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Title: A Stable Graphitic, Nanocarbon-Encapsulated, Cobalt-Rich Core-Shell Electrocatalyst as an Oxygen Electrode in a Water Electrolyzer

Abstract

The oxygen electrode plays a vital role in the successful commercialization of renewable energy technologies, such as fuel cells and water electrolyzers. In this study, the Prussian blue analogue-derived nitrogen-doped nanocarbon (NC) layer-trapped, cobalt-rich, core–shell nanostructured electrocatalysts (core–shell Co@NC) are reported. The electrode exhibits an improved oxygen evolution activity and stability compared to that of the commercial noble electrodes. The core–shell Co@NC-loaded nickel foam exhibits a lower overpotential of 330 mV than that of IrO2 on nickel foam at 10 mA cm-2 and has a durability of over 400 h. The commercial Pt/C cathode-assisted, core–shell Co@NC–anode water electrolyzer delivers 10 mA cm-2 at a cell voltage of 1.59 V, which is 70 mV lower than that of the IrO2–anode water electrolyzer. Over the long-term chronopotentiometry durability testing, the IrO2–anode water electrolyzer shows a cell voltage loss of 230 mV (14%) at 95 h, but the loss of the core–shell Co@NC–anode electrolyzer is only 60 mV (4%) even after 350 h cell-operation. The findings indicate that the Prussian blue analogue is a class of inorganic nanoporous materials that can be used to derive metal-rich, core–shell electrocatalysts with enriched active centers.

Authors:
 [1];  [1];  [2];  [2];  [2]; ORCiD logo [1]
  1. Department of Energy Science & Engineering, Daegu Gyeongbuk Institute of Science & Technology (DGIST), Daegu 42988 Republic of Korea
  2. Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1439684
Report Number(s):
PNNL-SA-127978
Journal ID: ISSN 1614-6832; GT0200000
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 8; Journal Issue: 14; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English

Citation Formats

Sivanantham, Arumugam, Ganesan, Pandian, Estevez, Luis, McGrail, B. Peter, Motkuri, Radha Kishan, and Shanmugam, Sangaraju. A Stable Graphitic, Nanocarbon-Encapsulated, Cobalt-Rich Core-Shell Electrocatalyst as an Oxygen Electrode in a Water Electrolyzer. United States: N. p., 2018. Web. doi:10.1002/aenm.201702838.
Sivanantham, Arumugam, Ganesan, Pandian, Estevez, Luis, McGrail, B. Peter, Motkuri, Radha Kishan, & Shanmugam, Sangaraju. A Stable Graphitic, Nanocarbon-Encapsulated, Cobalt-Rich Core-Shell Electrocatalyst as an Oxygen Electrode in a Water Electrolyzer. United States. doi:10.1002/aenm.201702838.
Sivanantham, Arumugam, Ganesan, Pandian, Estevez, Luis, McGrail, B. Peter, Motkuri, Radha Kishan, and Shanmugam, Sangaraju. Thu . "A Stable Graphitic, Nanocarbon-Encapsulated, Cobalt-Rich Core-Shell Electrocatalyst as an Oxygen Electrode in a Water Electrolyzer". United States. doi:10.1002/aenm.201702838.
@article{osti_1439684,
title = {A Stable Graphitic, Nanocarbon-Encapsulated, Cobalt-Rich Core-Shell Electrocatalyst as an Oxygen Electrode in a Water Electrolyzer},
author = {Sivanantham, Arumugam and Ganesan, Pandian and Estevez, Luis and McGrail, B. Peter and Motkuri, Radha Kishan and Shanmugam, Sangaraju},
abstractNote = {The oxygen electrode plays a vital role in the successful commercialization of renewable energy technologies, such as fuel cells and water electrolyzers. In this study, the Prussian blue analogue-derived nitrogen-doped nanocarbon (NC) layer-trapped, cobalt-rich, core–shell nanostructured electrocatalysts (core–shell Co@NC) are reported. The electrode exhibits an improved oxygen evolution activity and stability compared to that of the commercial noble electrodes. The core–shell Co@NC-loaded nickel foam exhibits a lower overpotential of 330 mV than that of IrO2 on nickel foam at 10 mA cm-2 and has a durability of over 400 h. The commercial Pt/C cathode-assisted, core–shell Co@NC–anode water electrolyzer delivers 10 mA cm-2 at a cell voltage of 1.59 V, which is 70 mV lower than that of the IrO2–anode water electrolyzer. Over the long-term chronopotentiometry durability testing, the IrO2–anode water electrolyzer shows a cell voltage loss of 230 mV (14%) at 95 h, but the loss of the core–shell Co@NC–anode electrolyzer is only 60 mV (4%) even after 350 h cell-operation. The findings indicate that the Prussian blue analogue is a class of inorganic nanoporous materials that can be used to derive metal-rich, core–shell electrocatalysts with enriched active centers.},
doi = {10.1002/aenm.201702838},
journal = {Advanced Energy Materials},
issn = {1614-6832},
number = 14,
volume = 8,
place = {United States},
year = {2018},
month = {1}
}

