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Title: High-performance oxygen reduction and evolution carbon catalysis: From mechanistic studies to device integration

Abstract

The development of high-performance and low-cost oxygen reduction and evolution catalysts that can be easily integrated into existing devices is crucial for the wide deployment of energy storage systems that utilize O 2-H 2O chemistries, such as regenerative fuel cells and metal-air batteries. Herein, we report an NH 3-activated N-doped hierarchical carbon (NHC) catalyst synthesized via a scalable route, and demonstrate its device integration. The NHC catalyst exhibited good performance for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), as demonstrated by means of electrochemical studies and evaluation when integrated into the oxygen electrode of a regenerative fuel cell. The activities observed for both the ORR and the OER were comparable to those achieved by state-of-the-art Pt and Ir catalysts in alkaline environments. We have further identified the critical role of carbon defects as active sites for electrochemical activity through density functional theory calculations and high-resolution TEM visualization. As a result, this work highlights the potential of NHC to replace commercial precious metals in regenerative fuel cells and possibly metal-air batteries for cost-effective storage of intermittent renewable energy.

Authors:
 [1];  [2];  [1];  [1];  [3];  [1];  [1];  [1];  [4];  [1];  [4];  [3];  [3];  [5];  [6];  [1];  [1]
  1. Stanford Univ., Stanford, CA (United States)
  2. Stanford Univ., Stanford, CA (United States); Institute of Chemical and Engineering Sciences, Jurong Island (Singapore)
  3. Ulsan National Institute of Science and Technology (UNIST), Ulsan (Republic of Korea)
  4. Colorado School of Mines, Golden, CO (United States)
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States); Karlsruhe Institute of Technology, Eggenstein-Leopoldshafen (Germany); Karlsruhe Institute of Technology, Karlsruhe (Germany)
  6. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1349293
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Nano Research
Additional Journal Information:
Journal Volume: 10; Journal Issue: 4; Journal ID: ISSN 1998-0124
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; electrocatalysis; porous carbon; density functional theory

Citation Formats

To, John W. F., Ng, Jia Wei Desmond, Siahrostami, Samira, Koh, Ai Leen, Lee, Yangjin, Chen, Zhihua, Fong, Kara D., Chen, Shucheng, He, Jiajun, Bae, Won -Gyu, Wilcox, Jennifer, Jeong, Hu Young, Kim, Kwanpyo, Studt, Felix, Nørskov, Jens K., Jaramillo, Thomas F., and Bao, Zhenan. High-performance oxygen reduction and evolution carbon catalysis: From mechanistic studies to device integration. United States: N. p., 2016. Web. doi:10.1007/s12274-016-1347-8.
To, John W. F., Ng, Jia Wei Desmond, Siahrostami, Samira, Koh, Ai Leen, Lee, Yangjin, Chen, Zhihua, Fong, Kara D., Chen, Shucheng, He, Jiajun, Bae, Won -Gyu, Wilcox, Jennifer, Jeong, Hu Young, Kim, Kwanpyo, Studt, Felix, Nørskov, Jens K., Jaramillo, Thomas F., & Bao, Zhenan. High-performance oxygen reduction and evolution carbon catalysis: From mechanistic studies to device integration. United States. doi:10.1007/s12274-016-1347-8.
To, John W. F., Ng, Jia Wei Desmond, Siahrostami, Samira, Koh, Ai Leen, Lee, Yangjin, Chen, Zhihua, Fong, Kara D., Chen, Shucheng, He, Jiajun, Bae, Won -Gyu, Wilcox, Jennifer, Jeong, Hu Young, Kim, Kwanpyo, Studt, Felix, Nørskov, Jens K., Jaramillo, Thomas F., and Bao, Zhenan. Wed . "High-performance oxygen reduction and evolution carbon catalysis: From mechanistic studies to device integration". United States. doi:10.1007/s12274-016-1347-8. https://www.osti.gov/servlets/purl/1349293.
@article{osti_1349293,
title = {High-performance oxygen reduction and evolution carbon catalysis: From mechanistic studies to device integration},
author = {To, John W. F. and Ng, Jia Wei Desmond and Siahrostami, Samira and Koh, Ai Leen and Lee, Yangjin and Chen, Zhihua and Fong, Kara D. and Chen, Shucheng and He, Jiajun and Bae, Won -Gyu and Wilcox, Jennifer and Jeong, Hu Young and Kim, Kwanpyo and Studt, Felix and Nørskov, Jens K. and Jaramillo, Thomas F. and Bao, Zhenan},
abstractNote = {The development of high-performance and low-cost oxygen reduction and evolution catalysts that can be easily integrated into existing devices is crucial for the wide deployment of energy storage systems that utilize O2-H2O chemistries, such as regenerative fuel cells and metal-air batteries. Herein, we report an NH3-activated N-doped hierarchical carbon (NHC) catalyst synthesized via a scalable route, and demonstrate its device integration. The NHC catalyst exhibited good performance for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), as demonstrated by means of electrochemical studies and evaluation when integrated into the oxygen electrode of a regenerative fuel cell. The activities observed for both the ORR and the OER were comparable to those achieved by state-of-the-art Pt and Ir catalysts in alkaline environments. We have further identified the critical role of carbon defects as active sites for electrochemical activity through density functional theory calculations and high-resolution TEM visualization. As a result, this work highlights the potential of NHC to replace commercial precious metals in regenerative fuel cells and possibly metal-air batteries for cost-effective storage of intermittent renewable energy.},
doi = {10.1007/s12274-016-1347-8},
journal = {Nano Research},
number = 4,
volume = 10,
place = {United States},
year = {2016},
month = {11}
}

