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Title: Elucidating the alkaline oxygen evolution reaction mechanism on platinum

Abstract

Understanding the interplay between surface chemistry, electronic structure, and reaction mechanism of the catalyst at the electrified solid/liquid interface will enable the design of more efficient materials systems for sustainable energy production. The substantial progress in operando characterization, particularly using synchrotron based X-ray spectroscopies, provides the unprecedented opportunity to uncover surface chemical and structural transformations under various (electro)chemical reaction environments. In this work, we study a polycrystalline platinum surface under oxygen evolution conditions in an alkaline electrolyte by means of ambient pressure X-ray photoelectron spectroscopy performed at the electrified solid/liquid interface. We elucidate previously inaccessible aspects of the surface chemistry and structure as a function of the applied potential, allowing us to propose a reaction mechanism for oxygen evolution on a platinum electrode in alkaline solutions.

Authors:
 [1];  [2];  [3]; ORCiD logo [3];  [4];  [5];  [6]; ORCiD logo [2]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source. Joint Center for Artificial Photosynthesis. Chemical Sciences Division
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source. Joint Center for Energy Storage Research
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis. Molecular Biophysics and Integrated Bioimaging Division
  6. Chinese Academy of Sciences (CAS), Shanghai (China). State Key Lab. of Functional Materials for Informatics. Shanghai Inst. of Microsystem and Information Technology; ShanghaiTech Univ. (China). Division of Condensed Matter Physics and Photon Science. School of Physical Science and Technology
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); LBNL Laboratory Directed Research and Development (LDRD) Program; National Natural Science Foundation of China (NNSFC)
OSTI Identifier:
1436336
Grant/Contract Number:  
AC02-05CH11231; SC0004993; 11227902
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 5; Journal Issue: 23; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Favaro, M., Valero-Vidal, C., Eichhorn, J., Toma, F. M., Ross, P. N., Yano, J., Liu, Z., and Crumlin, E. J. Elucidating the alkaline oxygen evolution reaction mechanism on platinum. United States: N. p., 2017. Web. doi:10.1039/c7ta00409e.
Favaro, M., Valero-Vidal, C., Eichhorn, J., Toma, F. M., Ross, P. N., Yano, J., Liu, Z., & Crumlin, E. J. Elucidating the alkaline oxygen evolution reaction mechanism on platinum. United States. doi:10.1039/c7ta00409e.
Favaro, M., Valero-Vidal, C., Eichhorn, J., Toma, F. M., Ross, P. N., Yano, J., Liu, Z., and Crumlin, E. J. Tue . "Elucidating the alkaline oxygen evolution reaction mechanism on platinum". United States. doi:10.1039/c7ta00409e. https://www.osti.gov/servlets/purl/1436336.
@article{osti_1436336,
title = {Elucidating the alkaline oxygen evolution reaction mechanism on platinum},
author = {Favaro, M. and Valero-Vidal, C. and Eichhorn, J. and Toma, F. M. and Ross, P. N. and Yano, J. and Liu, Z. and Crumlin, E. J.},
abstractNote = {Understanding the interplay between surface chemistry, electronic structure, and reaction mechanism of the catalyst at the electrified solid/liquid interface will enable the design of more efficient materials systems for sustainable energy production. The substantial progress in operando characterization, particularly using synchrotron based X-ray spectroscopies, provides the unprecedented opportunity to uncover surface chemical and structural transformations under various (electro)chemical reaction environments. In this work, we study a polycrystalline platinum surface under oxygen evolution conditions in an alkaline electrolyte by means of ambient pressure X-ray photoelectron spectroscopy performed at the electrified solid/liquid interface. We elucidate previously inaccessible aspects of the surface chemistry and structure as a function of the applied potential, allowing us to propose a reaction mechanism for oxygen evolution on a platinum electrode in alkaline solutions.},
doi = {10.1039/c7ta00409e},
journal = {Journal of Materials Chemistry. A},
number = 23,
volume = 5,
place = {United States},
year = {2017},
month = {3}
}

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Cited by: 15 works
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Works referenced in this record:

Operando Near Ambient Pressure XPS (NAP-XPS) Study of the Pt Electrochemical Oxidation in H 2 O and H 2 O/O 2 Ambients
journal, March 2016

