in acidic media. And the remarkably enhanced catalytic activities approaching that of benchmark Pt/C in acidic medium has been obtained on the catalyst dominated with cobalt-nitrogen sites, confirmed by the advanced spectroscopic . In conclusion, our finding demonstrates a general paradigm of anion-regulated evolution of distinctive TMSs, providing a new pathway for enhancing performances of various targeted reactions related with TMSs.},
doi = {10.1002/adma.201703436},
journal = {Advanced Materials},
number = 47,
volume = 29,
place = {United States},
year = {2017},
month = {11}
}

Journal Article:
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Cited by: 33 works
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Figures / Tables:

Figure 1 Figure 1: Illustration of anion-regulated selective generation of catalytic cobalt sites in carbon via pyrolysis with NO3- or Cl- anions for hydrogen evolution and oxygen reduction in acidic medium.

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.