Artículo
Water Self-Dissociation is Insensitive to Nanoscale Environments
Di Pino, Solana Magalí
; Pérez Sirkin, Yamila Anahí
; Morzan, Uriel
; Sanchez, Veronica Muriel
; Hassanali, Ali; Scherlis Perel, Damian Ariel
Fecha de publicación:
07/2023
Editorial:
Wiley-VCH
Revista:
Angewandte Chemie
ISSN:
0044-8249
e-ISSN:
1521-3757
Idioma:
Inglés
Tipo de recurso:
Artículo publicado
Clasificación temática:
Resumen
Nanoconfinement effects on water dissociation and reactivity remain controversial, despite their importance to understand the aqueous chemistry at interfaces, pores, or aerosols. The pKw in confined environments has been assessed from experiments and simulations in a few specific cases, leading to dissimilar conclusions. Here, with the use of carefully designed ab initio simulations, we demonstrate that the energetics of bulk water dissociation is conserved intact to unexpectedly small length-scales, down to aggregates of only a dozen molecules or pores of widths below 2 nm. The reason is that most of the free-energy involved in water autoionization comes from breaking the O−H covalent bond, which has a comparable barrier in the bulk liquid, in a small droplet of nanometer size, or in a nanopore in the absence of strong interfacial interactions. Thus, dissociation free-energy profiles in nanoscopic aggregates or in 2D slabs of 1 nm width reproduce the behavior corresponding to the bulk liquid, regardless of whether the corresponding nanophase is delimited by a solid or a gas interface. The present work provides a definite and fundamental description of the mechanism and thermodynamics of water dissociation at different scales with broader implications on reactivity and self-ionization at the air-liquid interface.
Palabras clave:
WATER
,
NANOSCALE
,
DISSOCIATION
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Articulos(INQUIMAE)
Articulos de INST.D/QUIM FIS D/L MATERIALES MEDIOAMB Y ENERGIA
Articulos de INST.D/QUIM FIS D/L MATERIALES MEDIOAMB Y ENERGIA
Citación
Di Pino, Solana Magalí; Pérez Sirkin, Yamila Anahí; Morzan, Uriel; Sanchez, Veronica Muriel; Hassanali, Ali; et al.; Water Self-Dissociation is Insensitive to Nanoscale Environments; Wiley-VCH; Angewandte Chemie; 135; 34; 7-2023; 1-9
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