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Works referenced in this record:

Addressing the terawatt challenge: scalability in the supply of chemical elements for renewable energy
journal, January 2012

  • Vesborg, Peter C. K.; Jaramillo, Thomas F.
  • RSC Advances, Vol. 2, Issue 21
  • DOI: 10.1039/c2ra20839c

A review on non-precious metal electrocatalysts for PEM fuel cells
journal, January 2011

  • Chen, Zhongwei; Higgins, Drew; Yu, Aiping
  • Energy & Environmental Science, Vol. 4, Issue 9
  • DOI: 10.1039/c0ee00558d

Recent progress on nitrogen/carbon structures designed for use in energy and sustainability applications
journal, January 2014

  • Wood, Kevin N.; O'Hayre, Ryan; Pylypenko, Svitlana
  • Energy Environ. Sci., Vol. 7, Issue 4
  • DOI: 10.1039/C3EE44078H

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


Synthesis of Mesoporous Carbon Materials via Enhanced Hydrogen-Bonding Interaction
journal, April 2006

  • Liang, Chengdu; Dai, Sheng
  • Journal of the American Chemical Society, Vol. 128, Issue 16, p. 5316-5317
  • DOI: 10.1021/ja060242k

Nanostructured Manganese Oxide Supported onto Particulate Glassy Carbon as an Active and Stable Oxygen Reduction Catalyst in Alkaline-Based Fuel Cells
journal, January 2014

  • Ng, Jia Wei Desmond; Gorlin, Yelena; Nordlund, Dennis
  • Journal of The Electrochemical Society, Vol. 161, Issue 7
  • DOI: 10.1149/2.014407jes

Electrochemically Active Nitrogen-Enriched Nanocarbons with Well-Defined Morphology Synthesized by Pyrolysis of Self-Assembled Block Copolymer
journal, September 2012

  • Zhong, Mingjiang; Kim, Eun Kyung; McGann, John P.
  • Journal of the American Chemical Society, Vol. 134, Issue 36
  • DOI: 10.1021/ja304352n

Electrochemical reduction of oxygen on thin-film Pt electrodes in 0.1 M KOH
journal, January 1997


