DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Designed Iron Single Atom Catalysts for Highly Efficient Oxygen Reduction Reaction in Alkaline and Acid Media

Abstract

Abstract Single atom catalysts (SACs) have attracted much attentions due to their advantages of high catalysis efficiency and excellent selectivity. However, for industrial applications, synthesis of SACs in large and practical quantities is very important. The challenge is to develop synthesis methods with controllability and scalability. Herein, a well‐characterized and scalable method is demonstrated to synthesize atomically dispersed iron atoms coordinated with nitrogen on graphene, SAFe @ NG, with high atomic loading (≈4.6 wt%) through a one‐pot pyrolysis process. The method is scalable for the fabrication of Fe SACs with high quantities. The Fe–N–G catalyst exhibits high intrinsic oxygen reduction reaction (ORR) performance, reaching half potential of 0.876 and 0.702 V in alkaline and acidic solutions, respectively, with excellent microstructure stability. Furthermore, the density functional theory (DFT) simulation confirms that the Fe atoms in coordination with four nitrogen atoms, FeN4, in graphene is the active center for the 4‐electron ORR process. This work demonstrates an efficient design pathway for single atom catalysts as highly active and stable electrocatalysts for high‐performance ORR applications.

Authors:
 [1];  [2];  [3];  [4];  [5];  [6]; ORCiD logo [1]
  1. WA School of Mines: Minerals Energy and Chemical Engineering Curtin University Perth Western Australia 6102 Australia
  2. School of Materials Science and Engineering Zhengzhou University Zhengzhou 450001 China
  3. Australian Synchrotron Clayton Victoria 3168 Australia
  4. Centre for Microscopy Characterization and Analysis (CMCA) and School of Molecular Sciences The University of Western Australia Perth Western Australia 6009 Australia
  5. Advanced Carbon Division Shenyang National Laboratory for Materials Science Institute of Metal Research Chinese Academy of Sciences Shenyang Liaoning 110016 China
  6. Eyring Materials Center Arizona State University Tempe AZ 85287 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1804167
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Advanced Materials Interfaces
Additional Journal Information:
Journal Name: Advanced Materials Interfaces Journal Volume: 8 Journal Issue: 8; Journal ID: ISSN 2196-7350
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Zhao, Shiyong, Zhang, Lianji, Johannessen, Bernt, Saunders, Martin, Liu, Chang, Yang, Shi‐Ze, and Jiang, San Ping. Designed Iron Single Atom Catalysts for Highly Efficient Oxygen Reduction Reaction in Alkaline and Acid Media. Germany: N. p., 2020. Web. doi:10.1002/admi.202001788.
Zhao, Shiyong, Zhang, Lianji, Johannessen, Bernt, Saunders, Martin, Liu, Chang, Yang, Shi‐Ze, & Jiang, San Ping. Designed Iron Single Atom Catalysts for Highly Efficient Oxygen Reduction Reaction in Alkaline and Acid Media. Germany. https://doi.org/10.1002/admi.202001788
Zhao, Shiyong, Zhang, Lianji, Johannessen, Bernt, Saunders, Martin, Liu, Chang, Yang, Shi‐Ze, and Jiang, San Ping. Thu . "Designed Iron Single Atom Catalysts for Highly Efficient Oxygen Reduction Reaction in Alkaline and Acid Media". Germany. https://doi.org/10.1002/admi.202001788.
@article{osti_1804167,
title = {Designed Iron Single Atom Catalysts for Highly Efficient Oxygen Reduction Reaction in Alkaline and Acid Media},
author = {Zhao, Shiyong and Zhang, Lianji and Johannessen, Bernt and Saunders, Martin and Liu, Chang and Yang, Shi‐Ze and Jiang, San Ping},
abstractNote = {Abstract Single atom catalysts (SACs) have attracted much attentions due to their advantages of high catalysis efficiency and excellent selectivity. However, for industrial applications, synthesis of SACs in large and practical quantities is very important. The challenge is to develop synthesis methods with controllability and scalability. Herein, a well‐characterized and scalable method is demonstrated to synthesize atomically dispersed iron atoms coordinated with nitrogen on graphene, SAFe @ NG, with high atomic loading (≈4.6 wt%) through a one‐pot pyrolysis process. The method is scalable for the fabrication of Fe SACs with high quantities. The Fe–N–G catalyst exhibits high intrinsic oxygen reduction reaction (ORR) performance, reaching half potential of 0.876 and 0.702 V in alkaline and acidic solutions, respectively, with excellent microstructure stability. Furthermore, the density functional theory (DFT) simulation confirms that the Fe atoms in coordination with four nitrogen atoms, FeN4, in graphene is the active center for the 4‐electron ORR process. This work demonstrates an efficient design pathway for single atom catalysts as highly active and stable electrocatalysts for high‐performance ORR applications.},
doi = {10.1002/admi.202001788},
journal = {Advanced Materials Interfaces},
number = 8,
volume = 8,
place = {Germany},
year = {Thu Dec 03 00:00:00 EST 2020},
month = {Thu Dec 03 00:00:00 EST 2020}
}

Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Biomass Derived N-Doped Porous Carbon Supported Single Fe Atoms as Superior Electrocatalysts for Oxygen Reduction
journal, April 2017


Iron Single Atoms on Graphene as Nonprecious Metal Catalysts for High‐Temperature Polymer Electrolyte Membrane Fuel Cells
journal, March 2019


Atomically Dispersed Transition Metals on Carbon Nanotubes with Ultrahigh Loading for Selective Electrochemical Carbon Dioxide Reduction
journal, February 2018

  • Cheng, Yi; Zhao, Shiyong; Johannessen, Bernt
  • Advanced Materials, Vol. 30, Issue 13
  • DOI: 10.1002/adma.201706287

