Molecular Structure of Adsorbed Water Phases in Silica Nanopores

Rother, Gernot; Gautam, Siddharth; Liu, Tingting; Cole, David R.; Busch, Andreas; Stack, Andrew G.

doi:10.1021/acs.jpcc.1c10162

Molecular Structure of Adsorbed Water Phases in Silica Nanopores

Journal Article · Tue Feb 01 00:00:00 EST 2022 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.1c10162· OSTI ID:1843705

^[1]; ^[2]; ^[2]; Cole, David R. ^[2]; Busch, Andreas ^[3]; ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
The Ohio State Univ., Columbus, OH (United States)
Heriot-Watt Univ, Scotland (United Kingdom)

The adsorption of water vapor in silica nanopores with different pore morphologies and surface hydrophilicities was studied to quantify the densities and thicknesses of the water sorption layers and deduce their molecular structures. Water adsorption to surface hydroxyls is described by a multilayer sorption model. At low pressure, the water adsorption isotherms are largely independent of pore size and the adsorbed amounts scale with the surface hydroxyl density. Adsorbed-phase densities corresponding to the adsorption of two water molecules per surface hydroxyl group are found in the first adsorbed water layer for a wide range of surface hydroxyl densities. The densities and layer thickness values found in narrow pores indicate that patchy adsorbed layers form if not enough water molecules exist for a full layer, which coexist with dry pore surface regions. This behavior indicates cooperative adsorption effects, i.e., a preference for the formation of hydrogen bonds between water molecules bound to surface hydroxyls. In narrow pores, pore condensation limits further growth of the sorption layer, and in larger pores and at the planar quartz surface, a second adsorbed water layer is formed, which can hold up to approximately 4 additional water molecules per surface hydroxyl group. The water molecules in these thicker adsorption layers arrange such that the sorption layer density is similar to the bulk water density. Pore confinement limitations on the sorption layers are observed in pores with radii of as large as 8 nm. Molecular dynamics modeling reveals two preferential orientations for water molecules adsorbing to surface hydroxyl groups and suggests an intralayer structuring in the adsorbed monolayer. Furthermore, adsorbed water molecules in the sorption layer are bonded to the surface hydroxyl group via the donation and acceptance of hydrogen bonds.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1843705

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 5 Vol. 126; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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