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

Title: Cascade anchoring strategy for general mass production of high-loading single-atomic metal-nitrogen catalysts

Abstract

Although single-atomically dispersed metal-Nx on carbon support (M-NC) has great potential in heterogeneous catalysis, the scalable synthesis of such single-atom catalysts (SACs) with high-loading metal-N x is greatly challenging since the loading and single-atomic dispersion have to be balanced at high temperature for forming metal-N x. Herein, we develop a general cascade anchoring strategy for the mass production of a series of M-NC SACs with a metal loading up to 12.1 wt%. Systematic investigation reveals that the chelation of metal ions, physical isolation of chelate complex upon high loading, and the binding with N-species at elevated temperature are essential to achieving high-loading M-NC SACs. As a demonstration, high-loading Fe-NC SAC shows superior electrocatalytic performance for O 2 reduction and Ni-NC SAC exhibits high electrocatalytic activity for CO 2 reduction. The strategy paves a universal way to produce stable M-NC SAC with high-density metal-N x sites for diverse high-performance applications.

Authors:
 [1];  [2];  [1];  [3];  [4];  [1];  [1];  [5]; ORCiD logo [6]; ORCiD logo [6]; ORCiD logo [4];  [4];  [4]
  1. Chinese Academy of Sciences (CAS), Beijing (China); Univ. of Chinese Academy of Sciences, Beijing (China)
  2. Chinese Academy of Sciences (CAS), Beijing (China); Sichuan Normal Univ., Chengdu (China)
  3. Univ. of Chinese Academy of Sciences, Beijing (China); Chinese Academy of Sciences (CAS), Beijing (China)
  4. Chinese Academy of Sciences (CAS), Beijing (China)
  5. Univ. of Chinese Academy of Sciences, Beijing (China); Chinese Academy of Sciences, Shanghai (China)
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1559195
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhao, Lu, Zhang, Yun, Huang, Lin-Bo, Liu, Xiao-Zhi, Zhang, Qing-Hua, He, Chao, Wu, Ze-Yuan, Zhang, Lin-Juan, Wu, Jinpeng, Yang, Wanli, Gu, Lin, Hu, Jin-Song, and Wan, Li-Jun. Cascade anchoring strategy for general mass production of high-loading single-atomic metal-nitrogen catalysts. United States: N. p., 2019. Web. doi:10.1038/s41467-019-09290-y.
Zhao, Lu, Zhang, Yun, Huang, Lin-Bo, Liu, Xiao-Zhi, Zhang, Qing-Hua, He, Chao, Wu, Ze-Yuan, Zhang, Lin-Juan, Wu, Jinpeng, Yang, Wanli, Gu, Lin, Hu, Jin-Song, & Wan, Li-Jun. Cascade anchoring strategy for general mass production of high-loading single-atomic metal-nitrogen catalysts. United States. doi:10.1038/s41467-019-09290-y.
Zhao, Lu, Zhang, Yun, Huang, Lin-Bo, Liu, Xiao-Zhi, Zhang, Qing-Hua, He, Chao, Wu, Ze-Yuan, Zhang, Lin-Juan, Wu, Jinpeng, Yang, Wanli, Gu, Lin, Hu, Jin-Song, and Wan, Li-Jun. Wed . "Cascade anchoring strategy for general mass production of high-loading single-atomic metal-nitrogen catalysts". United States. doi:10.1038/s41467-019-09290-y. https://www.osti.gov/servlets/purl/1559195.
@article{osti_1559195,
title = {Cascade anchoring strategy for general mass production of high-loading single-atomic metal-nitrogen catalysts},
author = {Zhao, Lu and Zhang, Yun and Huang, Lin-Bo and Liu, Xiao-Zhi and Zhang, Qing-Hua and He, Chao and Wu, Ze-Yuan and Zhang, Lin-Juan and Wu, Jinpeng and Yang, Wanli and Gu, Lin and Hu, Jin-Song and Wan, Li-Jun},
abstractNote = {Although single-atomically dispersed metal-Nx on carbon support (M-NC) has great potential in heterogeneous catalysis, the scalable synthesis of such single-atom catalysts (SACs) with high-loading metal-Nx is greatly challenging since the loading and single-atomic dispersion have to be balanced at high temperature for forming metal-Nx. Herein, we develop a general cascade anchoring strategy for the mass production of a series of M-NC SACs with a metal loading up to 12.1 wt%. Systematic investigation reveals that the chelation of metal ions, physical isolation of chelate complex upon high loading, and the binding with N-species at elevated temperature are essential to achieving high-loading M-NC SACs. As a demonstration, high-loading Fe-NC SAC shows superior electrocatalytic performance for O2 reduction and Ni-NC SAC exhibits high electrocatalytic activity for CO2 reduction. The strategy paves a universal way to produce stable M-NC SAC with high-density metal-Nx sites for diverse high-performance applications.},
doi = {10.1038/s41467-019-09290-y},
journal = {Nature Communications},
issn = {2041-1723},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {3}
}

