DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: The Roles of Oxide Growth and Sub-Surface Facets in Oxygen Evolution Activity of Iridium and Its Impact on Electrolysis

Abstract

This paper combines density functional theory calculations and electrochemical testing to study activity differences among iridium (Ir) surfaces in the oxygen evolution reaction. Ir metal/hydroxide is significantly more active than Ir oxide, which may be due to oxide skins at the surface weakening O-binding relative to pure metal or oxide surfaces. Here we report a disparity in activity between Ir and Ir oxide in half-cells not observed in single-cells. Extended operation at elevated temperature and potential were found to result in oxide growth, limiting how surface differences affect electrolyzer performance. Comparisons of half- and single-cell testing were used to assess how well rotating disk electrode testing predicts membrane electrode assembly performance and durability. Although oxygen evolution activities in half-cells can translate to single-cells, standard rotating disk electrode test procedures can exaggerate the activity benefit of a metal/hydroxide surface relative to membrane electrode assembly performance under typical operating conditions; it also appears that a half-cell test cannot reasonably accelerate activity loss from continual operation. While a variety of novel catalyst approaches, including alloying, faceting, morphology, and supports can improve oxygen evolution kinetics, these results suggest that Ir surfaces at different oxide states may struggle to improve performance at the device level.

Authors:
ORCiD logo [1];  [1];  [1];  [2]; ORCiD logo [2]; ORCiD logo [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. Colorado School of Mines, Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office
OSTI Identifier:
1580496
Report Number(s):
NREL/JA-5900-75286
Journal ID: ISSN 0013-4651; TRN: US2102319
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 166; Journal Issue: 15; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; electrocatalysis; electrode kinetics; energy conversion

Citation Formats

Alia, Shaun M., Ha, Mai-Anh, Anderson, Grace C., Ngo, Chilan, Pylypenko, Svitlana, and Larsen, Ross E. The Roles of Oxide Growth and Sub-Surface Facets in Oxygen Evolution Activity of Iridium and Its Impact on Electrolysis. United States: N. p., 2019. Web. doi:10.1149/2.0771915jes.
Alia, Shaun M., Ha, Mai-Anh, Anderson, Grace C., Ngo, Chilan, Pylypenko, Svitlana, & Larsen, Ross E. The Roles of Oxide Growth and Sub-Surface Facets in Oxygen Evolution Activity of Iridium and Its Impact on Electrolysis. United States. https://doi.org/10.1149/2.0771915jes
Alia, Shaun M., Ha, Mai-Anh, Anderson, Grace C., Ngo, Chilan, Pylypenko, Svitlana, and Larsen, Ross E. Wed . "The Roles of Oxide Growth and Sub-Surface Facets in Oxygen Evolution Activity of Iridium and Its Impact on Electrolysis". United States. https://doi.org/10.1149/2.0771915jes. https://www.osti.gov/servlets/purl/1580496.
@article{osti_1580496,
title = {The Roles of Oxide Growth and Sub-Surface Facets in Oxygen Evolution Activity of Iridium and Its Impact on Electrolysis},
author = {Alia, Shaun M. and Ha, Mai-Anh and Anderson, Grace C. and Ngo, Chilan and Pylypenko, Svitlana and Larsen, Ross E.},
abstractNote = {This paper combines density functional theory calculations and electrochemical testing to study activity differences among iridium (Ir) surfaces in the oxygen evolution reaction. Ir metal/hydroxide is significantly more active than Ir oxide, which may be due to oxide skins at the surface weakening O-binding relative to pure metal or oxide surfaces. Here we report a disparity in activity between Ir and Ir oxide in half-cells not observed in single-cells. Extended operation at elevated temperature and potential were found to result in oxide growth, limiting how surface differences affect electrolyzer performance. Comparisons of half- and single-cell testing were used to assess how well rotating disk electrode testing predicts membrane electrode assembly performance and durability. Although oxygen evolution activities in half-cells can translate to single-cells, standard rotating disk electrode test procedures can exaggerate the activity benefit of a metal/hydroxide surface relative to membrane electrode assembly performance under typical operating conditions; it also appears that a half-cell test cannot reasonably accelerate activity loss from continual operation. While a variety of novel catalyst approaches, including alloying, faceting, morphology, and supports can improve oxygen evolution kinetics, these results suggest that Ir surfaces at different oxide states may struggle to improve performance at the device level.},
doi = {10.1149/2.0771915jes},
journal = {Journal of the Electrochemical Society},
number = 15,
volume = 166,
place = {United States},
year = {Wed Nov 20 00:00:00 EST 2019},
month = {Wed Nov 20 00:00:00 EST 2019}
}

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

Citation Metrics:
Cited by: 19 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Amorphous-nonmetal—to—crystalline-metal transition in electrochromic iridium oxide films
journal, July 1982


Easily prepared, high activity Ir–Ni oxide catalysts for water oxidation
journal, November 2015


An efficiently tuned d-orbital occupation of IrO 2 by doping with Cu for enhancing the oxygen evolution reaction activity
journal, January 2015