Works referenced in this record:

Carbonized Nanoscale Metal–Organic Frameworks as High Performance Electrocatalyst for Oxygen Reduction Reaction
journal, November 2014

  • Zhao, Shenlong; Yin, Huajie; Du, Lei
  • ACS Nano, Vol. 8, Issue 12
  • DOI: 10.1021/nn505582e

Metal–Organic Frameworks for Electrocatalytic Reduction of Carbon Dioxide
journal, October 2015

  • Kornienko, Nikolay; Zhao, Yingbo; Kley, Christopher S.
  • Journal of the American Chemical Society, Vol. 137, Issue 44
  • DOI: 10.1021/jacs.5b08212

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

Hierarchical NiCo 2 S 4 Nanowire Arrays Supported on Ni Foam: An Efficient and Durable Bifunctional Electrocatalyst for Oxygen and Hydrogen Evolution Reactions
journal, April 2016

  • Sivanantham, Arumugam; Ganesan, Pandian; Shanmugam, Sangaraju
  • Advanced Functional Materials, Vol. 26, Issue 26
  • DOI: 10.1002/adfm.201600566

Hydrogen Storage in the Dehydrated Prussian Blue Analogues M 3 [Co(CN) 6 ] 2 (M = Mn, Fe, Co, Ni, Cu, Zn)
journal, May 2005

  • Kaye, Steven S.; Long, Jeffrey R.
  • Journal of the American Chemical Society, Vol. 127, Issue 18
  • DOI: 10.1021/ja051168t

Coupling multiphase-Fe and hierarchical N-doped graphitic carbon as trifunctional electrocatalysts by supramolecular preorganization of precursors
journal, January 2017

  • Zhou, Zhixin; He, Fei; Shen, Yanfei
  • Chemical Communications, Vol. 53, Issue 12
  • DOI: 10.1039/C6CC09442B

Pore-Engineered Metal–Organic Frameworks with Excellent Adsorption of Water and Fluorocarbon Refrigerant for Cooling Applications
journal, July 2017

  • Zheng, Jian; Vemuri, Rama S.; Estevez, Luis
  • Journal of the American Chemical Society, Vol. 139, Issue 31
  • DOI: 10.1021/jacs.7b04872

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


Nitrogen-Doped Graphene on Transition Metal Substrates as Efficient Bifunctional Catalysts for Oxygen Reduction and Oxygen Evolution Reactions
journal, June 2017

  • Zhou, Si; Liu, Nanshu; Wang, Zhiyu
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 27
  • DOI: 10.1021/acsami.7b05755

Inexpensive electrochemical synthesis of nickel iron sulphides on nickel foam: super active and ultra-durable electrocatalysts for alkaline electrolyte membrane water electrolysis
journal, January 2016

  • Ganesan, Pandian; Sivanantham, Arumugam; Shanmugam, Sangaraju
  • Journal of Materials Chemistry A, Vol. 4, Issue 42
  • DOI: 10.1039/C6TA04499A

Recent Progress in Metal-Organic Frameworks for Applications in Electrocatalytic and Photocatalytic Water Splitting
journal, January 2017


Au/Ni12P5 core/shell single-crystal nanoparticles as oxygen evolution reaction catalyst
journal, April 2017


