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

Rasmus Kronberg, Kari Laasonen*

*Tämän työn vastaava kirjoittaja

Tutkimustuotos: LehtiartikkeliArticleScientificvertaisarvioitu

3 Sitaatiot (Scopus)
78 Lataukset (Pure)

Abstrakti

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 H₃O⁺ 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.
AlkuperäiskieliEnglanti
Sivut10128-10134
Sivumäärä7
JulkaisuJournal of Physical Chemistry Letters
Vuosikerta12
Numero41
Varhainen verkossa julkaisun päivämäärä12 lokak. 2021
DOI - pysyväislinkit
TilaJulkaistu - 21 lokak. 2021
OKM-julkaisutyyppiA1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

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