Interplay between nitrogen dopants and native point defects in graphene
journal, April 2012


Supramolecular Aggregates as Templates: Ordered Mesoporous Polymers and Carbons
journal, February 2008

  • Wan, Ying; Shi, Yifeng; Zhao, Dongyuan
  • Chemistry of Materials, Vol. 20, Issue 3
  • DOI: 10.1021/cm7024125

Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs
journal, March 2005

  • Gasteiger, Hubert A.; Kocha, Shyam S.; Sompalli, Bhaskar
  • Applied Catalysis B: Environmental, Vol. 56, Issue 1-2, p. 9-35
  • DOI: 10.1016/j.apcatb.2004.06.021

Active and stable carbon nanotube/nanoparticle composite electrocatalyst for oxygen reduction
journal, May 2013

  • Chung, Hoon T.; Won, Jong H.; Zelenay, Piotr
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms2944

Facile One-Pot, One-Step Synthesis of a Carbon Nanoarchitecture for an Advanced Multifunctonal Electrocatalyst
journal, May 2014

  • Wen, Zhenhai; Ci, Suqin; Hou, Yang
  • Angewandte Chemie International Edition, Vol. 53, Issue 25
  • DOI: 10.1002/anie.201402574

Mixed-Metal Pt Monolayer Electrocatalysts for Enhanced Oxygen Reduction Kinetics
journal, September 2005

  • Zhang, Junliang; Vukmirovic, Miomir B.; Sasaki, Kotaro
  • Journal of the American Chemical Society, Vol. 127, Issue 36
  • DOI: 10.1021/ja053695i

Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction
journal, September 2014

  • Liang, Hai-Wei; Zhuang, Xiaodong; Brüller, Sebastian
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5973

Noble-Metal-Free Electrocatalysts with Enhanced ORR Performance by Task-Specific Functionalization of Carbon using Ionic Liquid Precursor Systems
journal, September 2014

  • Ranjbar Sahraie, Nastaran; Paraknowitsch, Jens Peter; Göbel, Caren
  • Journal of the American Chemical Society, Vol. 136, Issue 41
  • DOI: 10.1021/ja506553r

Heterogeneous nanocarbon materials for oxygen reduction reaction
journal, January 2014

  • Wang, Da-Wei; Su, Dangsheng
  • Energy & Environmental Science, Vol. 7, Issue 2
  • DOI: 10.1039/c3ee43463j

Electrocatalysis of the hydrogen oxidation and of the oxygen reduction reactions of Pt and some alloys in alkaline medium
journal, July 1987


Fe-N-C Oxygen Reduction Fuel Cell Catalyst Derived from Carbendazim: Synthesis, Structure, and Reactivity
journal, March 2014

  • Serov, Alexey; Artyushkova, Kateryna; Atanassov, Plamen
  • Advanced Energy Materials, Vol. 4, Issue 10
  • DOI: 10.1002/aenm.201301735

Significant Contribution of Intrinsic Carbon Defects to Oxygen Reduction Activity
journal, October 2015


Nanoporous graphene by quantum dots removal from graphene and its conversion to a potential oxygen reduction electrocatalyst via nitrogen doping
journal, January 2014

  • Palaniselvam, Thangavelu; Valappil, Manila Ozhukil; Illathvalappil, Rajith
  • Energy & Environmental Science, Vol. 7, Issue 3
  • DOI: 10.1039/c3ee43648a

Electrical Energy Storage for the Grid: A Battery of Choices
journal, November 2011


Nanostructured Thermosets from Self-Assembled Amphiphilic Block Copolymer/Epoxy Resin Mixtures
journal, September 1998

  • Lipic, Paul M.; Bates, Frank S.; Hillmyer, Marc A.
  • Journal of the American Chemical Society, Vol. 120, Issue 35
  • DOI: 10.1021/ja981544s