Interaction of Cobalt Nanoparticles with Oxygen- and Nitrogen-Functionalized Carbon Nanotubes and Impact on Nitrobenzene Hydrogenation Catalysis
journal, April 2014

  • Chen, Peirong; Yang, Fengkai; Kostka, Aleksander
  • ACS Catalysis, Vol. 4, Issue 5
  • DOI: 10.1021/cs500173t

Metal–Organic Framework Thin Films as Platforms for Atomic Layer Deposition of Cobalt Ions To Enable Electrocatalytic Water Oxidation
journal, December 2015

  • Kung, Chung-Wei; Mondloch, Joseph E.; Wang, Timothy C.
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 51
  • DOI: 10.1021/acsami.5b06901

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

First-Principles Design of Graphene-Based Active Catalysts for Oxygen Reduction and Evolution Reactions in the Aprotic Li–O2 Battery
journal, June 2016

  • Kang, Joonhee; Yu, Jong-Sung; Han, Byungchan
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 14, p. 2803-2808
  • DOI: 10.1021/acs.jpclett.6b01071

Mesoporous Metal–Nitrogen-Doped Carbon Electrocatalysts for Highly Efficient Oxygen Reduction Reaction
journal, October 2013

  • Liang, Hai-Wei; Wei, Wei; Wu, Zhong-Shuai
  • Journal of the American Chemical Society, Vol. 135, Issue 43
  • DOI: 10.1021/ja407552k

Cover Picture: Asymmetric Catalytic Aza-Diels-Alder/Ring-Closing Cascade Reaction Forming Bicyclic Azaheterocycles by Trienamine Catalysis (Chem. Eur. J. 1/2017)
journal, December 2016

  • Li, Yang; Barløse, Casper; Jørgensen, Julie
  • Chemistry - A European Journal, Vol. 23, Issue 1
  • DOI: 10.1002/chem.201605561

Nanocarbon Electrocatalysts for Oxygen Reduction in Alkaline Media for Advanced Energy Conversion and Storage
journal, January 2014


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

Enhancing Activity for the Oxygen Evolution Reaction: The Beneficial Interaction of Gold with Manganese and Cobalt Oxides
journal, November 2014


A highly active and stable IrO x /SrIrO 3 catalyst for the oxygen evolution reaction
journal, September 2016


Highly Active and Durable Non-Precious Metal Catalyst for the Oxygen Reduction Reaction in Acidic Medium
journal, January 2016

  • Karthikayini, M. P.; Thirupathi, T.; Wang, Guanxiong
  • Journal of The Electrochemical Society, Vol. 163, Issue 6
  • DOI: 10.1149/2.1001606jes

Metal-Organic-Framework-Derived Hybrid Carbon Nanocages as a Bifunctional Electrocatalyst for Oxygen Reduction and Evolution
journal, June 2017


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

Interfacial Charge Carrier Dynamics in Core−Shell Au-CdS Nanocrystals
journal, June 2010

  • Yang, Ting-Ting; Chen, Wei-Ta; Hsu, Yung-Jung
  • The Journal of Physical Chemistry C, Vol. 114, Issue 26
  • DOI: 10.1021/jp103294c

Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds
journal, November 2010

  • Cook, Timothy R.; Dogutan, Dilek K.; Reece, Steven Y.
  • Chemical Reviews, Vol. 110, Issue 11
  • DOI: 10.1021/cr100246c

XPS analysis of new lithium cobalt oxide thin-films before and after lithium deintercalation
journal, March 2001


Redox and electrochemical water splitting catalytic properties of hydrated metal oxide modified electrodes
journal, January 2013

  • Doyle, Richard L.; Godwin, Ian J.; Brandon, Michael P.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 33
  • DOI: 10.1039/c3cp51213d

Single layer graphene encapsulating non-precious metals as high-performance electrocatalysts for water oxidation
journal, January 2016

  • Cui, Xiaoju; Ren, Pengju; Deng, Dehui
  • Energy & Environmental Science, Vol. 9, Issue 1
  • DOI: 10.1039/C5EE03316K

Prussian Blue Analogues for CO2 and SO2 Capture and Separation Applications
journal, June 2010

