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Title: Energy Landscape of Water and Ethanol on Silica Surfaces

Abstract

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 (Δhads) 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 speciesmore » on silica glass), whereas ethanol can interact strongly with both silanols and the hydrophobic areas of the silica surface.« less

Authors:
 [1];  [2];  [3];  [1]
+ Show Author Affiliations
  1. Univ. of California, Davis, CA (United States)
  2. Univ. of California, Davis, CA (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. East China Univ. of Science and Technology, Shanghai (China)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1221610
Report Number(s):
LA-UR-15-24271
Journal ID: ISSN 1932-7447
Grant/Contract Number:  
FG02-97ER14749; AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 119; Journal Issue: 27; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wu, Di, Guo, Xiaofeng, Sun, Hui, and Navrotsky, Alexandra. Energy Landscape of Water and Ethanol on Silica Surfaces. United States: N. p., 2015. Web. doi:10.1021/acs.jpcc.5b04271.
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Wu, Di, Guo, Xiaofeng, Sun, Hui, & Navrotsky, Alexandra. Energy Landscape of Water and Ethanol on Silica Surfaces. United States. https://doi.org/10.1021/acs.jpcc.5b04271
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Wu, Di, Guo, Xiaofeng, Sun, Hui, and Navrotsky, Alexandra. Fri . "Energy Landscape of Water and Ethanol on Silica Surfaces". United States. https://doi.org/10.1021/acs.jpcc.5b04271. https://www.osti.gov/servlets/purl/1221610.
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@article{osti_1221610,
title = {Energy Landscape of Water and Ethanol on Silica Surfaces},
author = {Wu, Di and Guo, Xiaofeng and Sun, Hui and Navrotsky, Alexandra},
abstractNote = {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 (Δhads) 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.},
doi = {10.1021/acs.jpcc.5b04271},
journal = {Journal of Physical Chemistry. C},
number = 27,
volume = 119,
place = {United States},
year = {Fri Jun 26 00:00:00 EDT 2015},
month = {Fri Jun 26 00:00:00 EDT 2015}
}
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https://doi.org/10.1021/acs.jpcc.5b04271
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