Energy Landscape of Water and Ethanol on Silica Surfaces

Di Wu, Xiaofeng Guo, Hui Sun, Alexandra Navrotsky

Research output: Contribution to journalArticlepeer-review

22 Scopus citations

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. The 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.

Original languageEnglish (US)
Pages (from-to)15428-15433
Number of pages6
JournalJournal of Physical Chemistry C
Volume119
Issue number27
DOIs
StatePublished - Jul 9 2015
Externally publishedYes

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

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