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Title: MO-Co@N-Doped Carbon (M = Zn or Co): Vital Roles of Inactive Zn and Highly Efficient Activity toward Oxygen Reduction/Evolution Reactions for Rechargeable Zn-Air Battery

Abstract

A highly efficient bifunctional oxygen catalyst is required for practical applications of fuel cells and metal-air batteries, as oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are their core electrode reactions. Here, the MO-Co@ N-doped carbon (NC, M = Zn or Co) is developed as a highly active ORR/OER bifunctional catalyst via pyrolysis of a bimetal metal-organic framework containing Zn and Co, i.e., precursor (CoZn). The vital roles of inactive Zn in developing highly active bifunctional oxygen catalysts are unraveled. When the precursors include Zn, the surface contents of pyridinic N for ORR and the surface contents of Co-N-x and Co3+/Co2+ ratios for OER are enhanced, while the high specific surface areas, high porosity, and high electrochemical active surface areas are also achieved. Furthermore, the synergistic effects between Zn-based and Co-based species can promote the well growth of multiwalled carbon nanotubes (MWCNTs) at high pyrolysis temperatures (>= 700 degrees C), which is favorable for charge transfer. The optimized CoZn-NC-700 shows the highly bifunctional ORR/OER activity and the excellent durability during the ORR/OER processes, even better than 20 wt% Pt/C (for ORR) and IrO2 (for OER). CoZn-NC-700 also exhibits the prominent Zn-air battery performance and even outperforms the mixture ofmore » 20 wt% Pt/C and IrO2.« less

Authors:
 [1];  [2];  [3];  [4];  [5];  [6];  [6];  [6]
  1. State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 P. R. China; Beijing Key Laboratory of Energy Environmental Catalysis, Beijing University of Chemical Technology, Beijing 100029 P. R. China
  2. Changzhou Institute of Advanced Materials, Beijing University of Chemical Technology, Changzhou 213164 P. R. China
  3. State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 P. R. China; Beijing Key Laboratory of Energy Environmental Catalysis, Beijing University of Chemical Technology, Beijing 100029 P. R. China; Changzhou Institute of Advanced Materials, Beijing University of Chemical Technology, Changzhou 213164 P. R. China
  4. State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 P. R. China; Beijing Key Laboratory of Energy Environmental Catalysis, Beijing University of Chemical Technology, Beijing 100029 P. R. China; Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA
  5. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA
  6. State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 P. R. China
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Natural Science Foundation of China (NNSFC); Fundamental Research Funds for the Central Universities
OSTI Identifier:
1411443
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Volume: 27; Journal Issue: 37; Journal ID: ISSN 1616-301X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Chen, Biaohua, He, Xiaobo, Yin, Fengxiang, Wang, Hao, Liu, Di-Jia, Shi, Ruixing, Chen, Jinnan, and Yin, Hongwei. MO-Co@N-Doped Carbon (M = Zn or Co): Vital Roles of Inactive Zn and Highly Efficient Activity toward Oxygen Reduction/Evolution Reactions for Rechargeable Zn-Air Battery. United States: N. p., 2017. Web. doi:10.1002/adfm.201700795.
Chen, Biaohua, He, Xiaobo, Yin, Fengxiang, Wang, Hao, Liu, Di-Jia, Shi, Ruixing, Chen, Jinnan, & Yin, Hongwei. MO-Co@N-Doped Carbon (M = Zn or Co): Vital Roles of Inactive Zn and Highly Efficient Activity toward Oxygen Reduction/Evolution Reactions for Rechargeable Zn-Air Battery. United States. doi:10.1002/adfm.201700795.
Chen, Biaohua, He, Xiaobo, Yin, Fengxiang, Wang, Hao, Liu, Di-Jia, Shi, Ruixing, Chen, Jinnan, and Yin, Hongwei. Wed . "MO-Co@N-Doped Carbon (M = Zn or Co): Vital Roles of Inactive Zn and Highly Efficient Activity toward Oxygen Reduction/Evolution Reactions for Rechargeable Zn-Air Battery". United States. doi:10.1002/adfm.201700795.
@article{osti_1411443,
title = {MO-Co@N-Doped Carbon (M = Zn or Co): Vital Roles of Inactive Zn and Highly Efficient Activity toward Oxygen Reduction/Evolution Reactions for Rechargeable Zn-Air Battery},
author = {Chen, Biaohua and He, Xiaobo and Yin, Fengxiang and Wang, Hao and Liu, Di-Jia and Shi, Ruixing and Chen, Jinnan and Yin, Hongwei},
abstractNote = {A highly efficient bifunctional oxygen catalyst is required for practical applications of fuel cells and metal-air batteries, as oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are their core electrode reactions. Here, the MO-Co@ N-doped carbon (NC, M = Zn or Co) is developed as a highly active ORR/OER bifunctional catalyst via pyrolysis of a bimetal metal-organic framework containing Zn and Co, i.e., precursor (CoZn). The vital roles of inactive Zn in developing highly active bifunctional oxygen catalysts are unraveled. When the precursors include Zn, the surface contents of pyridinic N for ORR and the surface contents of Co-N-x and Co3+/Co2+ ratios for OER are enhanced, while the high specific surface areas, high porosity, and high electrochemical active surface areas are also achieved. Furthermore, the synergistic effects between Zn-based and Co-based species can promote the well growth of multiwalled carbon nanotubes (MWCNTs) at high pyrolysis temperatures (>= 700 degrees C), which is favorable for charge transfer. The optimized CoZn-NC-700 shows the highly bifunctional ORR/OER activity and the excellent durability during the ORR/OER processes, even better than 20 wt% Pt/C (for ORR) and IrO2 (for OER). CoZn-NC-700 also exhibits the prominent Zn-air battery performance and even outperforms the mixture of 20 wt% Pt/C and IrO2.},
doi = {10.1002/adfm.201700795},
journal = {Advanced Functional Materials},
issn = {1616-301X},
number = 37,
volume = 27,
place = {United States},
year = {2017},
month = {6}
}

