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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 Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and 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. https://doi.org/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. https://doi.org/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}
}

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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

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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

The road from animal electricity to green energy: combining experiment and theory in electrocatalysis
journal, January 2012

  • Greeley, Jeffrey; Markovic, Nenad M.
  • Energy & Environmental Science, Vol. 5, Issue 11
  • DOI: 10.1039/c2ee21754f

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

Van der Waals density functionals applied to solids
journal, May 2011


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


Voltage- and time-dependent valence state transition in cobalt oxide catalysts during the oxygen evolution reaction
journal, April 2020


Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets
journal, May 2021


High-resolution X-ray luminescence extension imaging
journal, February 2021


Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect
journal, February 2020


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