skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: General synthesis and definitive structural identification of MN 4C 4 single-atom catalysts with tunable electrocatalytic activities

Abstract

Single-atom catalysts (SACs) have recently attracted broad research interest as they combine the merits of both homogeneous and heterogeneous catalysts. Rational design and synthesis of SACs are of immense significance but have so far been plagued by the lack of a definitive correlation between structure and catalytic properties. Here, we report a general approach to a series of monodispersed atomic transition metals (for example, Fe, Co, Ni) embedded in nitrogen-doped graphene with a common MNsub>4C 4 moiety, identified by systematic X-ray absorption fine structure analyses and direct transmission electron microscopy imaging. The unambiguous structure determination allows density functional theoretical prediction of MNsub>4C 4 moieties as efficient oxygen evolution catalysts with activities following the trend Ni > Co > Fe, which is confirmed by electrochemical measurements. Determination of atomistic structure and its correlation with catalytic properties represents a critical step towards the rational design and synthesis of precious or nonprecious SACs with exceptional atom utilization efficiency and catalytic activities.

Authors:
 [1]; ORCiD logo [2];  [3]; ORCiD logo [4];  [1];  [1];  [1];  [1];  [1]; ORCiD logo [1];  [2]; ORCiD logo [5];  [2];  [1];  [2];  [6];  [7];  [2];  [5];  [4] more »;  [1];  [1] « less
  1. Univ. of California, Los Angeles, CA (United States)
  2. Chinese Academy of Sciences (CAS), Beijing (China)
  3. Hunan Univ., Changsha (China)
  4. Univ. of Oxford (United Kingdom); Science and Technology Facilities Council (STFC), Harwell Campus, Oxford (United Kingdom). Diamond Light Source, Ltd.
  5. Tsinghua Univ., Beijing (China)
  6. King Saud Univ., Riyadh (Saudi Arabia)
  7. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1425042
Report Number(s):
BNL-200041-2018-JAAM
Journal ID: ISSN 2520-1158
Grant/Contract Number:  
SC0012704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Catalysis
Additional Journal Information:
Journal Volume: 1; Journal Issue: 1; Journal ID: ISSN 2520-1158
Publisher:
Springer Nature
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Fei, Huilong, Dong, Juncai, Feng, Yexin, Allen, Christopher S., Wan, Chengzhang, Volosskiy, Boris, Li, Mufan, Zhao, Zipeng, Wang, Yiliu, Sun, Hongtao, An, Pengfei, Chen, Wenxing, Guo, Zhiying, Lee, Chain, Chen, Dongliang, Shakir, Imran, Liu, Mingjie, Hu, Tiandou, Li, Yadong, Kirkland, Angus I., Duan, Xiangfeng, and Huang, Yu. General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities. United States: N. p., 2018. Web. doi:10.1038/s41929-017-0008-y.
Fei, Huilong, Dong, Juncai, Feng, Yexin, Allen, Christopher S., Wan, Chengzhang, Volosskiy, Boris, Li, Mufan, Zhao, Zipeng, Wang, Yiliu, Sun, Hongtao, An, Pengfei, Chen, Wenxing, Guo, Zhiying, Lee, Chain, Chen, Dongliang, Shakir, Imran, Liu, Mingjie, Hu, Tiandou, Li, Yadong, Kirkland, Angus I., Duan, Xiangfeng, & Huang, Yu. General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities. United States. doi:10.1038/s41929-017-0008-y.
Fei, Huilong, Dong, Juncai, Feng, Yexin, Allen, Christopher S., Wan, Chengzhang, Volosskiy, Boris, Li, Mufan, Zhao, Zipeng, Wang, Yiliu, Sun, Hongtao, An, Pengfei, Chen, Wenxing, Guo, Zhiying, Lee, Chain, Chen, Dongliang, Shakir, Imran, Liu, Mingjie, Hu, Tiandou, Li, Yadong, Kirkland, Angus I., Duan, Xiangfeng, and Huang, Yu. Mon . "General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities". United States. doi:10.1038/s41929-017-0008-y. https://www.osti.gov/servlets/purl/1425042.
@article{osti_1425042,
title = {General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities},
author = {Fei, Huilong and Dong, Juncai and Feng, Yexin and Allen, Christopher S. and Wan, Chengzhang and Volosskiy, Boris and Li, Mufan and Zhao, Zipeng and Wang, Yiliu and Sun, Hongtao and An, Pengfei and Chen, Wenxing and Guo, Zhiying and Lee, Chain and Chen, Dongliang and Shakir, Imran and Liu, Mingjie and Hu, Tiandou and Li, Yadong and Kirkland, Angus I. and Duan, Xiangfeng and Huang, Yu},
abstractNote = {Single-atom catalysts (SACs) have recently attracted broad research interest as they combine the merits of both homogeneous and heterogeneous catalysts. Rational design and synthesis of SACs are of immense significance but have so far been plagued by the lack of a definitive correlation between structure and catalytic properties. Here, we report a general approach to a series of monodispersed atomic transition metals (for example, Fe, Co, Ni) embedded in nitrogen-doped graphene with a common MNsub>4C4 moiety, identified by systematic X-ray absorption fine structure analyses and direct transmission electron microscopy imaging. The unambiguous structure determination allows density functional theoretical prediction of MNsub>4C4 moieties as efficient oxygen evolution catalysts with activities following the trend Ni > Co > Fe, which is confirmed by electrochemical measurements. Determination of atomistic structure and its correlation with catalytic properties represents a critical step towards the rational design and synthesis of precious or nonprecious SACs with exceptional atom utilization efficiency and catalytic activities.},
doi = {10.1038/s41929-017-0008-y},
journal = {Nature Catalysis},
issn = {2520-1158},
number = 1,
volume = 1,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 93 works
Citation information provided by
Web of Science