Works referenced in this record:

MOF-Derived Hierarchically Porous Carbon with Exceptional Porosity and Hydrogen Storage Capacity
journal, December 2011

  • Yang, Seung Jae; Kim, Taehoon; Im, Ji Hyuk
  • Chemistry of Materials, Vol. 24, Issue 3
  • DOI: 10.1021/cm202554j

From Metal–Organic Framework to Nanoporous Carbon: Toward a Very High Surface Area and Hydrogen Uptake
journal, August 2011

  • Jiang, Hai-Long; Liu, Bo; Lan, Ya-Qian
  • Journal of the American Chemical Society, Vol. 133, Issue 31
  • DOI: 10.1021/ja203184k

A mini review of NiFe-based materials as highly active oxygen evolution reaction electrocatalysts
journal, November 2014


Nitrogen-Doped Carbon Nanotube Arrays with High Electrocatalytic Activity for Oxygen Reduction
journal, February 2009


A Bifunctional Nonprecious Metal Catalyst for Oxygen Reduction and Water Oxidation
journal, October 2010

  • Gorlin, Yelena; Jaramillo, Thomas F.
  • Journal of the American Chemical Society, Vol. 132, Issue 39, p. 13612-13614
  • DOI: 10.1021/ja104587v

A metal–organic framework-derived bifunctional oxygen electrocatalyst
journal, January 2016


Molecule-Level g-C 3 N 4 Coordinated Transition Metals as a New Class of Electrocatalysts for Oxygen Electrode Reactions
journal, February 2017

  • Zheng, Yao; Jiao, Yan; Zhu, Yihan
  • Journal of the American Chemical Society, Vol. 139, Issue 9
  • DOI: 10.1021/jacs.6b13100

Engineering surface atomic structure of single-crystal cobalt (II) oxide nanorods for superior electrocatalysis
journal, September 2016

  • Ling, Tao; Yan, Dong-Yang; Jiao, Yan
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12876

Nickel nitride as an efficient electrocatalyst for water splitting
journal, January 2015

  • Shalom, Menny; Ressnig, Debora; Yang, Xiaofei
  • Journal of Materials Chemistry A, Vol. 3, Issue 15
  • DOI: 10.1039/C5TA00078E

Sulfur and Nitrogen Dual-Doped Mesoporous Graphene Electrocatalyst for Oxygen Reduction with Synergistically Enhanced Performance
journal, October 2012

  • Liang, Ji; Jiao, Yan; Jaroniec, Mietek
  • Angewandte Chemie International Edition, Vol. 51, Issue 46
  • DOI: 10.1002/anie.201206720

