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

Title: Migration of Cobalt Species within Mixed Platinum-Cobalt Oxide Bifunctional Electrocatalysts in Alkaline Electrolytes

Abstract

Bifunctional oxygen electrocatalysts have significant potentials for energy storage and conversion applications. Here we report a facile strategy toward bifunctional electrocatalysts by supporting mixed platinum and cobalt oxide nanoparticles on carbon black. The composite electrocatalyst (denoted as Pt+CoOx/C) is found to exhibit higher oxygen evolution reaction (OER) activity than CoOx/C, but slightly lower oxygen reduction reaction (ORR) activity than Pt/C in alkaline electrolytes. The bifunctional catalytic performance is ascribed to the in situ formation of heterogenous platinum-cobalt (hydro)oxide (Pt-CoOxHy) interfaces under the electrochemical reaction conditions. Calculated electrochemical phase (Pourbaix) diagrams suggest that the migration of Co species was driven by the relative stability of Pt-CoOxHy interfaces versus bulk (hydroxy)oxides or aqueous ions of cobalt.

Authors:
 [1];  [2];  [3];  [1];  [1];  [3];  [2]; ORCiD logo [1]
  1. Johns Hopkins Univ., Baltimore, MD (United States)
  2. Purdue Univ., West Lafayette, IN (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1530404
Grant/Contract Number:  
SC0010379; EE0007270; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 166; Journal Issue: 7; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Electrocatalysis; cobalt; electrocatalyst; platinum

Citation Formats

Wang, Lei, Zeng, Zhenhua, Ma, Cheng, Xu, Fei, Giroux, Michael, Chi, Miaofang, Greeley, Jeffrey, and Wang, Chao. Migration of Cobalt Species within Mixed Platinum-Cobalt Oxide Bifunctional Electrocatalysts in Alkaline Electrolytes. United States: N. p., 2019. Web. doi:10.1149/2.0061907jes.
Wang, Lei, Zeng, Zhenhua, Ma, Cheng, Xu, Fei, Giroux, Michael, Chi, Miaofang, Greeley, Jeffrey, & Wang, Chao. Migration of Cobalt Species within Mixed Platinum-Cobalt Oxide Bifunctional Electrocatalysts in Alkaline Electrolytes. United States. doi:10.1149/2.0061907jes.
Wang, Lei, Zeng, Zhenhua, Ma, Cheng, Xu, Fei, Giroux, Michael, Chi, Miaofang, Greeley, Jeffrey, and Wang, Chao. Sat . "Migration of Cobalt Species within Mixed Platinum-Cobalt Oxide Bifunctional Electrocatalysts in Alkaline Electrolytes". United States. doi:10.1149/2.0061907jes. https://www.osti.gov/servlets/purl/1530404.
@article{osti_1530404,
title = {Migration of Cobalt Species within Mixed Platinum-Cobalt Oxide Bifunctional Electrocatalysts in Alkaline Electrolytes},
author = {Wang, Lei and Zeng, Zhenhua and Ma, Cheng and Xu, Fei and Giroux, Michael and Chi, Miaofang and Greeley, Jeffrey and Wang, Chao},
abstractNote = {Bifunctional oxygen electrocatalysts have significant potentials for energy storage and conversion applications. Here we report a facile strategy toward bifunctional electrocatalysts by supporting mixed platinum and cobalt oxide nanoparticles on carbon black. The composite electrocatalyst (denoted as Pt+CoOx/C) is found to exhibit higher oxygen evolution reaction (OER) activity than CoOx/C, but slightly lower oxygen reduction reaction (ORR) activity than Pt/C in alkaline electrolytes. The bifunctional catalytic performance is ascribed to the in situ formation of heterogenous platinum-cobalt (hydro)oxide (Pt-CoOxHy) interfaces under the electrochemical reaction conditions. Calculated electrochemical phase (Pourbaix) diagrams suggest that the migration of Co species was driven by the relative stability of Pt-CoOxHy interfaces versus bulk (hydroxy)oxides or aqueous ions of cobalt.},
doi = {10.1149/2.0061907jes},
journal = {Journal of the Electrochemical Society},
number = 7,
volume = 166,
place = {United States},
year = {2019},
month = {3}
}

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

Figures / Tables:

