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Title: Single-Atomic Ruthenium Catalytic Sites on Nitrogen-Doped Graphene for Oxygen Reduction Reaction in Acidic Medium

Abstract

The cathodic oxygen reduction reaction (ORR) is essential in the electrochemical energy conversion of fuel cells. Here, through the NH3 atmosphere annealing of a graphene oxide (GO) precursor containing trace amounts of Ru, we have synthesized atomically dispersed Ru on nitrogen-doped graphene that performs as an electrocatalyst for the ORR in acidic medium. The Ru/nitrogen-doped GO catalyst exhibits excellent four-electron ORR activity, offering onset and half-wave potentials of 0.89 and 0.75 V, respectively, vs a reversible hydrogen electrode (RHE) in 0.1 M HClO4, together with better durability and tolerance toward methanol and carbon monoxide poisoning than seen in commercial Pt/C catalysts. X-ray adsorption fine structure analysis and aberration-corrected high-angle annular dark-field scanning transmission electron microscopy are performed and indicate that the chemical structure of Ru is predominantly composed of isolated Ru atoms coordinated with nitrogen atoms on the graphene substrate. Furthermore, a density function theory study of the ORR mechanism suggests that a Ru-oxo-N4 structure appears to be responsible for the ORR catalytic activity in the acidic medium. These findings provide a route for the design of efficient ORR single-atom catalysts.

Authors:
; ORCiD logo [1]; ; ; ; ; ; ;  [1];  [2]; ORCiD logo [2]; ; ;  [3];  [3]; ORCiD logo
  1. School of Materials Science and Engineering, Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300350, China, Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300350, China
  2. Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204, China
  3. Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
Publication Date:
Research Org.:
Rice Univ., Houston, TX (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1414051
Alternate Identifier(s):
OSTI ID: 1473883; OSTI ID: 1508003
Grant/Contract Number:  
SC0012547
Resource Type:
Journal Article: Published Article
Journal Name:
ACS Nano
Additional Journal Information:
Journal Name: ACS Nano Journal Volume: 11 Journal Issue: 7; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; oxygen reduction reaction; nitrogen-doped graphene oxide; atomically dispersed ruthenium; electrocatalysts

Citation Formats

Zhang, Chenhao, Sha, Junwei, Fei, Huilong, Liu, Mingjie, Yazdi, Sadegh, Zhang, Jibo, Zhong, Qifeng, Zou, Xiaolong, Zhao, Naiqin, Yu, Haisheng, Jiang, Zheng, Ringe, Emilie, Yakobson, Boris I., Dong, Juncai, Chen, Dongliang, and Tour, James M. Single-Atomic Ruthenium Catalytic Sites on Nitrogen-Doped Graphene for Oxygen Reduction Reaction in Acidic Medium. United States: N. p., 2017. Web. doi:10.1021/acsnano.7b02148.
Zhang, Chenhao, Sha, Junwei, Fei, Huilong, Liu, Mingjie, Yazdi, Sadegh, Zhang, Jibo, Zhong, Qifeng, Zou, Xiaolong, Zhao, Naiqin, Yu, Haisheng, Jiang, Zheng, Ringe, Emilie, Yakobson, Boris I., Dong, Juncai, Chen, Dongliang, & Tour, James M. Single-Atomic Ruthenium Catalytic Sites on Nitrogen-Doped Graphene for Oxygen Reduction Reaction in Acidic Medium. United States. https://doi.org/10.1021/acsnano.7b02148
Zhang, Chenhao, Sha, Junwei, Fei, Huilong, Liu, Mingjie, Yazdi, Sadegh, Zhang, Jibo, Zhong, Qifeng, Zou, Xiaolong, Zhao, Naiqin, Yu, Haisheng, Jiang, Zheng, Ringe, Emilie, Yakobson, Boris I., Dong, Juncai, Chen, Dongliang, and Tour, James M. Wed . "Single-Atomic Ruthenium Catalytic Sites on Nitrogen-Doped Graphene for Oxygen Reduction Reaction in Acidic Medium". United States. https://doi.org/10.1021/acsnano.7b02148.
@article{osti_1414051,
title = {Single-Atomic Ruthenium Catalytic Sites on Nitrogen-Doped Graphene for Oxygen Reduction Reaction in Acidic Medium},
author = {Zhang, Chenhao and Sha, Junwei and Fei, Huilong and Liu, Mingjie and Yazdi, Sadegh and Zhang, Jibo and Zhong, Qifeng and Zou, Xiaolong and Zhao, Naiqin and Yu, Haisheng and Jiang, Zheng and Ringe, Emilie and Yakobson, Boris I. and Dong, Juncai and Chen, Dongliang and Tour, James M.},
abstractNote = {The cathodic oxygen reduction reaction (ORR) is essential in the electrochemical energy conversion of fuel cells. Here, through the NH3 atmosphere annealing of a graphene oxide (GO) precursor containing trace amounts of Ru, we have synthesized atomically dispersed Ru on nitrogen-doped graphene that performs as an electrocatalyst for the ORR in acidic medium. The Ru/nitrogen-doped GO catalyst exhibits excellent four-electron ORR activity, offering onset and half-wave potentials of 0.89 and 0.75 V, respectively, vs a reversible hydrogen electrode (RHE) in 0.1 M HClO4, together with better durability and tolerance toward methanol and carbon monoxide poisoning than seen in commercial Pt/C catalysts. X-ray adsorption fine structure analysis and aberration-corrected high-angle annular dark-field scanning transmission electron microscopy are performed and indicate that the chemical structure of Ru is predominantly composed of isolated Ru atoms coordinated with nitrogen atoms on the graphene substrate. Furthermore, a density function theory study of the ORR mechanism suggests that a Ru-oxo-N4 structure appears to be responsible for the ORR catalytic activity in the acidic medium. These findings provide a route for the design of efficient ORR single-atom catalysts.},
doi = {10.1021/acsnano.7b02148},
url = {https://www.osti.gov/biblio/1414051}, journal = {ACS Nano},
issn = {1936-0851},
number = 7,
volume = 11,
place = {United States},
year = {2017},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at https://doi.org/10.1021/acsnano.7b02148

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