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Title: Water as a Promoter and Catalyst for Dioxygen Electrochemistry in Aqueous and Organic Media

Abstract

Water and oxygen electrochemistry lies at the heart of interfacial processes controlling energy transformations in fuel cells, electrolyzers, and batteries. Here, by comparing results for the ORR obtained in alkaline aqueous media to those obtained in ultradry organic electrolytes with known amounts of H2O added intentionally, we propose a new rationale in which water itself plays an important role in determining the reaction kinetics. This effect derives from the formation of HOad···H2O (aqueous solutions) and LiO2···H2O (organic solvents) complexes that place water in a configurationally favorable position for proton transfer to weakly adsorbed intermediates. We also find that, even at low concentrations (<10 ppm), water acts simultaneously as a promoter and as a catalyst in the production of Li2O2, regenerating itself through a sequence of steps that include the formation and recombination of H+ and OH–. We conclude that, although the binding energy between metal surfaces and oxygen intermediates is an important descriptor in electrocatalysis, understanding the role of water as a proton-donor reactant may explain many anomalous features in electrocatalysis at metal–liquid interfaces

Authors:
 [1];  [2];  [1];  [3];  [4];  [1];  [5];  [6];  [2];  [7];  [1];  [1];  [1];  [1];  [4];  [3];  [1]
+ Show Author Affiliations
  1. Materials Science Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States, Joint Center for Energy Storage Research, Argonne National Laboratory, 9700 S Cass Avenue, Argonne, Illinois 60439, United States
  2. Materials Science Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States
  3. Sandia National Laboratory, P.O. Box 5800, Albuquerque, New Mexico 87185, United States, Joint Center for Energy Storage Research, Argonne National Laboratory, 9700 S Cass Avenue, Argonne, Illinois 60439, United States
  4. University of Illinois at Urbana−Champaign, Urbana, Illinois 61801, United States, Joint Center for Energy Storage Research, Argonne National Laboratory, 9700 S Cass Avenue, Argonne, Illinois 60439, United States
  5. Department of Electrochemical Materials, J. Heyrovsky Institute of Physical Chemistry, Prague, Czech Republic
  6. Northwestern University, Evanston, Illinois 60208, United States
  7. Materials Science Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States, Faculty of Chemistry and Chemical Technology, University of Ljubljana, Ljubljana, Slovenia, Joint Center for Energy Storage Research, Argonne National Laboratory, 9700 S Cass Avenue, Argonne, Illinois 60439, United States
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1223600
Alternate Identifier(s):
OSTI ID: 1249103; OSTI ID: 1343272; OSTI ID: 1365808
Report Number(s):
SAND-2014-18453J; SAND-2017-1617J
Journal ID: ISSN 2155-5435
Grant/Contract Number:  
AC02-06CH11357; AC04-94AL85000
Resource Type:
Published Article
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Name: ACS Catalysis Journal Volume: 5 Journal Issue: 11; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
batteries; lithium-oxygen; oxygen reduction reaction; activated water; electrocatalysis; water networks; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; lithium−oxygen