  • Thallapally, Praveen K.; Motkuri, Radha Kishan; Fernandez, Carlos A.
  • Inorganic Chemistry, Vol. 49, Issue 11, p. 4909-4915
  • DOI: 10.1021/ic902397w

MOF-derived self-assembled ZnO/Co 3 O 4 nanocomposite clusters as high-performance anodes for lithium-ion batteries
journal, January 2015

  • Zhu, Dequan; Zheng, Fangcai; Xu, Shihao
  • Dalton Transactions, Vol. 44, Issue 38
  • DOI: 10.1039/C5DT02271A

Ni 3 Fe-N Doped Carbon Sheets as a Bifunctional Electrocatalyst for Air Cathodes
journal, September 2016

  • Fu, Gengtao; Cui, Zhiming; Chen, Yifan
  • Advanced Energy Materials, Vol. 7, Issue 1
  • DOI: 10.1002/aenm.201601172

Fluorocarbon adsorption in hierarchical porous frameworks
journal, July 2014

  • Motkuri, Radha Kishan; Annapureddy, Harsha V. R.; Vijaykumar, M.
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5368

Cobalt nanoparticles encapsulated in nitrogen-doped carbon as a bifunctional catalyst for water electrolysis
journal, January 2014

  • Wang, Jing; Gao, Dunfeng; Wang, Guoxiong
  • J. Mater. Chem. A, Vol. 2, Issue 47
  • DOI: 10.1039/C4TA04337E

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

Iron Encapsulated within Pod-like Carbon Nanotubes for Oxygen Reduction Reaction
journal, December 2012

  • Deng, Dehui; Yu, Liang; Chen, Xiaoqi
  • Angewandte Chemie International Edition, Vol. 52, Issue 1
  • DOI: 10.1002/anie.201204958

Facile Synthesis of Surfactant-Free Au Cluster/Graphene Hybrids for High-Performance Oxygen Reduction Reaction
journal, August 2012

  • Yin, Huajie; Tang, Hongjie; Wang, Dan
  • ACS Nano, Vol. 6, Issue 9
  • DOI: 10.1021/nn302984x

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

Trends in activity for the water electrolyser reactions on 3d M(Ni,Co,Fe,Mn) hydr(oxy)oxide catalysts
journal, May 2012

  • Subbaraman, Ram; Tripkovic, Dusan; Chang, Kee-Chul
  • Nature Materials, Vol. 11, Issue 6
  • DOI: 10.1038/nmat3313

Bi-Functional Iron-Only Electrodes for Efficient Water Splitting with Enhanced Stability through In Situ Electrochemical Regeneration
journal, December 2015

  • Martindale, Benjamin C. M.; Reisner, Erwin
  • Advanced Energy Materials, Vol. 6, Issue 6
  • DOI: 10.1002/aenm.201502095

Spinel-type lithium cobalt oxide as a bifunctional electrocatalyst for the oxygen evolution and oxygen reduction reactions
journal, May 2014

  • Maiyalagan, Thandavarayan; Jarvis, Karalee A.; Therese, Soosairaj
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4949

Bimetallic Metal-Organic Frameworks for Controlled Catalytic Graphitization of Nanoporous Carbons
journal, July 2016

  • Tang, Jing; Salunkhe, Rahul R.; Zhang, Huabin
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep30295

Ultrathin metal–organic framework nanosheets for electrocatalytic oxygen evolution
journal, November 2016


“Metal-Free” Catalytic Oxygen Reduction Reaction on Heteroatom-Doped Graphene is Caused by Trace Metal Impurities
journal, November 2013

  • Wang, Lu; Ambrosi, Adriano; Pumera, Martin
  • Angewandte Chemie International Edition, Vol. 52, Issue 51
  • DOI: 10.1002/anie.201309171

Probing the Metal-Support Interaction in Carbon-Supported Catalysts by using Electron Microscopy
journal, October 2015


Metal-organic frameworks: Evolved oxygen evolution catalysts
journal, November 2016


Activation of surface oxygen sites on an iridium-based model catalyst for the oxygen evolution reaction
journal, December 2016