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

Citation Metrics:
Cited by: 68 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Atomic cobalt on nitrogen-doped graphene for hydrogen generation
journal, October 2015

  • Fei, Huilong; Dong, Juncai; Arellano-Jiménez, M. Josefina
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9668

Spectroscopic studies of iron(III) complexes of D-saccharose and D-glucose in the solid state and in solution
journal, September 1996

  • Nagy, L.; Gajda, T.; Kürti, J.
  • Journal of Radioanalytical and Nuclear Chemistry Articles, Vol. 209, Issue 1
  • DOI: 10.1007/BF02063547

Photodegradation Performance of g-C 3 N 4 Fabricated by Directly Heating Melamine
journal, September 2009

  • Yan, S. C.; Li, Z. S.; Zou, Z. G.
  • Langmuir, Vol. 25, Issue 17
  • DOI: 10.1021/la900923z

Transition-metal saccharide chemistry: synthesis, spectroscopy, electrochemistry and magnetic susceptibility studies of iron(III) complexes of mono- and disaccharides
journal, July 1995

  • Geetha, Kuppuswamy; Raghavan, Meenakshi S. S.; Kulshreshtha, Shailendra K.
  • Carbohydrate Research, Vol. 271, Issue 2
  • DOI: 10.1016/0008-6215(95)00050-4

Au Sub-Nanoclusters on TiO 2 toward Highly Efficient and Selective Electrocatalyst for N 2 Conversion to NH 3 at Ambient Conditions
journal, February 2017


In situ electrochemical quantification of active sites in Fe–N/C non-precious metal catalysts
journal, October 2016

  • Malko, Daniel; Kucernak, Anthony; Lopes, Thiago
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms13285

Uncoordinated Amine Groups of Metal–Organic Frameworks to Anchor Single Ru Sites as Chemoselective Catalysts toward the Hydrogenation of Quinoline
journal, July 2017

  • Wang, Xin; Chen, Wenxing; Zhang, Lei
  • Journal of the American Chemical Society, Vol. 139, Issue 28
  • DOI: 10.1021/jacs.7b01686

Low-Temperature Cluster Catalysis
journal, March 2004

  • Judai, Ken; Abbet, Stéphane; Wörz, Anke S.
  • Journal of the American Chemical Society, Vol. 126, Issue 9
  • DOI: 10.1021/ja039037k

Iced photochemical reduction to synthesize atomically dispersed metals by suppressing nanocrystal growth
journal, November 2017


Recent Advances in Atomic Metal Doping of Carbon-based Nanomaterials for Energy Conversion
journal, April 2017


Iron(III) complexes of sugar-type ligands
journal, May 1986


Stabilization of Single Metal Atoms on Graphitic Carbon Nitride
journal, January 2017

  • Chen, Zupeng; Mitchell, Sharon; Vorobyeva, Evgeniya
  • Advanced Functional Materials, Vol. 27, Issue 8
  • DOI: 10.1002/adfm.201605785

N-doped carbon nanomaterials are durable catalysts for oxygen reduction reaction in acidic fuel cells
journal, February 2015


Promotion of oxygen reduction by a bio-inspired tethered iron phthalocyanine carbon nanotube-based catalyst
journal, June 2013

  • Cao, Ruiguo; Thapa, Ranjit; Kim, Hyejung
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3076

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

Operando spectroscopy study of the carbon dioxide electro-reduction by iron species on nitrogen-doped carbon
journal, March 2018


Simultaneous Nitrogen Doping and Reduction of Graphene Oxide
journal, November 2009

  • Li, Xiaolin; Wang, Hailiang; Robinson, Joshua T.
  • Journal of the American Chemical Society, Vol. 131, Issue 43
  • DOI: 10.1021/ja907098f

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

High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt
journal, April 2011


Understanding nano effects in catalysis
journal, May 2015

  • Yang, Fan; Deng, Dehui; Pan, Xiulian
  • National Science Review, Vol. 2, Issue 2
  • DOI: 10.1093/nsr/nwv024