Citation Formats

Staszak-Jirkovský, Jakub, Subbaraman, Ram, Strmcnik, Dusan, Harrison, Katharine L., Diesendruck, Charles E., Assary, Rajeev, Frank, Otakar, Kobr, Lukáš, Wiberg, Gustav K. H., Genorio, Bostjan, Connell, Justin G., Lopes, Pietro P., Stamenkovic, Vojislav R., Curtiss, Larry, Moore, Jeffrey S., Zavadil, Kevin R., and Markovic, Nenad M. Water as a Promoter and Catalyst for Dioxygen Electrochemistry in Aqueous and Organic Media. United States: N. p., 2015. Web. doi:10.1021/acscatal.5b01779.
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Staszak-Jirkovský, Jakub, Subbaraman, Ram, Strmcnik, Dusan, Harrison, Katharine L., Diesendruck, Charles E., Assary, Rajeev, Frank, Otakar, Kobr, Lukáš, Wiberg, Gustav K. H., Genorio, Bostjan, Connell, Justin G., Lopes, Pietro P., Stamenkovic, Vojislav R., Curtiss, Larry, Moore, Jeffrey S., Zavadil, Kevin R., & Markovic, Nenad M. Water as a Promoter and Catalyst for Dioxygen Electrochemistry in Aqueous and Organic Media. United States. https://doi.org/10.1021/acscatal.5b01779
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Staszak-Jirkovský, Jakub, Subbaraman, Ram, Strmcnik, Dusan, Harrison, Katharine L., Diesendruck, Charles E., Assary, Rajeev, Frank, Otakar, Kobr, Lukáš, Wiberg, Gustav K. H., Genorio, Bostjan, Connell, Justin G., Lopes, Pietro P., Stamenkovic, Vojislav R., Curtiss, Larry, Moore, Jeffrey S., Zavadil, Kevin R., and Markovic, Nenad M. Fri . "Water as a Promoter and Catalyst for Dioxygen Electrochemistry in Aqueous and Organic Media". United States. https://doi.org/10.1021/acscatal.5b01779.
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@article{osti_1223600,
title = {Water as a Promoter and Catalyst for Dioxygen Electrochemistry in Aqueous and Organic Media},
author = {Staszak-Jirkovský, Jakub and Subbaraman, Ram and Strmcnik, Dusan and Harrison, Katharine L. and Diesendruck, Charles E. and Assary, Rajeev and Frank, Otakar and Kobr, Lukáš and Wiberg, Gustav K. H. and Genorio, Bostjan and Connell, Justin G. and Lopes, Pietro P. and Stamenkovic, Vojislav R. and Curtiss, Larry and Moore, Jeffrey S. and Zavadil, Kevin R. and Markovic, Nenad M.},
abstractNote = {Water and oxygen electrochemistry lies at the heart of interfacial processes controlling energy transformations in fuel cells, electrolyzers, and batteries. Here, by comparing results for the ORR obtained in alkaline aqueous media to those obtained in ultradry organic electrolytes with known amounts of H2O added intentionally, we propose a new rationale in which water itself plays an important role in determining the reaction kinetics. This effect derives from the formation of HOad···H2O (aqueous solutions) and LiO2···H2O (organic solvents) complexes that place water in a configurationally favorable position for proton transfer to weakly adsorbed intermediates. We also find that, even at low concentrations (<10 ppm), water acts simultaneously as a promoter and as a catalyst in the production of Li2O2, regenerating itself through a sequence of steps that include the formation and recombination of H+ and OH–. We conclude that, although the binding energy between metal surfaces and oxygen intermediates is an important descriptor in electrocatalysis, understanding the role of water as a proton-donor reactant may explain many anomalous features in electrocatalysis at metal–liquid interfaces},
doi = {10.1021/acscatal.5b01779},
journal = {ACS Catalysis},
number = 11,
volume = 5,
place = {United States},
year = {Fri Oct 16 00:00:00 EDT 2015},
month = {Fri Oct 16 00:00:00 EDT 2015}
}
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https://doi.org/10.1021/acscatal.5b01779
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Works referenced in this record:

Why is Gold such a Good Catalyst for Oxygen Reduction in Alkaline Media?
journal, November 2012

  • Quaino, P.; Luque, N. B.; Nazmutdinov, R.
  • Angewandte Chemie International Edition, Vol. 51, Issue 52
  • DOI: 10.1002/anie.201205902

Water Catalysis of a Radical-Molecule Gas-Phase Reaction
journal, January 2007

Impedance Spectroscopy of Self-Assembled Monolayers on Au(111):  Sodium Ferrocyanide Charge Transfer at Modified Electrodes
journal, May 1998

  • Janek, Richard P.; Fawcett, W. Ronald; Ulman, Abraham
  • Langmuir, Vol. 14, Issue 11
  • DOI: 10.1021/la970980+

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 International Edition, Vol. 45, Issue 18
  • DOI: 10.1002/anie.200504386