  • Saveleva, Viktoriia A.; Papaefthimiou, Vasiliki; Daletou, Maria K.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 29
  • DOI: 10.1021/acs.jpcc.5b12410

Unique Activity of Platinum Adislands in the CO Electrooxidation Reaction
journal, November 2008

  • Strmcnik, Dusan S.; Tripkovic, Dusan V.; van der Vliet, Dennis
  • Journal of the American Chemical Society, Vol. 130, Issue 46
  • DOI: 10.1021/ja8032185

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

Powering the planet: Chemical challenges in solar energy utilization
journal, October 2006

  • Lewis, N. S.; Nocera, D. G.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735
  • DOI: 10.1073/pnas.0603395103

Thermodynamic explanation of the universal correlation between oxygen evolution activity and corrosion of oxide catalysts
journal, July 2015

  • Binninger, Tobias; Mohamed, Rhiyaad; Waltar, Kay
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep12167

In situ investigation of dissociation and migration phenomena at the Pt/electrolyte interface of an electrochemical cell
journal, January 2015

  • Law, Yeuk Ting; Zafeiratos, Spyridon; Neophytides, Stylianos G.
  • Chemical Science, Vol. 6, Issue 10
  • DOI: 10.1039/C5SC01421B

Interlayer Mass Transport in Homoepitaxial and Heteroepitaxial Metal Growth
journal, July 1995


The role of non-covalent interactions in electrocatalytic fuel-cell reactions on platinum
journal, August 2009

  • Strmcnik, D.; Kodama, K.; van der Vliet, D.
  • Nature Chemistry, Vol. 1, Issue 6
  • DOI: 10.1038/nchem.330

An Operando Investigation of (Ni–Fe–Co–Ce)O x System as Highly Efficient Electrocatalyst for Oxygen Evolution Reaction
journal, January 2017


Changes in the kinetics of the oxygen evolution reaction induced by oxide films at platinum electrodes
journal, September 1994


Mass-selected nanoparticles of PtxY as model catalysts for oxygen electroreduction
journal, July 2014

  • Hernandez-Fernandez, Patricia; Masini, Federico; McCarthy, David N.
  • Nature Chemistry, Vol. 6, Issue 8
  • DOI: 10.1038/nchem.2001

A multifunctional biphasic water splitting catalyst tailored for integration with high-performance semiconductor photoanodes
journal, November 2016

  • Yang, Jinhui; Cooper, Jason K.; Toma, Francesca M.
  • Nature Materials, Vol. 16, Issue 3
  • DOI: 10.1038/nmat4794

Element-specific anisotropic growth of shaped platinum alloy nanocrystals
journal, December 2014


The 16 and 18 electron rule in organometallic chemistry and homogeneous catalysis
journal, January 1972


The Study of Reactive Intermediates in Condensed Phases
journal, March 2016

  • Carpenter, Barry K.; Harvey, Jeremy N.; Orr-Ewing, Andrew J.
  • Journal of the American Chemical Society, Vol. 138, Issue 14
  • DOI: 10.1021/jacs.6b01761

X-ray spectroscopy of energy materials under in situ/operando conditions
journal, April 2015

  • Crumlin, Ethan J.; Liu, Zhi; Bluhm, Hendrik
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 200
  • DOI: 10.1016/j.elspec.2015.06.008

The Mechanism of Water Oxidation: From Electrolysis via Homogeneous to Biological Catalysis
journal, June 2010


Simulation of Electron Spectra for Surface Analysis (SESSA)for quantitative interpretation of (hard) X-ray photoelectron spectra(HAXPES)
journal, October 2013

  • Werner, Wolfgang S. M.; Smekal, Werner; Hisch, Thomas
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 190
  • DOI: 10.1016/j.elspec.2013.06.007

Oxygen Reduction on Platinum Low-Index Single-Crystal Surfaces in Alkaline Solution:  Rotating Ring Disk Pt( hkl ) Studies
journal, April 1996

  • Marković, Nenad M.; Gasteiger, Hubert A.; Ross, Philip N.
  • The Journal of Physical Chemistry, Vol. 100, Issue 16
  • DOI: 10.1021/jp9533382