Figures / Tables:

Fig. 1 Fig. 1 : The preparation route to M–NHGFs. The graphene oxide solution in the presence of H2O2 and metal precursors was hydrothermally treated to form a 3D graphene hydrogel. After freeze drying the hydrogel, a thermal annealing process in an NH3 atmosphere was used to further reduce the graphene andmore » incorporate N-dopants into the 2D graphene lattice.« less

Save / Share:

Works referenced in this record:

Ultrathin Cobalt–Manganese Layered Double Hydroxide Is an Efficient Oxygen Evolution Catalyst
journal, November 2014

  • Song, Fang; Hu, Xile
  • Journal of the American Chemical Society, Vol. 136, Issue 47
  • DOI: 10.1021/ja5096733

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


Spectroscopic insights into the nature of active sites in iron–nitrogen–carbon electrocatalysts for oxygen reduction in acid
journal, November 2016


Tailoring Metal-Porphyrin-Like Active Sites on Graphene to Improve the Efficiency and Selectivity of Electrochemical CO 2 Reduction
journal, September 2015

  • Cheng, Mu-Jeng; Kwon, Youngkook; Head-Gordon, Martin
  • The Journal of Physical Chemistry C, Vol. 119, Issue 37
  • DOI: 10.1021/acs.jpcc.5b05518

Catalysis by Supported Single Metal Atoms
journal, November 2016


Metal–air batteries: from oxygen reduction electrochemistry to cathode catalysts
journal, January 2012

  • Cheng, Fangyi; Chen, Jun
  • Chemical Society Reviews, Vol. 41, Issue 6, p. 2172-2192
  • DOI: 10.1039/c1cs15228a

Dual Electrical-Behavior Regulation on Electrocatalysts Realizing Enhanced Electrochemical Water Oxidation
journal, March 2016


Catalysis by clusters with precise numbers of atoms
journal, July 2015


A General Approach to Preferential Formation of Active Fe–N x Sites in Fe–N/C Electrocatalysts for Efficient Oxygen Reduction Reaction
journal, November 2016

  • Sa, Young Jin; Seo, Dong-Jun; Woo, Jinwoo
  • Journal of the American Chemical Society, Vol. 138, Issue 45
  • DOI: 10.1021/jacs.6b09470

Solution Processable Holey Graphene Oxide and Its Derived Macrostructures for High-Performance Supercapacitors
journal, June 2015


Earth-abundant inorganic electrocatalysts and their nanostructures for energy conversion applications
journal, January 2014

  • Faber, Matthew S.; Jin, Song
  • Energy Environ. Sci., Vol. 7, Issue 11
  • DOI: 10.1039/C4EE01760A

Isolated Single Iron Atoms Anchored on N-Doped Porous Carbon as an Efficient Electrocatalyst for the Oxygen Reduction Reaction
journal, April 2017

  • Chen, Yuanjun; Ji, Shufang; Wang, Yanggang
  • Angewandte Chemie International Edition, Vol. 56, Issue 24
  • DOI: 10.1002/anie.201702473

An Advanced Ni–Fe Layered Double Hydroxide Electrocatalyst for Water Oxidation
journal, May 2013

  • Gong, Ming; Li, Yanguang; Wang, Hailiang
  • Journal of the American Chemical Society, Vol. 135, Issue 23
  • DOI: 10.1021/ja4027715

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

Effect of Transition Metals on the Structure and Performance of the Doped Carbon Catalysts Derived From Polyaniline and Melamine for ORR Application
journal, September 2014