Figure 1 Figure 1: (a) ORR and OER polarization curves recorded for the Pt/C, CoOx/C and Pt+CoOx/C catalysts in 0.1 M KOH. (b) Summary of the bifunctional catalytic activities, represented as the current density (J) at 1.6 V for the OER and the half-wave potential (E1/2) for the ORR. (c) ORR andmore » OER galvanostatic curves recorded at a current density of 5 mA/cm2 for the Pt/C and Pt+CoOx/C catalysts over a period of 1 hour in 0.1 M KOH. (d) Summary of the initial and final potential gaps between the ORR and OER galvanostatic curves as shown in (c).« less

Save / Share:

Works referenced in this record:

A review on unitized regenerative fuel cell technologies, part-A: Unitized regenerative proton exchange membrane fuel cells
journal, November 2016


A review of unitized regenerative fuel cell stack: Material, design and research achievements
journal, October 2014

  • Gabbasa, Mohamed; Sopian, Kamaruzzaman; Fudholi, Ahmad
  • International Journal of Hydrogen Energy, Vol. 39, Issue 31
  • DOI: 10.1016/j.ijhydene.2014.08.121

Oxygen electrocatalysts in metal–air batteries: from aqueous to nonaqueous electrolytes
journal, January 2014

  • Wang, Zhong-Li; Xu, Dan; Xu, Ji-Jing
  • Chem. Soc. Rev., Vol. 43, Issue 22
  • DOI: 10.1039/C3CS60248F

Recent progress and perspectives on bi-functional oxygen electrocatalysts for advanced rechargeable metal–air batteries
journal, January 2016

  • Lee, Dong Un; Xu, Pan; Cano, Zachary P.
  • Journal of Materials Chemistry A, Vol. 4, Issue 19
  • DOI: 10.1039/C6TA00173D

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

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

Development of Supported Bifunctional Electrocatalysts for Unitized Regenerative Fuel Cells
journal, January 2002

  • Chen, Guoying; Bare, Simon R.; Mallouk, Thomas E.
  • Journal of The Electrochemical Society, Vol. 149, Issue 8
  • DOI: 10.1149/1.1491237

A review of the latest developments in electrodes for unitised regenerative polymer electrolyte fuel cells
journal, June 2006


Iridium Oxide/Platinum Electrocatalysts for Unitized Regenerative Polymer Electrolyte Fuel Cells
journal, January 2000

  • Ioroi, Tsutomu; Kitazawa, Naohisa; Yasuda, Kazuaki
  • Journal of The Electrochemical Society, Vol. 147, Issue 6
  • DOI: 10.1149/1.1393478

Activity and Stability of Pt/IrO 2 Bifunctional Materials as Catalysts for the Oxygen Evolution/Reduction Reactions
journal, January 2018

  • da Silva, Gabriel C.; Fernandes, Mauro R.; Ticianelli, Edson A.
  • ACS Catalysis, Vol. 8, Issue 3
  • DOI: 10.1021/acscatal.7b03429

Compositional segregation in shaped Pt alloy nanoparticles and their structural behaviour during electrocatalysis
journal, June 2013

  • Cui, Chunhua; Gan, Lin; Heggen, Marc
  • Nature Materials, Vol. 12, Issue 8
  • DOI: 10.1038/nmat3668

Electrochemical dissolution of surface alloys in acids: Thermodynamic trends from first-principles calculations
journal, May 2007


Correlation Between Surface Chemistry and Electrocatalytic Properties of Monodisperse PtxNi1-x Nanoparticles
journal, November 2010

  • Wang, Chao; Chi, Miaofang; Wang, Guofeng
  • Advanced Functional Materials, Vol. 21, Issue 1, p. 147-152
  • DOI: 10.1002/adfm.201001138

Benchmarking the Stability of Oxygen Evolution Reaction Catalysts: The Importance of Monitoring Mass Losses
journal, October 2014

  • Frydendal, Rasmus; Paoli, Elisa A.; Knudsen, Brian P.
  • ChemElectroChem, Vol. 1, Issue 12
  • DOI: 10.1002/celc.201402262

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

Co3O4 nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction
journal, August 2011

  • Liang, Yongye; Li, Yanguang; Wang, Hailiang
  • Nature Materials, Vol. 10, Issue 10, p. 780-786
  • DOI: 10.1038/nmat3087

Advanced zinc-air batteries based on high-performance hybrid electrocatalysts
journal, May 2013

