Energy Landscape of Water and Ethanol on Silica Surfaces

Wu, Di; Guo, Xiaofeng; Sun, Hui; Navrotsky, Alexandra

doi:10.1021/acs.jpcc.5b04271

Title: Energy Landscape of Water and Ethanol on Silica Surfaces

Journal Article · Fri Jun 26 00:00:00 EDT 2015 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.5b04271· OSTI ID:1221610

Wu, Di ^[1]; Guo, Xiaofeng ^[2]; Sun, Hui ^[3]; Navrotsky, Alexandra ^[1]

Univ. of California, Davis, CA (United States)
Univ. of California, Davis, CA (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
East China Univ. of Science and Technology, Shanghai (China)

Fundamental understanding of small molecule–silica surface interactions at their interfaces is essential for the scientific, technological, and medical communities. We report direct enthalpy of adsorption (Δh_ads) measurements for ethanol and water vapor on porous silica glass (CPG-10), in both hydroxylated and dehydroxylated (hydrophobic) forms. Results suggest a spectrum of energetics as a function of coverage, stepwise for ethanol but continuous for water. The zero-coverage enthalpy of adsorption for hydroxylated silica shows the most exothermic enthalpies for both water (-72.7 ± 3.1 kJ/mol water) and ethanol (-78.0 ± 1.9 kJ/mol ethanol). The water adsorption enthalpy becomes less exothermic gradually until reaching its only plateau (-20.7 ± 2.2 kJ/mol water) reflecting water clustering on a largely hydrophobic surface, while the enthalpy of ethanol adsorption profile presents two well separated plateaus, corresponding to strong chemisorption of ethanol on adsorbate-free silica surface (-66.4 ± 4.8 kJ/mol ethanol), and weak physisorption of ethanol on ethanol covered silica (-4.0 ± 1.6 kJ/mol ethanol). On the other hand, dehydroxylation leads to missing water–silica interactions, whereas the number of ethanol binding sites is not impacted. The isotherms and partial molar properties of adsorption suggest that water may only bind strongly onto the silanols (which are a minor species on silica glass), whereas ethanol can interact strongly with both silanols and the hydrophobic areas of the silica surface.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

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

Grant/Contract Number:: FG02-97ER14749; AC52-06NA25396

OSTI ID:: 1221610

Report Number(s):: LA-UR-15-24271

Journal Information:: Journal of Physical Chemistry. C, Vol. 119, Issue 27; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 30 works

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