  • Grimaud, Alexis; Demortière, Arnaud; Saubanère, Matthieu
  • Nature Energy, Vol. 2, Issue 1
  • DOI: 10.1038/nenergy.2016.189

New Heterometallic Zirconium Metalloporphyrin Frameworks and Their Heteroatom-Activated High-Surface-Area Carbon Derivatives
journal, February 2015

  • Lin, Qipu; Bu, Xianhui; Kong, Aiguo
  • Journal of the American Chemical Society, Vol. 137, Issue 6
  • DOI: 10.1021/jacs.5b00076

Stability investigations of electrocatalysts on the nanoscale
journal, January 2012

  • Meier, Josef C.; Katsounaros, Ioannis; Galeano, Carolina
  • Energy & Environmental Science, Vol. 5, Issue 11
  • DOI: 10.1039/c2ee22550f

Metallic Cobalt@Nitrogen-Doped Carbon Nanocomposites: Carbon-Shell Regulation toward Efficient Bi-Functional Electrocatalysis
journal, October 2017

  • Mo, Qijie; Chen, Nana; Deng, Mengdie
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 43
  • DOI: 10.1021/acsami.7b10853

Metal-semiconductor-transition observed in Bi 2 Ca(Sr, Ba) 2 Co 2 O 8+δ single crystals
journal, July 2014

  • Dong, Song-Tao; Zhang, Bin-Bin; Zhang, Lun-Yong
  • Applied Physics Letters, Vol. 105, Issue 4
  • DOI: 10.1063/1.4891845

NiFe-Based (Oxy)hydroxide Catalysts for Oxygen Evolution Reaction in Non-Acidic Electrolytes
journal, July 2016


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

Investigation of the Interactions and Bonding between Carbon and Group VIII Metals at the Atomic Scale
journal, February 2016

  • Zoberbier, Thilo; Chamberlain, Thomas W.; Biskupek, Johannes
  • Small, Vol. 12, Issue 12
  • DOI: 10.1002/smll.201502210

Carbon–metal nanosheets from the water–hexane interface
journal, January 2015

  • Hamoudi, Hicham
  • Journal of Materials Chemistry C, Vol. 3, Issue 15
  • DOI: 10.1039/C5TC00228A

Gold-supported cerium-doped NiOx catalysts for water oxidation
journal, April 2016

  • Ng, Jia Wei Desmond; García-Melchor, Max; Bajdich, Michal
  • Nature Energy, Vol. 1, Issue 5
  • DOI: 10.1038/nenergy.2016.53

Oxygen reduction reaction: A framework for success
journal, May 2016


Nickel selenide supported on nickel foam as an efficient and durable non-precious electrocatalyst for the alkaline water electrolysis
journal, April 2017


Highly active and durable non-precious-metal catalysts encapsulated in carbon nanotubes for hydrogen evolution reaction
journal, January 2014

  • Deng, Jiao; Ren, Pengju; Deng, Dehui
  • Energy Environ. Sci., Vol. 7, Issue 6
  • DOI: 10.1039/C4EE00370E

Cobalt Nanoparticles Embedded in Nitrogen-Doped Carbon for the Hydrogen Evolution Reaction
journal, April 2015

  • Fei, Huilong; Yang, Yang; Peng, Zhiwei
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 15
  • DOI: 10.1021/acsami.5b00652

Li–O2 and Li–S batteries with high energy storage
journal, January 2012

  • Bruce, Peter G.; Freunberger, Stefan A.; Hardwick, Laurence J.
  • Nature Materials, Vol. 11, Issue 1, p. 19-29
  • DOI: 10.1038/nmat3191

On the Electrolytic Stability of Iron-Nickel Oxides
journal, April 2017


Active Site Structures in Nitrogen-Doped Carbon-Supported Cobalt Catalysts for the Oxygen Reduction Reaction
journal, November 2016

  • Qian, Yingdan; Liu, Zheng; Zhang, Hui
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 48
  • DOI: 10.1021/acsami.6b11927

Influence of Particle Size Distribution on the Performance of Ionic Liquid-based Electrochemical Double Layer Capacitors
journal, February 2016

  • Rennie, Anthony J. R.; Martins, Vitor L.; Smith, Rachel M.
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep22062