  • Peng, Hongliang; Liu, Fangfang; Liu, Xiaojun
  • ACS Catalysis, Vol. 4, Issue 10
  • DOI: 10.1021/cs500744x

Understanding the High Activity of Fe–N–C Electrocatalysts in Oxygen Reduction: Fe/Fe 3 C Nanoparticles Boost the Activity of Fe–N x
journal, March 2016

  • Jiang, Wen-Jie; Gu, Lin; Li, Li
  • Journal of the American Chemical Society, Vol. 138, Issue 10
  • DOI: 10.1021/jacs.6b00757

Photochemical route for synthesizing atomically dispersed palladium catalysts
journal, May 2016


On an Easy Way To Prepare Metal–Nitrogen Doped Carbon with Exclusive Presence of MeN 4 -type Sites Active for the ORR
journal, January 2016

  • Kramm, Ulrike I.; Herrmann-Geppert, Iris; Behrends, Jan
  • Journal of the American Chemical Society, Vol. 138, Issue 2
  • DOI: 10.1021/jacs.5b11015

Ab initiomolecular dynamics for liquid metals
journal, January 1993


A Graphene Composite Material with Single Cobalt Active Sites: A Highly Efficient Counter Electrode for Dye-Sensitized Solar Cells
journal, April 2016

  • Cui, Xiaoju; Xiao, Jianping; Wu, Yihui
  • Angewandte Chemie International Edition, Vol. 55, Issue 23
  • DOI: 10.1002/anie.201602097

Single Atom Excels as the Smallest Functional Material
journal, April 2016


Homogeneous and Heterogeneous Catalysis: Bridging the Gap through Surface Organometallic Chemistry
journal, January 2003

  • Copéret, Christophe; Chabanas, Mathieu; Petroff Saint-Arroman, Romain
  • Angewandte Chemie International Edition, Vol. 42, Issue 2, p. 156-181
  • DOI: 10.1002/anie.200390072

Thermally stable single-atom platinum-on-ceria catalysts via atom trapping
journal, July 2016


Electrochemical CO 2 and CO Reduction on Metal-Functionalized Porphyrin-like Graphene
journal, April 2013

  • Tripkovic, Vladimir; Vanin, Marco; Karamad, Mohammedreza
  • The Journal of Physical Chemistry C, Vol. 117, Issue 18
  • DOI: 10.1021/jp306172k

Ligand Effects in Homogeneous Au Catalysis
journal, August 2008

  • Gorin, David J.; Sherry, Benjamin D.; Toste, F. Dean
  • Chemical Reviews, Vol. 108, Issue 8
  • DOI: 10.1021/cr068430g

MXAN  : a new software procedure to perform geometrical fitting of experimental XANES spectra
journal, March 2001

  • Benfatto, M.; Congiu-Castellano, A.; Daniele, A.
  • Journal of Synchrotron Radiation, Vol. 8, Issue 2
  • DOI: 10.1107/S0909049500015338

Water Oxidation on Pure and Doped Hematite (0001) Surfaces: Prediction of Co and Ni as Effective Dopants for Electrocatalysis
journal, August 2012

  • Liao, Peilin; Keith, John A.; Carter, Emily A.
  • Journal of the American Chemical Society, Vol. 134, Issue 32
  • DOI: 10.1021/ja301567f

Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials
journal, August 2015

  • Zitolo, Andrea; Goellner, Vincent; Armel, Vanessa
  • Nature Materials, Vol. 14, Issue 9
  • DOI: 10.1038/nmat4367

X-ray absorption near-edge structure calculations beyond the muffin-tin approximation
journal, March 2001


The Reaction Mechanism with Free Energy Barriers at Constant Potentials for the Oxygen Evolution Reaction at the IrO 2 (110) Surface
journal, December 2016

  • Ping, Yuan; Nielsen, Robert J.; Goddard, William A.
  • Journal of the American Chemical Society, Vol. 139, Issue 1
  • DOI: 10.1021/jacs.6b07557

Wavelet analysis of extended x-ray absorption fine structure data
journal, March 2005


Self-consistent aspects of x-ray absorption calculations
journal, August 2009


Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions
journal, January 2015

  • Jiao, Yan; Zheng, Yao; Jaroniec, Mietek
  • Chemical Society Reviews, Vol. 44, Issue 8
  • DOI: 10.1039/C4CS00470A

Atomically Dispersed Supported Metal Catalysts
journal, July 2012


Coupling carbon dioxide reduction with water oxidation in nanoscale photocatalytic assemblies
journal, January 2016

  • Kim, Wooyul; McClure, Beth Anne; Edri, Eran
  • Chemical Society Reviews, Vol. 45, Issue 11
  • DOI: 10.1039/C6CS00062B