Catalyzing the Hydrogen Evolution Reaction (HER) with Molybdenum Sulfide Nanomaterials
journal, October 2014

  • Benck, Jesse D.; Hellstern, Thomas R.; Kibsgaard, Jakob
  • ACS Catalysis, Vol. 4, Issue 11
  • DOI: 10.1021/cs500923c

Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation
journal, June 2012


Assessing the reliability of calculated catalytic ammonia synthesis rates
journal, July 2014


An object-oriented scripting interface to a legacy electronic structure code
journal, January 2002

  • Bahn, S. R.; Jacobsen, K. W.
  • Computing in Science & Engineering, Vol. 4, Issue 3
  • DOI: 10.1109/5992.998641

Controllable N-Doping of Graphene
journal, December 2010

  • Guo, Beidou; Liu, Qian; Chen, Erdan
  • Nano Letters, Vol. 10, Issue 12
  • DOI: 10.1021/nl103079j

Dynamics and stability of divacancy defects in graphene
journal, August 2011


Controllable graphene N-doping with ammonia plasma
journal, March 2010

  • Lin, Yung-Chang; Lin, Chih-Yueh; Chiu, Po-Wen
  • Applied Physics Letters, Vol. 96, Issue 13
  • DOI: 10.1063/1.3368697

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

Lattice-strain control of the activity in dealloyed core–shell fuel cell catalysts
journal, April 2010

  • Strasser, Peter; Koh, Shirlaine; Anniyev, Toyli
  • Nature Chemistry, Vol. 2, Issue 6
  • DOI: 10.1038/nchem.623

Meso-Structured Platinum Thin Films: Active and Stable Electrocatalysts for the Oxygen Reduction Reaction
journal, April 2012

  • Kibsgaard, Jakob; Gorlin, Yelena; Chen, Zhebo
  • Journal of the American Chemical Society, Vol. 134, Issue 18
  • DOI: 10.1021/ja2120162

Recommendations for the characterization of porous solids (Technical Report)
journal, January 1994

  • Rouquerol, J.; Avnir, D.; Fairbridge, C. W.
  • Pure and Applied Chemistry, Vol. 66, Issue 8, p. 1739-1758
  • DOI: 10.1351/pac199466081739

Ordered Mesoporous Polymers and Homologous Carbon Frameworks: Amphiphilic Surfactant Templating and Direct Transformation
journal, November 2005

  • Meng, Yan; Gu, Dong; Zhang, Fuqiang
  • Angewandte Chemie, Vol. 117, Issue 43, p. 7215-7221
  • DOI: 10.1002/ange.200501561

Polymer Electrolyte Membrane Electrolyzers Utilizing Non-precious Mo-based Hydrogen Evolution Catalysts
journal, September 2015

  • Ng, Jia Wei Desmond; Hellstern, Thomas R.; Kibsgaard, Jakob
  • ChemSusChem, Vol. 8, Issue 20
  • DOI: 10.1002/cssc.201500334

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

A Precious-Metal-Free Regenerative Fuel Cell for Storing Renewable Electricity
journal, July 2013

  • Desmond Ng, Jia Wei; Gorlin, Yelena; Hatsukade, Toru
  • Advanced Energy Materials, Vol. 3, Issue 12
  • DOI: 10.1002/aenm.201300492

Electrochemical Energy Storage for Green Grid
journal, May 2011

  • Yang, Zhenguo; Zhang, Jianlu; Kintner-Meyer, Michael C. W.
  • Chemical Reviews, Vol. 111, Issue 5, p. 3577-3613
  • DOI: 10.1021/cr100290v

Effect of Surface Composition on Electronic Structure, Stability, and Electrocatalytic Properties of Pt-Transition Metal Alloys:  Pt-Skin versus Pt-Skeleton Surfaces
journal, July 2006

  • Stamenkovic, Vojislav R.; Mun, Bongjin Simon; Mayrhofer, Karl J. J.
  • Journal of the American Chemical Society, Vol. 128, Issue 27
  • DOI: 10.1021/ja0600476

