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Methylene Blue Adsorption on the Basal Surfaces of Kaolinite: Structure and Thermodynamics from Quantum and Classical Molecular Simulation

Published online by Cambridge University Press:  01 January 2024

Jeffery A. Greathouse*
Geochemistry Department, Sandia National Laboratories, P.O. Box 5800, MS 0754, Albuquerque, NM 87185-0754, USA
Dawn L. Geatches
Energy Resources Engineering, Earth Sciences, Stanford University, CA 94305-2220, USA
Darin Q. Pike
Chemical and Biological Systems Department, Sandia National Laboratories, P.O. Box 5800, MS 0734, Albuquerque, NM 87185-0734, USA
H. Christopher Greenwell
Department of Earth Sciences, Durham University, South Road, Durham DH1 3LE, UK
Cliff T. Johnston
Crop, Soil, and Environmental Sciences, Purdue University, West Lafayette, IN, 47097, USA
Jennifer Wilcox
Energy Resources Engineering, Earth Sciences, Stanford University, CA 94305-2220, USA
Randall T. Cygan
Geochemistry Department, Sandia National Laboratories, P.O. Box 5800, MS 0754, Albuquerque, NM 87185-0754, USA
*E-mail address of corresponding author:


Organic dyes such as methylene blue (MB) are often used in the characterization of clays and related minerals, but details of the adsorption mechanisms of such dyes are only partially understood from spectroscopic data, which indicate the presence of monomers, dimers, and higher aggregates for varying mineral surfaces. A combination of quantum (density functional theory) and classical molecular simulation methods was used to provide molecular detail of such adsorption processes, specifically the adsorption of MB onto kaolinite basal surfaces. Slab models with vacuum-terminated surfaces were used to obtain detailed structural properties and binding energies at both levels of theory, while classical molecular dynamics simulations of aqueous pores were used to characterize MB adsorption at infinite dilution and at higher concentration in which MB dimers and one-dimensional chains formed. Results for the neutral MB molecules are compared with those for the corresponding cation. Simulations of the aqueous pore indicate preferred adsorption on the hydrophobic siloxane surface, while charge-balancing chloride ions adsorb at the aluminol surface. At infinite dilution and in the gas-phase models, MB adsorbs with its primary molecular plane parallel to the siloxane surface to enhance hydrophobic interactions. Sandwiched dimers and chains are oriented perpendicular to the surface to facilitate the strong hydrophobic intermolecular interactions. Compared with quantum results, the hybrid force field predicts a weaker MB adsorption energy but a stronger dimerization energy. The structure and energetics of adsorbed MB at infinite dilution are consistent with the gas-phase binding results, which indicate that monomer adsorption is driven by strong interfacial forces rather than by the hydration properties of the dye. These results inform spectroscopic studies of MB adsorption on mineral surfaces while also revealing critical areas for development of improved hybrid force fields.

Research Article
Copyright © Clay Minerals Society 2015

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