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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]
  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:
Journal Article: 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.
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
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. 2015. "Water as a Promoter and Catalyst for Dioxygen Electrochemistry in Aqueous and Organic Media". United States. https://doi.org/10.1021/acscatal.5b01779.
@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},
url = {https://www.osti.gov/biblio/1223600}, journal = {ACS Catalysis},
issn = {2155-5435},
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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at https://doi.org/10.1021/acscatal.5b01779

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Cited by: 85 works
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