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

Abstract

Abstract 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 are 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 oxygen reduction reaction and hydrogen evolution reaction in acidic media. The remarkably enhanced catalytic activities approaching that of benchmark Pt/C in an acidic medium have been obtained on the catalyst dominated with cobalt–nitrogen sites, confirmed by the advanced spectroscopic characterization. This finding demonstrates a general paradigm of anion‐regulated evolution of distinctive TMSs, providing a new pathway for enhancing performances of various targetedmore » reactions 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 Laboratory (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; DE‐AC02‐06CH11357
Resource Type:
Journal Article: 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. https://doi.org/10.1002/adma.201703436
Wan, Gang, Yang, Ce, Zhao, Wanpeng, Li, Qianru, Wang, Ning, Li, Tao, Zhou, Hua, Chen, Hangrong, and Shi, Jianlin. 2017. "Anion-Regulated Selective Generation of Cobalt Sites in Carbon: Toward Superior Bifunctional Electrocatalysis". United States. https://doi.org/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 = {Abstract 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 are 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 oxygen reduction reaction and hydrogen evolution reaction in acidic media. The remarkably enhanced catalytic activities approaching that of benchmark Pt/C in an acidic medium have been obtained on the catalyst dominated with cobalt–nitrogen sites, confirmed by the advanced spectroscopic characterization. This 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},
url = {https://www.osti.gov/biblio/1416001}, journal = {Advanced Materials},
issn = {0935-9648},
number = 47,
volume = 29,
place = {United States},
year = {Mon Nov 06 00:00:00 EST 2017},
month = {Mon Nov 06 00:00:00 EST 2017}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 110 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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Works referenced in this record:

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journal, January 2016


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journal, November 2015


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Co–N–C Catalyst for C–C Coupling Reactions: On the Catalytic Performance and Active Sites
journal, October 2015


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journal, October 2015


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Works referencing / citing this record:

Carbon-Rich Nanomaterials: Fascinating Hydrogen and Oxygen Electrocatalysts
journal, July 2018


Toward Efficient Carbon and Water Cycles: Emerging Opportunities with Single‐Site Catalysts Made of 3d Transition Metals
journal, November 2019


A review of anion-regulated multi-anion transition metal compounds for oxygen evolution electrocatalysis
journal, January 2018


Boosting the ORR performance of modified carbon black via C–O bonds
journal, January 2019


Constructing ultrathin CoP nanomeshes by Er-doping for highly efficient bifunctional electrocatalysts for overall water splitting
journal, January 2019


Aerobic selective oxidation of methylaromatics to benzoic acids over Co@N/Co-CNTs with high loading CoN 4 species
journal, January 2019


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