A carbon-free, precious-metal-free, high-performance O2 electrode for regenerative fuel cells and metal–air batteries
journal, January 2014

  • Ng, Jia Wei Desmond; Tang, Maureen; Jaramillo, Thomas F.
  • Energy & Environmental Science, Vol. 7, Issue 6
  • DOI: 10.1039/c3ee44059a

Hydrogenated Uniform Pt Clusters Supported on Porous CaMnO 3 as a Bifunctional Electrocatalyst for Enhanced Oxygen Reduction and Evolution
journal, December 2013

  • Han, Xiaopeng; Cheng, Fangyi; Zhang, Tianran
  • Advanced Materials, Vol. 26, Issue 13
  • DOI: 10.1002/adma.201304867

On the Role of Metals in Nitrogen-Doped Carbon Electrocatalysts for Oxygen Reduction
journal, July 2015

  • Masa, Justus; Xia, Wei; Muhler, Martin
  • Angewandte Chemie International Edition, Vol. 54, Issue 35
  • DOI: 10.1002/anie.201500569

Three-Dimensional Smart Catalyst Electrode for Oxygen Evolution Reaction
journal, July 2015

  • Chen, Sheng; Duan, Jingjing; Bian, Pengju
  • Advanced Energy Materials, Vol. 5, Issue 18
  • DOI: 10.1002/aenm.201500936

Self-Templating Synthesis of Hollow Co 3 O 4 Microtube Arrays for Highly Efficient Water Electrolysis
journal, November 2016

  • Zhu, Yun Pei; Ma, Tian Yi; Jaroniec, Mietek
  • Angewandte Chemie International Edition, Vol. 56, Issue 5
  • DOI: 10.1002/anie.201610413

Nonstoichiometric Oxides as Low-Cost and Highly-Efficient Oxygen Reduction/Evolution Catalysts for Low-Temperature Electrochemical Devices
journal, August 2015


A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles
journal, October 2011


Perspectives on Carbon Nanotubes and Graphene Raman Spectroscopy
journal, March 2010

  • Dresselhaus, Mildred S.; Jorio, Ado; Hofmann, Mario
  • Nano Letters, Vol. 10, Issue 3
  • DOI: 10.1021/nl904286r

Electrocatalytic Measurement Methodology of Oxide Catalysts Using a Thin-Film Rotating Disk Electrode
journal, January 2010

  • Suntivich, Jin; Gasteiger, Hubert A.; Yabuuchi, Naoaki
  • Journal of The Electrochemical Society, Vol. 157, Issue 8
  • DOI: 10.1149/1.3456630

Phosphorus-Doped Graphitic Carbon Nitrides Grown In Situ on Carbon-Fiber Paper: Flexible and Reversible Oxygen Electrodes
journal, December 2014

  • Ma, Tian Yi; Ran, Jingrun; Dai, Sheng
  • Angewandte Chemie International Edition, Vol. 54, Issue 15
  • DOI: 10.1002/anie.201411125

Toward Full Exposure of “Active Sites”: Nanocarbon Electrocatalyst with Surface Enriched Nitrogen for Superior Oxygen Reduction and Evolution Reactivity
journal, July 2014

  • Tian, Gui-Li; Zhang, Qiang; Zhang, Bingsen
  • Advanced Functional Materials, Vol. 24, Issue 38
  • DOI: 10.1002/adfm.201401264

Cross-Laboratory Experimental Study of Non-Noble-Metal Electrocatalysts for the Oxygen Reduction Reaction
journal, July 2009

  • Jaouen, Frédéric; Herranz, Juan; Lefèvre, Michel
  • ACS Applied Materials & Interfaces, Vol. 1, Issue 8, p. 1623-1639
  • DOI: 10.1021/am900219g

Scalable Fabrication of Nanoporous Carbon Fiber Films as Bifunctional Catalytic Electrodes for Flexible Zn-Air Batteries
journal, February 2016


Simple coordination complex-derived three-dimensional mesoporous graphene as an efficient bifunctional oxygen electrocatalyst
journal, January 2015

  • Lee, Kyung Joo; Sa, Young Jin; Jeong, Hu Young
  • Chemical Communications, Vol. 51, Issue 31
  • DOI: 10.1039/C5CC01123J

Oxygen Electrochemistry as a Cornerstone for Sustainable Energy Conversion
journal, December 2013