A single iron site confined in a graphene matrix for the catalytic oxidation of benzene at room temperature
journal, December 2015


Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994


Benchmarking Heterogeneous Electrocatalysts for the Oxygen Evolution Reaction
journal, October 2013

  • McCrory, Charles C. L.; Jung, Suho; Peters, Jonas C.
  • Journal of the American Chemical Society, Vol. 135, Issue 45
  • DOI: 10.1021/ja407115p

Atomically Dispersed Au–(OH) x Species Bound on Titania Catalyze the Low-Temperature Water-Gas Shift Reaction
journal, March 2013

  • Yang, Ming; Allard, Lawrence F.; Flytzani-Stephanopoulos, Maria
  • Journal of the American Chemical Society, Vol. 135, Issue 10
  • DOI: 10.1021/ja312646d

Homogeneously dispersed multimetal oxygen-evolving catalysts
journal, March 2016


Conversion of Dinitrogen to Ammonia by FeN 3 -Embedded Graphene
journal, July 2016

  • Li, Xiao-Fei; Li, Qin-Kun; Cheng, Jin
  • Journal of the American Chemical Society, Vol. 138, Issue 28
  • DOI: 10.1021/jacs.6b04778

Stability, Electronic and Magnetic Properties of In-Plane Defects in Graphene: A First-Principles Study
journal, March 2012

  • Kattel, Shyam; Atanassov, Plamen; Kiefer, Boris
  • The Journal of Physical Chemistry C, Vol. 116, Issue 14
  • DOI: 10.1021/jp2121609

Preparation of Graphitic Oxide
journal, March 1958

  • Hummers, William S.; Offeman, Richard E.
  • Journal of the American Chemical Society, Vol. 80, Issue 6, p. 1339-1339
  • DOI: 10.1021/ja01539a017

Quantifying the density and utilization of active sites in non-precious metal oxygen electroreduction catalysts
journal, October 2015

  • Sahraie, Nastaran Ranjbar; Kramm, Ulrike I.; Steinberg, Julian
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9618

Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode
journal, November 2004

  • Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 46
  • DOI: 10.1021/jp047349j

Remarkable Performance of Ir 1 /FeO x Single-Atom Catalyst in Water Gas Shift Reaction
journal, October 2013

  • Lin, Jian; Wang, Aiqin; Qiao, Botao
  • Journal of the American Chemical Society, Vol. 135, Issue 41
  • DOI: 10.1021/ja408574m

Iron-Based Catalysts with Improved Oxygen Reduction Activity in Polymer Electrolyte Fuel Cells
journal, April 2009

  • Lefèvre, Michel; Proietti, Eric; Jaouen, Frédéric
  • Science, Vol. 324, Issue 5923, p. 71-74
  • DOI: 10.1126/science.1170051

Single-atom dispersed Co–N–C catalyst: structure identification and performance for hydrogenative coupling of nitroarenes
journal, January 2016

  • Liu, Wengang; Zhang, Leilei; Yan, Wensheng
  • Chemical Science, Vol. 7, Issue 9
  • DOI: 10.1039/C6SC02105K

A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions
journal, April 2015

  • Zhang, Jintao; Zhao, Zhenghang; Xia, Zhenhai
  • Nature Nanotechnology, Vol. 10, Issue 5
  • DOI: 10.1038/nnano.2015.48

Efficient Water Oxidation Using Nanostructured α-Nickel-Hydroxide as an Electrocatalyst
journal, May 2014

  • Gao, Minrui; Sheng, Wenchao; Zhuang, Zhongbin
  • Journal of the American Chemical Society, Vol. 136, Issue 19
  • DOI: 10.1021/ja502128j

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


First-principles calculations of the ferroelastic transition between rutile-type and CaCl 2 -type SiO 2 at high pressures
journal, October 2008


Single Cobalt Atoms with Precise N-Coordination as Superior Oxygen Reduction Reaction Catalysts
journal, August 2016

  • Yin, Peiqun; Yao, Tao; Wu, Yuen
  • Angewandte Chemie International Edition, Vol. 55, Issue 36
  • DOI: 10.1002/anie.201604802

Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts
journal, January 2016


Nanoparticles as Recyclable Catalysts: The Frontier between Homogeneous and Heterogeneous Catalysis
journal, December 2005

  • Astruc, Didier; Lu, Feng; Aranzaes, Jaime Ruiz
  • Angewandte Chemie International Edition, Vol. 44, Issue 48
  • DOI: 10.1002/anie.200500766

A review of Fe–N/C and Co–N/C catalysts for the oxygen reduction reaction
journal, June 2008


    Works referencing / citing this record:

    Manganese acting as a high-performance heterogeneous electrocatalyst in carbon dioxide reduction
    journal, July 2019


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