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Dynamics and Surface Propensity of H(+) and OH(–) within Rigid Interfacial Water: Implications for Electrocatalysis

[Image: see text] Facile solvent reorganization promoting ion transfer across the solid–liquid interface is considered a prerequisite for efficient electrocatalysis. We provide first-principles insight into this notion by examining water self-ion dynamics at a highly rigid NaCl(100)–water interface....

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Autores principales: Kronberg, Rasmus, Laasonen, Kari
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8543677/
https://www.ncbi.nlm.nih.gov/pubmed/34636561
http://dx.doi.org/10.1021/acs.jpclett.1c02493
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author Kronberg, Rasmus
Laasonen, Kari
author_facet Kronberg, Rasmus
Laasonen, Kari
author_sort Kronberg, Rasmus
collection PubMed
description [Image: see text] Facile solvent reorganization promoting ion transfer across the solid–liquid interface is considered a prerequisite for efficient electrocatalysis. We provide first-principles insight into this notion by examining water self-ion dynamics at a highly rigid NaCl(100)–water interface. Through extensive density functional theory molecular dynamics simulations, we demonstrate for both acidic and alkaline solutions that Grotthuss dynamics is not impeded by a rigid water structure. Conversely, decreased proton transfer barriers and a striking propensity of H(3)O(+) and OH(–) for stationary interfacial water are found. Differences in the ideal hydration structure of the ions, however, distinguish their behavior at the water contact layer. While hydronium can maintain its optimal solvation, the preferentially hypercoordinated hydroxide is repelled from the immediate vicinity of the surface due to interfacial coordination reduction. This has implications for alkaline hydrogen electrosorption in which the formation of undercoordinated OH(–) at the surface is proposed to contribute to the observed sluggish kinetics.
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spelling pubmed-85436772021-10-26 Dynamics and Surface Propensity of H(+) and OH(–) within Rigid Interfacial Water: Implications for Electrocatalysis Kronberg, Rasmus Laasonen, Kari J Phys Chem Lett [Image: see text] Facile solvent reorganization promoting ion transfer across the solid–liquid interface is considered a prerequisite for efficient electrocatalysis. We provide first-principles insight into this notion by examining water self-ion dynamics at a highly rigid NaCl(100)–water interface. Through extensive density functional theory molecular dynamics simulations, we demonstrate for both acidic and alkaline solutions that Grotthuss dynamics is not impeded by a rigid water structure. Conversely, decreased proton transfer barriers and a striking propensity of H(3)O(+) and OH(–) for stationary interfacial water are found. Differences in the ideal hydration structure of the ions, however, distinguish their behavior at the water contact layer. While hydronium can maintain its optimal solvation, the preferentially hypercoordinated hydroxide is repelled from the immediate vicinity of the surface due to interfacial coordination reduction. This has implications for alkaline hydrogen electrosorption in which the formation of undercoordinated OH(–) at the surface is proposed to contribute to the observed sluggish kinetics. American Chemical Society 2021-10-12 2021-10-21 /pmc/articles/PMC8543677/ /pubmed/34636561 http://dx.doi.org/10.1021/acs.jpclett.1c02493 Text en © 2021 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Kronberg, Rasmus
Laasonen, Kari
Dynamics and Surface Propensity of H(+) and OH(–) within Rigid Interfacial Water: Implications for Electrocatalysis
title Dynamics and Surface Propensity of H(+) and OH(–) within Rigid Interfacial Water: Implications for Electrocatalysis
title_full Dynamics and Surface Propensity of H(+) and OH(–) within Rigid Interfacial Water: Implications for Electrocatalysis
title_fullStr Dynamics and Surface Propensity of H(+) and OH(–) within Rigid Interfacial Water: Implications for Electrocatalysis
title_full_unstemmed Dynamics and Surface Propensity of H(+) and OH(–) within Rigid Interfacial Water: Implications for Electrocatalysis
title_short Dynamics and Surface Propensity of H(+) and OH(–) within Rigid Interfacial Water: Implications for Electrocatalysis
title_sort dynamics and surface propensity of h(+) and oh(–) within rigid interfacial water: implications for electrocatalysis
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8543677/
https://www.ncbi.nlm.nih.gov/pubmed/34636561
http://dx.doi.org/10.1021/acs.jpclett.1c02493
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