  • Katsounaros, Ioannis; Cherevko, Serhiy; Zeradjanin, Aleksandar R.
  • Angewandte Chemie International Edition, Vol. 53, Issue 1
  • DOI: 10.1002/anie.201306588

Hierarchical mesoporous perovskite La0.5Sr0.5CoO2.91 nanowires with ultrahigh capacity for Li-air batteries
journal, November 2012

  • Zhao, Y.; Xu, L.; Mai, L.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 48
  • DOI: 10.1073/pnas.1210315109

Unraveling the Catalytic Mechanism of Co 3 O 4 for the Oxygen Evolution Reaction in a Li–O 2 Battery
journal, November 2014

  • Zhu, Jinzhen; Ren, Xiaodong; Liu, Jianjun
  • ACS Catalysis, Vol. 5, Issue 1
  • DOI: 10.1021/cs5014442

Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces
journal, March 2011

  • Man, Isabela C.; Su, Hai‐Yan; Calle‐Vallejo, Federico
  • ChemCatChem, Vol. 3, Issue 7
  • DOI: 10.1002/cctc.201000397

Activation of oxygen evolving perovskites for oxygen reduction by functionalization with Fe–N x /C groups
journal, January 2014

  • Rincón, Rosalba A.; Masa, Justus; Mehrpour, Sara
  • Chem. Commun., Vol. 50, Issue 94
  • DOI: 10.1039/C4CC06446A

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

Conversion of electrodeposited Co(OH)2 to CoOOH and Co3O4, and comparison of their catalytic activity for the oxygen evolution reaction
journal, September 2014


Recent advances in zinc–air batteries
journal, January 2014


Metal-Organic Framework as a Template for Porous Carbon Synthesis
journal, April 2008

  • Liu, Bo; Shioyama, Hiroshi; Akita, Tomoki
  • Journal of the American Chemical Society, Vol. 130, Issue 16
  • DOI: 10.1021/ja7106146

Ordered Mesoporous Cobalt Oxide as Highly Efficient Oxygen Evolution Catalyst
journal, March 2013

  • Rosen, Jonathan; Hutchings, Gregory S.; Jiao, Feng
  • Journal of the American Chemical Society, Vol. 135, Issue 11
  • DOI: 10.1021/ja400555q

A two-dimensional zeolitic imidazolate framework with a cushion-shaped cavity for CO2 adsorption
journal, January 2013

  • Chen, Rizhi; Yao, Jianfeng; Gu, Qinfen
  • Chemical Communications, Vol. 49, Issue 82
  • DOI: 10.1039/c3cc44342f

Topological Defects in Metal-Free Nanocarbon for Oxygen Electrocatalysis
journal, May 2016


Cobalt Imidazolate Framework as Precursor for Oxygen Reduction Reaction Electrocatalysts
journal, January 2011

  • Ma, Shengqian; Goenaga, Gabriel A.; Call, Ann V.
  • Chemistry - A European Journal, Vol. 17, Issue 7
  • DOI: 10.1002/chem.201003080

Metal-Organic Framework-Based Nanomaterials for Electrocatalysis
journal, May 2016

  • Mahmood, Asif; Guo, Wenhan; Tabassum, Hassina
  • Advanced Energy Materials, Vol. 6, Issue 17
  • DOI: 10.1002/aenm.201600423

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

Nonstoichiometric Perovskite CaMnO 3−δ for Oxygen Electrocatalysis with High Activity
journal, August 2014

  • Du, Jing; Zhang, Tianran; Cheng, Fangyi
  • Inorganic Chemistry, Vol. 53, Issue 17
  • DOI: 10.1021/ic501631h

Carbon-based metal-free catalysts
journal, September 2016


Ultrathin Co 3 S 4 Nanosheets that Synergistically Engineer Spin States and Exposed Polyhedra that Promote Water Oxidation under Neutral Conditions
journal, July 2015

  • Liu, Youwen; Xiao, Chong; Lyu, Mengjie
  • Angewandte Chemie International Edition, Vol. 54, Issue 38
  • DOI: 10.1002/anie.201505320

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

Earth-Abundant Nanomaterials for Oxygen Reduction
journal, December 2015

  • Xia, Wei; Mahmood, Asif; Liang, Zibin
  • Angewandte Chemie International Edition, Vol. 55, Issue 8
  • DOI: 10.1002/anie.201504830

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