  • Sun, Wei; Song, Ya; Gong, Xue-Qing
  • Chemical Science, Vol. 6, Issue 8
  • DOI: 10.1039/C5SC01251A

Highly textured nanostructure of pulsed laser deposited IrO 2 thin films as investigated by transmission electron microscopy
journal, August 2001

  • Serventi, A. M.; El Khakani, M. A.; Saint-Jacques, R. G.
  • Journal of Materials Research, Vol. 16, Issue 8
  • DOI: 10.1557/JMR.2001.0320

Self-Supported Hydrous Iridium–Nickel Oxide Two-Dimensional Nanoframes for High Activity Oxygen Evolution Electrocatalysts
journal, September 2018

  • Godínez-Salomón, Fernando; Albiter, Luis; Alia, Shaun M.
  • ACS Catalysis, Vol. 8, Issue 11
  • DOI: 10.1021/acscatal.8b02171

Finding Correlations of the Oxygen Reduction Reaction Activity of Transition Metal Catalysts with Parameters Obtained from Quantum Mechanics
journal, December 2013

  • Yu, Ted H.; Hofmann, Timo; Sha, Yao
  • The Journal of Physical Chemistry C, Vol. 117, Issue 50
  • DOI: 10.1021/jp4071554

Growth and termination of a rutile IrO2(100) layer on Ir(111)
journal, October 2016


Polyol Synthesis of Uniform Silver Nanowires:  A Plausible Growth Mechanism and the Supporting Evidence
journal, July 2003

  • Sun, Yugang; Mayers, Brian; Herricks, Thurston
  • Nano Letters, Vol. 3, Issue 7
  • DOI: 10.1021/nl034312m

Fe Oxides on Ag Surfaces: Structure and Reactivity
journal, September 2016


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


Electrochemical Equilibria
book, January 1973

  • Pourbaix, Marcel; Staehle, Roger W.; Pourbaix, Marcel
  • Lectures on Electrochemical Corrosion, p 83-183
  • DOI: 10.1007/978-1-4684-1806-4_4

Structural effects in electrocatalysis: oxygen reduction on platinum low index single-crystal surfaces in perchloric acid solutions
journal, October 1994

  • Marković, N. M.; Adžić, R. R.; Cahan, B. D.
  • Journal of Electroanalytical Chemistry, Vol. 377, Issue 1-2
  • DOI: 10.1016/0022-0728(94)03467-2

In situ observation of reactive oxygen species forming on oxygen-evolving iridium surfaces
journal, January 2017

  • Pfeifer, Verena; Jones, Travis E.; Velasco Vélez, Juan J.
  • Chemical Science, Vol. 8, Issue 3
  • DOI: 10.1039/C6SC04622C

Direct Visualization of Catalytically Active Sites at the FeO–Pt(111) Interface
journal, June 2015


A fast and robust algorithm for Bader decomposition of charge density
journal, June 2006


Atomic-scale insights into surface species of electrocatalysts in three dimensions
journal, March 2018


Hydrogenation of CO 2 to Methanol: Importance of Metal–Oxide and Metal–Carbide Interfaces in the Activation of CO 2
journal, October 2015


Iridium Oxygen Evolution Activity and Durability Baselines in Rotating Disk Electrode Half-Cells
journal, January 2019

  • Alia, Shaun M.; Anderson, Grace C.
  • Journal of The Electrochemical Society, Vol. 166, Issue 4
  • DOI: 10.1149/2.0731904jes

Mercury Underpotential Deposition to Determine Iridium and Iridium Oxide Electrochemical Surface Areas
journal, January 2016

  • Alia, Shaun M.; Hurst, Katherine E.; Kocha, Shyam S.
  • Journal of The Electrochemical Society, Vol. 163, Issue 11
  • DOI: 10.1149/2.0071611jes

Towards accurate prediction of catalytic activity in IrO 2 nanoclusters via first principles-based variable charge force field
journal, January 2015

  • Sen, F. G.; Kinaci, A.; Narayanan, B.
  • Journal of Materials Chemistry A, Vol. 3, Issue 37
  • DOI: 10.1039/C5TA04678E

Hydrogen at Scale (H 2 @Scale): Key to a Clean, Economic, and Sustainable Energy System
journal, January 2018

  • Pivovar, Bryan; Rustagi, Neha; Satyapal, Sunita
  • The Electrochemical Society Interface, Vol. 27, Issue 1
  • DOI: 10.1149/2.F04181if

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


Deposition and Stripping Properties of Mercury on Iridium Electrodes
journal, January 1986

  • Kounaves, S. P.
  • Journal of The Electrochemical Society, Vol. 133, Issue 12
  • DOI: 10.1149/1.2108457

Structure–Property Relationship and Chemical Aspects of Oxide–Metal Hybrid Nanostructures
journal, December 2012

  • Surnev, Svetlozar; Fortunelli, Alessandro; Netzer, Falko P.
  • Chemical Reviews, Vol. 113, Issue 6
  • DOI: 10.1021/cr300307n

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


Oxidation of Ir(111): From O−Ir−O Trilayer to Bulk Oxide Formation
journal, July 2008

