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Title: The role of an interface in stabilizing reaction intermediates for hydrogen evolution in aprotic electrolytes

Abstract

By combining idealized experiments with realistic quantum mechanical simulations of an interface, we investigate electro-reduction reactions of HF, water and methanesulfonic acid (MSA) on the single crystal (111) facets of Au, Pt, Ir and Cu in organic aprotic electrolytes, 1 M LiPF6 in EC/EMC 3:7W (LP57), the aprotic electrolyte commonly used in Li-ion batteries, 1 M LiClO4 in EC/EMC 3:7W and 0.2 M TBAPF6 in 3 : 7 EC/EMC. In our previous work, we have established that LiF formation, accompanied by H2 evolution, is caused by a reduction of HF impurities and requires the presence of Li at the interface, which catalyzes the HF dissociation. In the present paper, we find that the measured potential of the electrochemical response for these reduction reactions correlates with the work function of the electrode surfaces and that the work function determines the potential for Li+ adsorption. The reaction path is investigated further by electrochemical simulations suggesting that the overpotential of the reaction is related to stabilizing the active structure of the interface having adsorbed Li+. Li+ is needed to facilitate the dissociation of HF which is the source of protons. Further experiments on other proton sources, water and methanesulfonic acid, show that ifmore » the hydrogen evolution involves negatively charged intermediates, F- or HO-, a cation at the interface can stabilize them and facilitate the reaction kinetics. When the proton source is already significantly dissociated (in the case of a strong acid), there is no negatively charged intermediate and thus the hydrogen evolution can proceed at much lower overpotentials. This reveals a situation where the overpotential for electrocatalysis is related to stabilizing the active structure of the interface, facilitating the reaction rather than providing the reaction energy.« less

Authors:
ORCiD logo [1];  [2];  [1];  [2]; ORCiD logo [2];  [3]; ORCiD logo [4];  [2];  [2]; ORCiD logo [1]
  1. Nano-Science Center; Department of Chemistry; University of Copenhagen; Copenhagen Ø; Denmark
  2. Materials Science Division; Argonne National Laboratory; Argonne; USA
  3. Battery Cell Technology; BMW Group; München; Germany
  4. Battery Cell Technology; BMW Group; München; Germany; Institute for Advanced Study
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; BMW Technology Corporation; Technical University of Munich
OSTI Identifier:
1607944
Alternate Identifier(s):
OSTI ID: 1633428
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 15; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Castelli, Ivano E., Zorko, Milena, Østergaard, Thomas M., Martins, Pedro F. B. D., Lopes, Pietro P., Antonopoulos, Byron K., Maglia, Filippo, Markovic, Nenad M., Strmcnik, Dusan, and Rossmeisl, Jan. The role of an interface in stabilizing reaction intermediates for hydrogen evolution in aprotic electrolytes. United Kingdom: N. p., 2020. Web. doi:10.1039/C9SC05768D.
Castelli, Ivano E., Zorko, Milena, Østergaard, Thomas M., Martins, Pedro F. B. D., Lopes, Pietro P., Antonopoulos, Byron K., Maglia, Filippo, Markovic, Nenad M., Strmcnik, Dusan, & Rossmeisl, Jan. The role of an interface in stabilizing reaction intermediates for hydrogen evolution in aprotic electrolytes. United Kingdom. doi:https://doi.org/10.1039/C9SC05768D
Castelli, Ivano E., Zorko, Milena, Østergaard, Thomas M., Martins, Pedro F. B. D., Lopes, Pietro P., Antonopoulos, Byron K., Maglia, Filippo, Markovic, Nenad M., Strmcnik, Dusan, and Rossmeisl, Jan. Wed . "The role of an interface in stabilizing reaction intermediates for hydrogen evolution in aprotic electrolytes". United Kingdom. doi:https://doi.org/10.1039/C9SC05768D.
@article{osti_1607944,
title = {The role of an interface in stabilizing reaction intermediates for hydrogen evolution in aprotic electrolytes},
author = {Castelli, Ivano E. and Zorko, Milena and Østergaard, Thomas M. and Martins, Pedro F. B. D. and Lopes, Pietro P. and Antonopoulos, Byron K. and Maglia, Filippo and Markovic, Nenad M. and Strmcnik, Dusan and Rossmeisl, Jan},
abstractNote = {By combining idealized experiments with realistic quantum mechanical simulations of an interface, we investigate electro-reduction reactions of HF, water and methanesulfonic acid (MSA) on the single crystal (111) facets of Au, Pt, Ir and Cu in organic aprotic electrolytes, 1 M LiPF6 in EC/EMC 3:7W (LP57), the aprotic electrolyte commonly used in Li-ion batteries, 1 M LiClO4 in EC/EMC 3:7W and 0.2 M TBAPF6 in 3 : 7 EC/EMC. In our previous work, we have established that LiF formation, accompanied by H2 evolution, is caused by a reduction of HF impurities and requires the presence of Li at the interface, which catalyzes the HF dissociation. In the present paper, we find that the measured potential of the electrochemical response for these reduction reactions correlates with the work function of the electrode surfaces and that the work function determines the potential for Li+ adsorption. The reaction path is investigated further by electrochemical simulations suggesting that the overpotential of the reaction is related to stabilizing the active structure of the interface having adsorbed Li+. Li+ is needed to facilitate the dissociation of HF which is the source of protons. Further experiments on other proton sources, water and methanesulfonic acid, show that if the hydrogen evolution involves negatively charged intermediates, F- or HO-, a cation at the interface can stabilize them and facilitate the reaction kinetics. When the proton source is already significantly dissociated (in the case of a strong acid), there is no negatively charged intermediate and thus the hydrogen evolution can proceed at much lower overpotentials. This reveals a situation where the overpotential for electrocatalysis is related to stabilizing the active structure of the interface, facilitating the reaction rather than providing the reaction energy.},
doi = {10.1039/C9SC05768D},
journal = {Chemical Science},
number = 15,
volume = 11,
place = {United Kingdom},
year = {2020},
month = {1}
}

Journal Article:
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DOI: https://doi.org/10.1039/C9SC05768D

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