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

Single-atom catalysis of CO oxidation using Pt1/FeOx
journal, July 2011

  • Qiao, Botao; Wang, Aiqin; Yang, Xiaofeng
  • Nature Chemistry, Vol. 3, Issue 8
  • DOI: 10.1038/nchem.1095

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


Sintering of Catalytic Nanoparticles: Particle Migration or Ostwald Ripening?
journal, April 2013

  • Hansen, Thomas W.; DeLaRiva, Andrew T.; Challa, Sivakumar R.
  • Accounts of Chemical Research, Vol. 46, Issue 8
  • DOI: 10.1021/ar3002427

Platinum single-atom and cluster catalysis of the hydrogen evolution reaction
journal, November 2016

  • Cheng, Niancai; Stambula, Samantha; Wang, Da
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms13638

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


Graphitic Nanoshell/Mesoporous Carbon Nanohybrids as Highly Efficient and Stable Bifunctional Oxygen Electrocatalysts for Rechargeable Aqueous Na-Air Batteries
journal, January 2016

  • Cheon, Jae Yeong; Kim, Kyoungho; Sa, Young Jin
  • Advanced Energy Materials, Vol. 6, Issue 7
  • DOI: 10.1002/aenm.201501794

Synthesis–structure–performance correlation for polyaniline–Me–C non-precious metal cathode catalysts for oxygen reduction in fuel cells
journal, January 2011

  • Wu, Gang; Johnston, Christina M.; Mack, Nathan H.
  • Journal of Materials Chemistry, Vol. 21, Issue 30
  • DOI: 10.1039/c0jm03613g

Low-temperature carbon monoxide oxidation catalysed by regenerable atomically dispersed palladium on alumina
journal, September 2014

  • Peterson, Eric J.; DeLaRiva, Andrew T.; Lin, Sen
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5885

Single-Atom Catalysis in Mesoporous Photovoltaics: The Principle of Utility Maximization
journal, October 2014


Identification of active sites in CO oxidation and water-gas shift over supported Pt catalysts
journal, September 2015


Cobalt-Embedded Nitrogen-Rich Carbon Nanotubes Efficiently Catalyze Hydrogen Evolution Reaction at All pH Values
journal, March 2014

  • Zou, Xiaoxin; Huang, Xiaoxi; Goswami, Anandarup
  • Angewandte Chemie International Edition, Vol. 53, Issue 17
  • DOI: 10.1002/anie.201311111

Fe–N bonding in a carbon nanotube–graphene complex for oxygen reduction: an XAS study
journal, January 2014

  • Zhou, Jigang; Duchesne, Paul N.; Hu, Yongfeng
  • Physical Chemistry Chemical Physics, Vol. 16, Issue 30
  • DOI: 10.1039/C4CP01455C

Single Atom (Pd/Pt) Supported on Graphitic Carbon Nitride as an Efficient Photocatalyst for Visible-Light Reduction of Carbon Dioxide
journal, May 2016

  • Gao, Guoping; Jiao, Yan; Waclawik, Eric R.
  • Journal of the American Chemical Society, Vol. 138, Issue 19
  • DOI: 10.1021/jacs.6b02692

Understanding activity and selectivity of metal-nitrogen-doped carbon catalysts for electrochemical reduction of CO2
journal, October 2017


Tuning selectivity of electrochemical reactions by atomically dispersed platinum catalyst
journal, March 2016

  • Choi, Chang Hyuck; Kim, Minho; Kwon, Han Chang
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms10922

Direct Observations of Oxygen-induced Platinum Nanoparticle Ripening Studied by In Situ TEM
journal, June 2010

  • Simonsen, Søren B.; Chorkendorff, Ib; Dahl, Søren
  • Journal of the American Chemical Society, Vol. 132, Issue 23
  • DOI: 10.1021/ja910094r

An oxygen reduction electrocatalyst based on carbon nanotube–graphene complexes
journal, May 2012

  • Li, Yanguang; Zhou, Wu; Wang, Hailiang
  • Nature Nanotechnology, Vol. 7, Issue 6
  • DOI: 10.1038/nnano.2012.72

High performance platinum single atom electrocatalyst for oxygen reduction reaction
journal, July 2017

  • Liu, Jing; Jiao, Menggai; Lu, Lanlu
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15938

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


Review on Recent Progress in Nitrogen-Doped Graphene: Synthesis, Characterization, and Its Potential Applications
journal, April 2012

