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Energetics of ethanol and carbon dioxide adsorption on anatase, rutile, and γ-alumina nanoparticles

  • Lili Wu , Xin Guo and Alexandra Navrotsky EMAIL logo
Published/Copyright: April 26, 2019
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Abstract

Nanoparticles are widely present in the natural environment. Their surface reactivity, redox ability, and adsorption properties are related to geochemical processes. To explore the thermodynamics of interaction between nano oxides and small gas molecules, we applied gas adsorption calorimetry to investigate the energetics of ethanol and carbon dioxide adsorbed on surfaces of nanoscale anatase, rutile, and γ-alumina particles. The measured zero-coverage adsorption enthalpies per mole of gas adsorbed are –97.7, –107.3, and –84.8 kJ/mol for C2H5OH on anatase, rutile, and γ-Al2O3, respectively. The corresponding values for CO2 adsorption are –59.4, –47.4, and –47.1 kJ/mol. The results indicate the ethanol adsorption is generally more exothermic than carbon dioxide and water adsorption. The isotherm and differential enthalpies show type II isotherms and step-wise patterns for ethanol adsorption in all three oxides. However, CO2 adsorption shows simple continuous isotherms and energetics that suggest dominant physical adsorption occurred. The repeated adsorption cycle shows that ethanol adsorption on these nanoparticles is partially reversible at room temperature. This thermodynamic evidence indicates that ethanol and similar organics may protect mineral oxide surfaces from reaction with aqueous solutions, which may affect crystal growth, dissolution, and biomineralization.

Acknowledgments and Funding

This research was supported by the U. S. Department of Energy, Office of Basic Energy Sciences, grant ER97-14749. We thank Sergey Ushakov for assistance in the gas adsorption experiments and Pardha Saradhi Maram for help with Raman spectroscopy.

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Received: 2018-08-27
Accepted: 2019-01-15
Published Online: 2019-04-26
Published in Print: 2019-05-27

© 2019 Walter de Gruyter GmbH, Berlin/Boston

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