  • Li, Yanguang; Gong, Ming; Liang, Yongye
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms2812

Spinel Mn–Co Oxide in N-Doped Carbon Nanotubes as a Bifunctional Electrocatalyst Synthesized by Oxidative Cutting
journal, May 2014

  • Zhao, Anqi; Masa, Justus; Xia, Wei
  • Journal of the American Chemical Society, Vol. 136, Issue 21
  • DOI: 10.1021/ja502532y

Projector augmented-wave method
journal, December 1994


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Towards First Principles-Based Prediction of Highly Accurate Electrochemical Pourbaix Diagrams
journal, July 2015

  • Zeng, Zhenhua; Chan, Maria K. Y.; Zhao, Zhi-Jian
  • The Journal of Physical Chemistry C, Vol. 119, Issue 32
  • DOI: 10.1021/acs.jpcc.5b03169

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

  • Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
  • Physical Review B, Vol. 57, Issue 3, p. 1505-1509
  • DOI: 10.1103/PhysRevB.57.1505

Surface Pourbaix diagrams and oxygen reduction activity of Pt, Ag and Ni(111) surfaces studied by DFT
journal, January 2008

  • Hansen, Heine A.; Rossmeisl, Jan; Nørskov, Jens K.
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 25
  • DOI: 10.1039/b803956a

Generalized trends in the formation energies of perovskite oxides
journal, January 2013

  • Zeng, ZhenHua; Calle-Vallejo, Federico; Mogensen, Mogens B.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 20
  • DOI: 10.1039/c3cp50257k

Stabilization of ultrathin (hydroxy)oxide films on transition metal substrates for electrochemical energy conversion
journal, May 2017


Platinum-nickel hydroxide nanocomposites for electrocatalytic reduction of water
journal, January 2017


Surfactant Removal for Colloidal Nanoparticles from Solution Synthesis: The Effect on Catalytic Performance
journal, June 2012

  • Li, Dongguo; Wang, Chao; Tripkovic, Dusan
  • ACS Catalysis, Vol. 2, Issue 7
  • DOI: 10.1021/cs300219j

Surface science studies of model fuel cell electrocatalysts
journal, April 2002


On the chemical state of Co oxide electrocatalysts during alkaline water splitting
journal, January 2013

  • Friebel, Daniel; Bajdich, Michal; Yeo, Boon Siang
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 40
  • DOI: 10.1039/c3cp52981a

Reversible amorphization and the catalytically active state of crystalline Co3O4 during oxygen evolution
journal, October 2015

  • Bergmann, Arno; Martinez-Moreno, Elias; Teschner, Detre
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9625

Dynamic surface self-reconstruction is the key of highly active perovskite nano-electrocatalysts for water splitting
journal, July 2017

  • Fabbri, Emiliana; Nachtegaal, Maarten; Binninger, Tobias
  • Nature Materials, Vol. 16, Issue 9
  • DOI: 10.1038/nmat4938

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

In Situ Co K-Edge X-Ray Absorption Fine Structure of Cobalt Hydroxide Film Electrodes in Alkaline Solutions
journal, January 2000

  • Totir, Dana; Mo, Yibo; Kim, Sunghyun
  • Journal of The Electrochemical Society, Vol. 147, Issue 12
  • DOI: 10.1149/1.1394107

Anodic oxidation of cobalt in potassium hydroxide electrolytes
journal, June 1971

  • Behl, Wishvender K.; Toni, Jorge E.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 31, Issue 1
  • DOI: 10.1016/S0022-0728(71)80043-8

Theoretical Investigation of the Activity of Cobalt Oxides for the Electrochemical Oxidation of Water
journal, August 2013

  • Bajdich, Michal; García-Mota, Mónica; Vojvodic, Aleksandra
  • Journal of the American Chemical Society, Vol. 135, Issue 36
  • DOI: 10.1021/ja405997s

The Solubility of Cobalt Hydroxide, Co(OH) 2 , in Solutions of Hydrochloric Acid and Sodium Hydroxide at 25°
journal, September 1950

  • Gayer, Karl H.; Garrett, A. B.
  • Journal of the American Chemical Society, Vol. 72, Issue 9
  • DOI: 10.1021/ja01165a024

New insight in the behaviour of Co–H2O system at 25–150°C, based on revised Pourbaix diagrams
journal, January 2008


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