Cargando…
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....
Autores principales: | , |
---|---|
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 |
_version_ | 1784589667175235584 |
---|---|
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. |
format | Online Article Text |
id | pubmed-8543677 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
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 |
work_keys_str_mv | AT kronbergrasmus dynamicsandsurfacepropensityofhandohwithinrigidinterfacialwaterimplicationsforelectrocatalysis AT laasonenkari dynamicsandsurfacepropensityofhandohwithinrigidinterfacialwaterimplicationsforelectrocatalysis |