Effects of media and electrode materials on the electrochemical reduction of dioxygen
journal, September 1982

  • Sawyer, Donald T.; Chiericato, Glaico.; Angelis, Charles T.
  • Analytical Chemistry, Vol. 54, Issue 11
  • DOI: 10.1021/ac00248a014

Lithium Peroxide Surfaces Are Metallic, While Lithium Oxide Surfaces Are Not
journal, December 2011

  • Radin, Maxwell D.; Rodriguez, Jill F.; Tian, Feng
  • Journal of the American Chemical Society, Vol. 134, Issue 2
  • DOI: 10.1021/ja208944x

Adsorption and Electroreduction of Oxygen on Gold in Acidic Media: In Situ Spectroscopic Identification of Adsorbed Molecular Oxygen and Hydrogen Superoxide
journal, June 2012

  • Ohta, Narumi; Nomura, Kamba; Yagi, Ichizo
  • The Journal of Physical Chemistry C, Vol. 116, Issue 27
  • DOI: 10.1021/jp302857q

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

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

Monte Carlo, density functional theory, and Poisson–Boltzmann theory study of the structure of an electrolyte near an electrode
journal, April 2002

  • Boda, Dezsö; Fawcett, W. Ronald; Henderson, Douglas
  • The Journal of Chemical Physics, Vol. 116, Issue 16
  • DOI: 10.1063/1.1464826

Enhancing Hydrogen Evolution Activity in Water Splitting by Tailoring Li+-Ni(OH)2-Pt Interfaces
journal, December 2011

Stability of superoxide radicals in glyme solvents for non-aqueous Li–O2 battery electrolytes
journal, January 2013

  • Schwenke, K. Uta; Meini, Stefano; Wu, Xiaohan
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 28
  • DOI: 10.1039/c3cp51531a

Oxygen reduction on electrode surfaces modified by foreign metal ad-atoms: Lead ad-atoms on gold
journal, November 1980

  • Adžić, R. R.; Tripković, A. V.; Marković, N. M.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 114, Issue 1
  • DOI: 10.1016/S0022-0728(80)80434-7

Electrocatalysis of oxygen on single crystal gold electrodes
journal, July 1989

Influence of Nonaqueous Solvents on the Electrochemistry of Oxygen in the Rechargeable Lithium−Air Battery
journal, April 2010

  • Laoire, Cormac O.; Mukerjee, Sanjeev; Abraham, K. M.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 19
  • DOI: 10.1021/jp102019y

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

Oxygen Electroreduction through a Superoxide Intermediate on Bi-Modified Au Surfaces
journal, April 2005

  • Li, Xiao; Gewirth, Andrew A.
  • Journal of the American Chemical Society, Vol. 127, Issue 14
  • DOI: 10.1021/ja043170a

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

Building biomimetic membrane at a gold electrode surface
journal, January 2010

  • Lipkowski, Jacek
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 42
  • DOI: 10.1039/c0cp00658k

Structural effects in electrocatalysis
journal, May 1984

  • Adić, R. R.; Marković, N. M.; Vešović, V. B.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 165, Issue 1-2
  • DOI: 10.1016/S0022-0728(84)80090-X

Raman and Infrared Spectra of LiO 2 in Oxygen Matrices
journal, April 1972

  • Hatzenbuhler, Douglas A.; Andrews, Lester
  • The Journal of Chemical Physics, Vol. 56, Issue 7
  • DOI: 10.1063/1.1677711

Twin Problems of Interfacial Carbonate Formation in Nonaqueous Li–O 2 Batteries
journal, March 2012

  • McCloskey, B. D.; Speidel, A.; Scheffler, R.
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 8
  • DOI: 10.1021/jz300243r

Spectroscopic Identification of the Reaction Intermediates in Oxygen Reduction on Gold in Alkaline Solutions
journal, September 2005

  • Shao, M. H.; Adzic, R. R.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 35
  • DOI: 10.1021/jp053450s