Tuning the activity of Pt alloy electrocatalysts by means of the lanthanide contraction
journal, March 2016


Hydrogen Oxidation and Evolution Reaction Kinetics on Platinum: Acid vs Alkaline Electrolytes
journal, January 2010

  • Sheng, Wenchao; Gasteiger, Hubert A.; Shao-Horn, Yang
  • Journal of The Electrochemical Society, Vol. 157, Issue 11
  • DOI: 10.1149/1.3483106

Direct observation of the energetics at a semiconductor/liquid junction by operando X-ray photoelectron spectroscopy
journal, January 2015

  • Lichterman, Michael F.; Hu, Shu; Richter, Matthias H.
  • Energy & Environmental Science, Vol. 8, Issue 8
  • DOI: 10.1039/C5EE01014D

Kinetics of oxygen evolution and dissolution on platinum electrodes
journal, July 1966


Resolving overlapping peaks in ARXPS data: The effect of noise and fitting method
journal, January 2012

  • Muñoz-Flores, Jaime; Herrera-Gomez, Alberto
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 184, Issue 11-12
  • DOI: 10.1016/j.elspec.2011.08.004

Vibrational spectra of an oxidized platinum electrode
journal, January 1984


Electrochemical characteristics of nanostructured platinum electrodes – a cyclic voltammetry study
journal, January 2014

  • Daubinger, P.; Kieninger, J.; Unmüssig, T.
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 18
  • DOI: 10.1039/C4CP00342J

In Situ Study of the Gas-Phase Electrolysis of Water on Platinum by NAP-XPS
journal, September 2013

  • Arrigo, Rosa; Hävecker, Michael; Schuster, Manfred E.
  • Angewandte Chemie International Edition, Vol. 52, Issue 44
  • DOI: 10.1002/anie.201304765

The topological insulator in a fractal space
journal, June 2014

  • Song, Zhi-Gang; Zhang, Yan-Yang; Li, Shu-Shen
  • Applied Physics Letters, Vol. 104, Issue 23
  • DOI: 10.1063/1.4882166

Tuning the Activity of Pt(111) for Oxygen Electroreduction by Subsurface Alloying
journal, April 2011

  • Stephens, Ifan E. L.; Bondarenko, Alexander S.; Perez-Alonso, Francisco J.
  • Journal of the American Chemical Society, Vol. 133, Issue 14
  • DOI: 10.1021/ja111690g

Mechanistic insights into chemical and photochemical transformations of bismuth vanadate photoanodes
journal, July 2016

  • Toma, Francesca M.; Cooper, Jason K.; Kunzelmann, Viktoria
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12012

Unravelling the electrochemical double layer by direct probing of the solid/liquid interface
journal, August 2016

  • Favaro, Marco; Jeong, Beomgyun; Ross, Philip N.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12695

Study of hydroxyl formation on Pt(111) surface by EELS and low temperature reaction quenching
journal, April 1985


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

Mechanistic Studies of the Oxygen Evolution Reaction by a Cobalt-Phosphate Catalyst at Neutral pH
journal, November 2010

  • Surendranath, Yogesh; Kanan, Matthew W.; Nocera, Daniel G.
  • Journal of the American Chemical Society, Vol. 132, Issue 46
  • DOI: 10.1021/ja106102b

Will Solar-Driven Water-Splitting Devices See the Light of Day?
journal, September 2013

  • McKone, James R.; Lewis, Nathan S.; Gray, Harry B.
  • Chemistry of Materials, Vol. 26, Issue 1
  • DOI: 10.1021/cm4021518

Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption
journal, February 2013

  • Strmcnik, Dusan; Uchimura, Masanobu; Wang, Chao
  • Nature Chemistry, Vol. 5, Issue 4
  • DOI: 10.1038/nchem.1574

Operando Analyses of Solar Fuels Light Absorbers and Catalysts
journal, September 2016


Relationships between Atomic Level Surface Structure and Stability/Activity of Platinum Surface Atoms in Aqueous Environments
journal, March 2016


Simulation and Modeling of Self-Assembled Monolayers of Carboxylic Acid Thiols on Flat and Nanoparticle Gold Surfaces
journal, September 2011