Electrolyte effects on oxygen reduction kinetics at platinum: A rotating ring-disc electrode analysis
journal, May 1983


Spectroscopic Characterization of Mixed Fe–Ni Oxide Electrocatalysts for the Oxygen Evolution Reaction in Alkaline Electrolytes
journal, July 2012

  • Landon, James; Demeter, Ethan; İnoğlu, Nilay
  • ACS Catalysis, Vol. 2, Issue 8
  • DOI: 10.1021/cs3002644

Non-nitrogen doped and non-metal oxygen reduction electrocatalysts based on carbon nanotubes: mechanism and origin of ORR activity
journal, January 2014

  • Waki, Keiko; Wong, Raymond A.; Oktaviano, Haryo S.
  • Energy Environ. Sci., Vol. 7, Issue 6
  • DOI: 10.1039/C3EE43743D

Synthesis of Nitrogen-Doped Graphene Using Embedded Carbon and Nitrogen Sources
journal, January 2011


Hierarchical N-Doped Carbon as CO 2 Adsorbent with High CO 2 Selectivity from Rationally Designed Polypyrrole Precursor
journal, January 2016

  • To, John W. F.; He, Jiajun; Mei, Jianguo
  • Journal of the American Chemical Society, Vol. 138, Issue 3
  • DOI: 10.1021/jacs.5b11955

Understanding the electrocatalysis of oxygen reduction on platinum and its alloys
journal, January 2012

  • Stephens, Ifan E. L.; Bondarenko, Alexander S.; Grønbjerg, Ulrik
  • Energy & Environmental Science, Vol. 5, Issue 5
  • DOI: 10.1039/c2ee03590a

Nanostructured materials for advanced energy conversion and storage devices
journal, May 2005

  • Aricò, Antonino Salvatore; Bruce, Peter; Scrosati, Bruno
  • Nature Materials, Vol. 4, Issue 5, p. 366-377
  • DOI: 10.1038/nmat1368

Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces
journal, February 2007

  • Stamenkovic, Vojislav R.; Mun, Bongjin Simon; Arenz, Matthias
  • Nature Materials, Vol. 6, Issue 3, p. 241-247
  • DOI: 10.1038/nmat1840

Evolution of nitrogen functionalities in carbonaceous materials during pyrolysis
journal, January 1995


Advanced Materials for Energy Storage
journal, February 2010


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

Polypyrrole-derived mesoporous nitrogen-doped carbons with intrinsic catalytic activity in the oxygen reduction reaction
journal, January 2013

  • Sevilla, Marta; Yu, Linghui; Fellinger, Tim Patrick
  • RSC Advances, Vol. 3, Issue 25
  • DOI: 10.1039/c3ra41719k

Universality in Oxygen Reduction Electrocatalysis on Metal Surfaces
journal, July 2012

  • Viswanathan, Venkatasubramanian; Hansen, Heine Anton; Rossmeisl, Jan
  • ACS Catalysis, Vol. 2, Issue 8
  • DOI: 10.1021/cs300227s

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

Graphene-Based Non-Noble-Metal Catalysts for Oxygen Reduction Reaction in Acid
journal, August 2011

  • Byon, Hye Ryung; Suntivich, Jin; Shao-Horn, Yang
  • Chemistry of Materials, Vol. 23, Issue 15, p. 3421-3428
  • DOI: 10.1021/cm2000649

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


Facile and Gram-scale Synthesis of Metal-free Catalysts: Toward Realistic Applications for Fuel Cells
journal, March 2015

  • Kim, Ok-Hee; Cho, Yong-Hun; Chung, Dong Young
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep08376

Nitrogen-doped carbon nanomaterials as non-metal electrocatalysts for water oxidation
journal, August 2013

  • Zhao, Yong; Nakamura, Ryuhei; Kamiya, Kazuhide
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3390

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