  • Wang, Haibo; Maiyalagan, Thandavarayan; Wang, Xin
  • ACS Catalysis, Vol. 2, Issue 5
  • DOI: 10.1021/cs200652y

Single-Atom Pt as Co-Catalyst for Enhanced Photocatalytic H 2 Evolution
journal, January 2016


CO Oxidation on Au n /TiO 2 Catalysts Produced by Size-Selected Cluster Deposition
journal, May 2004

  • Lee, Sungsik; Fan, Chaoyang; Wu, Tianpin
  • Journal of the American Chemical Society, Vol. 126, Issue 18
  • DOI: 10.1021/ja049436v

Increased Silver Activity for Direct Propylene Epoxidation via Subnanometer Size Effects
journal, April 2010


Direct observation of noble metal nanoparticles transforming to thermally stable single atoms
journal, July 2018


A Polymer Encapsulation Strategy to Synthesize Porous Nitrogen-Doped Carbon-Nanosphere-Supported Metal Isolated-Single-Atomic-Site Catalysts
journal, March 2018

  • Han, Aijuan; Chen, Wenxing; Zhang, Shaolong
  • Advanced Materials, Vol. 30, Issue 15
  • DOI: 10.1002/adma.201706508

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

In Situ Thermal Atomization To Convert Supported Nickel Nanoparticles into Surface-Bound Nickel Single-Atom Catalysts
journal, October 2018

  • Yang, Jian; Qiu, Zongyang; Zhao, Changming
  • Angewandte Chemie International Edition, Vol. 57, Issue 43
  • DOI: 10.1002/anie.201808049

Aligned carbon nanotubes with built-in FeN 4 active sites for electrocatalytic reduction of oxygen
journal, January 2008

  • Yang, Junbing; Liu, Di-Jia; Kariuki, Nancy N.
  • Chem. Commun., Issue 3
  • DOI: 10.1039/B713096A

X-ray absorption spectroscopy of biomimetic dye molecules for solar cells
journal, January 2009

  • Cook, Peter L.; Liu, Xiaosong; Yang, Wanli
  • The Journal of Chemical Physics, Vol. 131, Issue 19
  • DOI: 10.1063/1.3257621

Phenylenediamine-Based FeN x /C Catalyst with High Activity for Oxygen Reduction in Acid Medium and Its Active-Site Probing
journal, July 2014

  • Wang, Qiang; Zhou, Zhi-You; Lai, Yu-Jiao
  • Journal of the American Chemical Society, Vol. 136, Issue 31
  • DOI: 10.1021/ja505777v

Characterization of iron oxides by x-ray absorption at the oxygen K edgeusing a full multiple-scattering approach
journal, January 1997


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


Synergetic interaction between neighbouring platinum monomers in CO2 hydrogenation
journal, March 2018


Gold Supported on Thin Oxide Films: From Single Atoms to Nanoparticles
journal, August 2008

  • Risse, Thomas; Shaikhutdinov, Shamil; Nilius, Niklas
  • Accounts of Chemical Research, Vol. 41, Issue 8
  • DOI: 10.1021/ar800078m

Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D
journal, September 2016

  • Liu, Lichen; Díaz, Urbano; Arenal, Raul
  • Nature Materials, Vol. 16, Issue 1
  • DOI: 10.1038/nmat4757

Edge-Site Engineering of Atomically Dispersed Fe–N 4 by Selective C–N Bond Cleavage for Enhanced Oxygen Reduction Reaction Activities
journal, August 2018

  • Jiang, Rui; Li, Li; Sheng, Tian
  • Journal of the American Chemical Society, Vol. 140, Issue 37
  • DOI: 10.1021/jacs.8b07294

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

Direct, Nonoxidative Conversion of Methane to Ethylene, Aromatics, and Hydrogen
journal, May 2014


Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst
journal, August 2017


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

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


Identification of Active Gold Nanoclusters on Iron Oxide Supports for CO Oxidation
journal, September 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

Subnanometre platinum clusters as highly active and selective catalysts for the oxidative dehydrogenation of propane
journal, February 2009

  • Vajda, Stefan; Pellin, Michael J.; Greeley, Jeffrey P.
  • Nature Materials, Vol. 8, Issue 3
  • DOI: 10.1038/nmat2384

The Effect of Size-Dependent Nanoparticle Energetics on Catalyst Sintering
journal, October 2002


Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts
journal, November 2017

  • Shan, Junjun; Li, Mengwei; Allard, Lawrence F.
  • Nature, Vol. 551, Issue 7682
  • DOI: 10.1038/nature24640