Projector augmented-wave method
journal, December 1994


Supported Single Atoms as New Class of Catalysts for Electrochemical Reduction of Carbon Dioxide
journal, February 2019


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Catalysis by Supported Single Metal Atoms
journal, November 2016


Structural evolution during annealing of thermally reduced graphene nanosheets for application in supercapacitors
journal, August 2012


Single-Atom Electrocatalysts
journal, October 2017

  • Zhu, Chengzhou; Fu, Shaofang; Shi, Qiurong
  • Angewandte Chemie International Edition, Vol. 56, Issue 45
  • DOI: 10.1002/anie.201703864

Synergistic effect of well-defined dual sites boosting the oxygen reduction reaction
journal, January 2018

  • Wang, Jing; Liu, Wei; Luo, Gan
  • Energy & Environmental Science, Vol. 11, Issue 12
  • DOI: 10.1039/C8EE02656D

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Oxygen Reduction Electrocatalyst Based on Strongly Coupled Cobalt Oxide Nanocrystals and Carbon Nanotubes
journal, September 2012

  • Liang, Yongye; Wang, Hailiang; Diao, Peng
  • Journal of the American Chemical Society, Vol. 134, Issue 38
  • DOI: 10.1021/ja305623m

Fe Isolated Single Atoms on S, N Codoped Carbon by Copolymer Pyrolysis Strategy for Highly Efficient Oxygen Reduction Reaction
journal, May 2018


Active Sites on Heterogeneous Single-Iron-Atom Electrocatalysts in CO 2 Reduction Reaction
journal, June 2019


Hierarchically porous Fe-N-doped carbon nanotubes as efficient electrocatalyst for oxygen reduction
journal, November 2016


Single-Atom Catalysts: A New Frontier in Heterogeneous Catalysis
journal, April 2013

  • Yang, Xiao-Feng; Wang, Aiqin; Qiao, Botao
  • Accounts of Chemical Research, Vol. 46, Issue 8
  • DOI: 10.1021/ar300361m

Atomically dispersed Ni(i) as the active site for electrochemical CO2 reduction
journal, February 2018


Bamboo-like Carbon Nanotube/Fe 3 C Nanoparticle Hybrids and Their Highly Efficient Catalysis for Oxygen Reduction
journal, January 2015

  • Yang, Wenxiu; Liu, Xiangjian; Yue, Xiaoyu
  • Journal of the American Chemical Society, Vol. 137, Issue 4
  • DOI: 10.1021/ja5129132

A 3D bi-functional porous N-doped carbon microtube sponge electrocatalyst for oxygen reduction and oxygen evolution reactions
journal, January 2016

  • Li, Jin-Cheng; Hou, Peng-Xiang; Zhao, Shi-Yong
  • Energy & Environmental Science, Vol. 9, Issue 10
  • DOI: 10.1039/C6EE02169G

A general route via formamide condensation to prepare atomically dispersed metal–nitrogen–carbon electrocatalysts for energy technologies
journal, January 2019

  • Zhang, Guoxin; Jia, Yin; Zhang, Cong
  • Energy & Environmental Science, Vol. 12, Issue 4
  • DOI: 10.1039/C9EE00162J

Hollow Spheres of Iron Carbide Nanoparticles Encased in Graphitic Layers as Oxygen Reduction Catalysts
journal, February 2014

  • Hu, Yang; Jensen, Jens Oluf; Zhang, Wei
  • Angewandte Chemie International Edition, Vol. 53, Issue 14
  • DOI: 10.1002/anie.201400358

From Metal-Organic Frameworks to Single-Atom Fe Implanted N-doped Porous Carbons: Efficient Oxygen Reduction in Both Alkaline and Acidic Media
journal, June 2018

  • Jiao, Long; Wan, Gang; Zhang, Rui
  • Angewandte Chemie International Edition, Vol. 57, Issue 28
  • DOI: 10.1002/anie.201803262

Single Cobalt Atom and N Codoped Carbon Nanofibers as Highly Durable Electrocatalyst for Oxygen Reduction Reaction
journal, September 2017


Efficient and Durable Bifunctional Oxygen Catalysts Based on NiFeO@MnO x Core–Shell Structures for Rechargeable Zn–Air Batteries
journal, February 2017

  • Cheng, Yi; Dou, Shuo; Veder, Jean-Pierre
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 9
  • DOI: 10.1021/acsami.6b16180

Reactivity and extent of poisoning during methanol electro-oxidation on platinum (100) and (111): A comparative study
journal, March 1998

  • Jarvi, T. D.; Sriramulu, S.; Stuve, E. M.
  • Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 134, Issue 1-2
  • DOI: 10.1016/S0927-7757(97)00313-0

IFEFFIT  : interactive XAFS analysis and FEFF fitting
journal, March 2001


Theoretical approaches to x-ray absorption fine structure
journal, July 2000


General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities
journal, January 2018


N-doped carbon nanotubes containing a high concentration of single iron atoms for efficient oxygen reduction
journal, January 2018

  • Li, Jin-Cheng; Yang, Zhi-Qing; Tang, Dai-Ming
  • NPG Asia Materials, Vol. 10, Issue 1
  • DOI: 10.1038/am.2017.212

Graphene-Like Carbon Nitride Nanosheets for Improved Photocatalytic Activities
journal, July 2012

  • Niu, Ping; Zhang, Lili; Liu, Gang
  • Advanced Functional Materials, Vol. 22, Issue 22
  • DOI: 10.1002/adfm.201200922

A universal principle for a rational design of single-atom electrocatalysts
journal, April 2018


Cascade anchoring strategy for general mass production of high-loading single-atomic metal-nitrogen catalysts
journal, March 2019