  • Techane, Sirnegeda; Baer, Donald R.; Castner, David G.
  • Analytical Chemistry, Vol. 83, Issue 17
  • DOI: 10.1021/ac201175a

Fuel Cells - Fundamentals and Applications
journal, May 2001


Commentary: The Materials Project: A materials genome approach to accelerating materials innovation
journal, July 2013

  • Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy
  • APL Materials, Vol. 1, Issue 1
  • DOI: 10.1063/1.4812323

Microscopic View of Nucleation on Surfaces
journal, October 1994


Oxygen Evolution at Platinum Electrodes in Alkaline Solutions
journal, January 1987

  • Birss, V. I.
  • Journal of The Electrochemical Society, Vol. 134, Issue 1
  • DOI: 10.1149/1.2100385

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

Formation enthalpies by mixing GGA and GGA + U calculations
journal, July 2011


Changing the Activity of Electrocatalysts for Oxygen Reduction by Tuning the Surface Electronic Structure
journal, April 2006

  • Stamenkovic, Vojislav; Mun, Bongjin Simon; Mayrhofer, Karl J. J.
  • Angewandte Chemie, Vol. 118, Issue 18
  • DOI: 10.1002/ange.200504386

A comparison between water adsorbed on Rh(111) and Pt(111), with and without predosed oxygen
journal, January 1987


Curve synthesis and optimization procedures for X-ray photoelectron spectroscopy
journal, February 1991


Identification of an Adsorbed Hydroxyl Species on the Pt(111) Surface
journal, March 1980


Using “Tender” X-ray Ambient Pressure X-Ray Photoelectron Spectroscopy as A Direct Probe of Solid-Liquid Interface
journal, May 2015

  • Axnanda, Stephanus; Crumlin, Ethan J.; Mao, Baohua
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep09788

Surface oxidation and reduction of platinum electrodes: Coverage, kinetic and hysteresis studies
journal, March 1968

  • Gilroy, D.; Conway, B. E.
  • Canadian Journal of Chemistry, Vol. 46, Issue 6
  • DOI: 10.1139/v68-149

Review of Pt-Based Bimetallic Catalysis: From Model Surfaces to Supported Catalysts
journal, August 2012

  • Yu, Weiting; Porosoff, Marc D.; Chen, Jingguang G.
  • Chemical Reviews, Vol. 112, Issue 11, p. 5780-5817
  • DOI: 10.1021/cr300096b

Heterogeneous Catalysis
journal, February 2015


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

Potential oscillations during electro-oxidation of ethanol on platinum in alkaline media: The role of surface sites
journal, November 2016

  • Sallum, Loriz Francisco; Gonzalez, Ernesto Rafael; Feliu, Juan Miguel
  • Electrochemistry Communications, Vol. 72
  • DOI: 10.1016/j.elecom.2016.09.005

Simulation of electron spectra for surface analysis (SESSA): a novel software tool for quantitative Auger-electron spectroscopy and X-ray photoelectron spectroscopy
journal, January 2005

  • Smekal, Werner; Werner, Wolfgang S. M.; Powell, Cedric J.
  • Surface and Interface Analysis, Vol. 37, Issue 11
  • DOI: 10.1002/sia.2097

Subsurface Oxygen in Oxide-Derived Copper Electrocatalysts for Carbon Dioxide Reduction
journal, December 2016

  • Eilert, André; Cavalca, Filippo; Roberts, F. Sloan
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 1
  • DOI: 10.1021/acs.jpclett.6b02273

    Works referencing / citing this record:

    A review of transition metal‐based bifunctional oxygen electrocatalysts
    journal, April 2019

    • Ibrahim, Kassa B.; Tsai, Meng‐Che; Chala, Soressa A.
    • Journal of the Chinese Chemical Society, Vol. 66, Issue 8
    • DOI: 10.1002/jccs.201900001

    A review of transition metal‐based bifunctional oxygen electrocatalysts
    journal, April 2019

    • Ibrahim, Kassa B.; Tsai, Meng‐Che; Chala, Soressa A.
    • Journal of the Chinese Chemical Society, Vol. 66, Issue 8
    • DOI: 10.1002/jccs.201900001