The influence of OH− chemisorption on the catalytic properties of gold single crystal surfaces for oxygen reduction in alkaline solutions
journal, February 1996

Ordered Anion Adlayers on Metal Electrode Surfaces
journal, March 2002

The interaction of water with solid surfaces: fundamental aspects revisited
journal, May 2002

Enhancing the Alkaline Hydrogen Evolution Reaction Activity through the Bifunctionality of Ni(OH) 2 /Metal Catalysts
journal, November 2012

  • Danilovic, N.; Subbaraman, Ram; Strmcnik, D.
  • Angewandte Chemie International Edition, Vol. 51, Issue 50
  • DOI: 10.1002/anie.201204842

Oxygen Reactions in a Non-Aqueous Li+ Electrolyte
journal, May 2011

  • Peng, Zhangquan; Freunberger, Stefan A.; Hardwick, Laurence J.
  • Angewandte Chemie International Edition, Vol. 50, Issue 28, p. 6351-6355
  • DOI: 10.1002/anie.201100879

Nonaqueous Li–Air Batteries: A Status Report
journal, October 2014

  • Luntz, Alan C.; McCloskey, Bryan D.
  • Chemical Reviews, Vol. 114, Issue 23
  • DOI: 10.1021/cr500054y

Water in Biological Systems
journal, March 1971

The Kinetics of the Oxygen Reduction Reaction on Gold in Alkaline Solution
journal, January 1978

  • Zurilla, R. W.
  • Journal of The Electrochemical Society, Vol. 125, Issue 7
  • DOI: 10.1149/1.2131628

Surface-Mediated Solvent Decomposition in Li–Air Batteries: Impact of Peroxide and Superoxide Surface Terminations
journal, April 2015

  • Kumar, Nitin; Radin, Maxwell D.; Wood, Brandon C.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 17
  • DOI: 10.1021/acs.jpcc.5b00256

Electrochemistry of oxygen and superoxide ion in dimethylsulfoxide at platinum, gold and mercury electrodes
journal, August 1966

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

Structure sensitivity and nanoscale effects in electrocatalysis
journal, January 2011

How super is superoxide?
journal, December 1981

  • Sawyer, Donald T.; Valentine, Joan S.
  • Accounts of Chemical Research, Vol. 14, Issue 12
  • DOI: 10.1021/ar00072a005

CHEMISTRY: Ions at the Air/Water Interface
journal, February 2004

The Influence of Water and Protons on Li 2 O 2 Crystal Growth in Aprotic Li-O 2 Cells
journal, January 2015

  • Schwenke, K. Uta; Metzger, Michael; Restle, Tassilo
  • Journal of The Electrochemical Society, Vol. 162, Issue 4
  • DOI: 10.1149/2.0201504jes

Structure and Stability of Lithium Superoxide Clusters and Relevance to Li–O2 Batteries
journal, February 2014

  • Das, Ujjal; Lau, Kah Chun; Redfern, Paul C.
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 5, p. 813-819
  • DOI: 10.1021/jz500084e

Structure of Water at the Electrified Platinum−Water Interface:  A Study by Surface-Enhanced Infrared Absorption Spectroscopy
journal, February 2008

  • Osawa, Masatoshi; Tsushima, Minoru; Mogami, Hirokazu
  • The Journal of Physical Chemistry C, Vol. 112, Issue 11
  • DOI: 10.1021/jp710386g

Catalytic Activity Trends of Oxygen Reduction Reaction for Nonaqueous Li-Air Batteries
journal, November 2011

  • Lu, Yi-Chun; Gasteiger, Hubert A.; Shao-Horn, Yang
  • Journal of the American Chemical Society, Vol. 133, Issue 47
  • DOI: 10.1021/ja208608s

Improved Oxygen Reduction Activity on Pt3Ni(111) via Increased Surface Site Availability
journal, January 2007

  • Stamenkovic, V. R.; Fowler, B.; Mun, B. S.
  • Science, Vol. 315, Issue 5811, p. 493-497
  • DOI: 10.1126/science.1135941
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