  • He, Y. B.; Stierle, A.; Li, W. X.
  • The Journal of Physical Chemistry C, Vol. 112, Issue 31
  • DOI: 10.1021/jp803607y

Pathways to ultra-low platinum group metal catalyst loading in proton exchange membrane electrolyzers
journal, March 2016


Electrocatalytic Oxygen Evolution Reaction (OER) on Ru, Ir, and Pt Catalysts: A Comparative Study of Nanoparticles and Bulk Materials
journal, July 2012

  • Reier, Tobias; Oezaslan, Mehtap; Strasser, Peter
  • ACS Catalysis, Vol. 2, Issue 8
  • DOI: 10.1021/cs3003098

Surface oxides of Ir(111) prepared by gas-phase oxygen atoms
journal, December 2012


Active, Simple Iridium–Copper Hydrous Oxide Electrocatalysts for Water Oxidation
journal, March 2017

  • Wang, Chao; Moghaddam, Reza B.; Bergens, Steven H.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 10
  • DOI: 10.1021/acs.jpcc.6b12164

Molecular Insight in Structure and Activity of Highly Efficient, Low-Ir Ir–Ni Oxide Catalysts for Electrochemical Water Splitting (OER)
journal, September 2015

  • Reier, Tobias; Pawolek, Zarina; Cherevko, Serhiy
  • Journal of the American Chemical Society, Vol. 137, Issue 40
  • DOI: 10.1021/jacs.5b07788

Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008


Oxidation State Changes and Structure of Electrochromic Iridium Oxide Films
journal, January 1980

  • McIntyre, J. D. E.
  • Journal of The Electrochemical Society, Vol. 127, Issue 6
  • DOI: 10.1149/1.2129868

Periodic DFT Study of Rutile IrO 2 : Surface Reactivity and Catechol Adsorption
journal, June 2017

  • Matz, Olivier; Calatayud, Monica
  • The Journal of Physical Chemistry C, Vol. 121, Issue 24
  • DOI: 10.1021/acs.jpcc.7b01990

Growth of Silver Nanowires from Solutions:  A Cyclic Penta-twinned-Crystal Growth Mechanism
journal, May 2005

  • Zhang, Shu-Hong; Jiang, Zhi-Yuan; Xie, Zhao-Xiong
  • The Journal of Physical Chemistry B, Vol. 109, Issue 19
  • DOI: 10.1021/jp0441036

Oxide-Supported IrNiO x Core-Shell Particles as Efficient, Cost-Effective, and Stable Catalysts for Electrochemical Water Splitting
journal, January 2015

  • Nong, Hong Nhan; Oh, Hyung-Suk; Reier, Tobias
  • Angewandte Chemie International Edition, Vol. 54, Issue 10
  • DOI: 10.1002/anie.201411072

Iridium-Based Nanowires as Highly Active, Oxygen Evolution Reaction Electrocatalysts
journal, January 2018


One-dimensional conductive IrO 2 nanocrystals
journal, April 2006


Metal supported oxide nanostructures: model systems for advanced catalysis
journal, September 2007


Activity and Durability of Iridium Nanoparticles in the Oxygen Evolution Reaction
journal, January 2016

  • Alia, Shaun M.; Rasimick, Brian; Ngo, Chilan
  • Journal of The Electrochemical Society, Vol. 163, Issue 11
  • DOI: 10.1149/2.0151611jes

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

Activity–Stability Trends for the Oxygen Evolution Reaction on Monometallic Oxides in Acidic Environments
journal, July 2014

  • Danilovic, Nemanja; Subbaraman, Ramachandran; Chang, Kee-Chul
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 14
  • DOI: 10.1021/jz501061n

Chemical Wave Patterns and Oxide Redistribution during Methanol Oxidation on a V-Oxide Promoted Rh(110) Surface
journal, March 2018

  • von Boehn, Bernhard; Imbihl, Ronald
  • The Journal of Physical Chemistry C, Vol. 122, Issue 24
  • DOI: 10.1021/acs.jpcc.8b00852

A Highly Active “NiO-on-Au” Surface Architecture for CO Oxidation
journal, July 2013

  • Xu, Xuejun; Fu, Qiang; Guo, Xiaoguang
  • ACS Catalysis, Vol. 3, Issue 8
  • DOI: 10.1021/cs400197t

Oxide-Supported IrNiO x Core-Shell Particles as Efficient, Cost-Effective, and Stable Catalysts for Electrochemical Water Splitting
journal, January 2015

  • Nong, Hong Nhan; Oh, Hyung-Suk; Reier, Tobias
  • Angewandte Chemie, Vol. 127, Issue 10
  • DOI: 10.1002/ange.201411072

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


Activity and Durability of Iridium Nanoparticles in the Oxygen Evolution Reaction
journal, September 2015


Fe Oxides on Ag Surfaces: Structure and Reactivity
text, January 2017

  • Shipilin, M.; Lundgren, E.; Gustafson, J.
  • Deutsches Elektronen-Synchrotron, DESY, Hamburg
  • DOI: 10.3204/pubdb-2016-04862