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Reversible vs Standard Hydrogen Electrode Scale in Interfacial Electrochemistry from a Theoretician’s Atomistic Point of View

Groß, Axel 1
1 Post Lithium Storage (POLiS), Karlsruher Institut für Technologie (KIT)


It is a general notion in interfacial electrochemistry that the stability of adsorbate phases that only contain hydrogen atoms should be independent of the pH value of the electrolyte on the scale of the reversible hydrogen electrode, whereas the stability of adsorbate phases that do not contain any hydrogen should be independent of the pH value on the scale of the standard hydrogen electrode. In this Perspective, it will be argued on the basis of a grand-canonical approach that such a Nernstian behavior can only be reproduced if the free energy of the adsorbate phase is independent of the electrochemical control parameters. In general, this should not be true, so that the Nernstian behavior should be the exception rather than the rule. Still, structural and chemical factors will be discussed that might lead to a Nernstian behavior. This requires an analysis of the electrochemical electrolyte/electrode interface on the atomistic level. At the same time, this analysis also provides a guideline for the validity of grand-canonical simulations using the concept of the computational hydrogen electrode in which the dependence of the energy of adsorbate phases on pH and electrode potential is neglected.

Verlagsausgabe §
DOI: 10.5445/IR/1000148022
Veröffentlicht am 22.06.2022
DOI: 10.1021/acs.jpcc.2c02734
Zitationen: 9
Web of Science
Zitationen: 7
Zitationen: 11
Cover der Publikation
Zugehörige Institution(en) am KIT Helmholtz-Institut Ulm (HIU)
Post Lithium Storage (POLiS)
Publikationstyp Zeitschriftenaufsatz
Publikationsjahr 2022
Sprache Englisch
Identifikator ISSN: 1932-7447, 1932-7455
KITopen-ID: 1000148022
HGF-Programm 38.02.02 (POF IV, LK 01) Components and Cells
Erschienen in The Journal of Physical Chemistry C
Verlag American Chemical Society (ACS)
Band 126
Heft 28
Seiten 11439–11446
Vorab online veröffentlicht am 15.06.2022
Nachgewiesen in Web of Science
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