Molecular-level controls on water and organics intercalation in layered minerals

Abstract: Layered minerals are naturally abundant and often display a large surface area in relation to their weight. For swelling layered minerals, most of this area is contained between the layers in the interlayer space. Their large surface area makes them interesting in many different fields and applications, such as adsorbents, catalysts or as carriers for other particles that can be intercalated and exchanged. In order for the materials to be used effectively, it is hence necessary to have a fundamental understanding of how these processes occur, and ways to predict them.To address adsorption of water, an isotherm model was created to describe the hydration process on layered materials. The model decomposed the process of adsorptions into internal and external, adsorption and condensation, and could specifically handle hydration in the expanding interlayer nanopores. Adsorption and desorption isotherms of two different materials, Montmorillonite and Birnessite was successfully modelled, where the former was ion-exchanged with the counter-cations Li+, Na+, K+, Cs+, Mg2+, Ca2+, Sr2+, Cu2+, whereas the latter contained K+. This indicated that this isotherm model is applicable to also other layered materials. The adsorption process was also characterized experimentally with vibrational spectroscopy (FTIR) and multivariate statistical techniques (MCR), in order to generate spectral- and concentration profiles of the involved components.In order to also investigate adsorption of different organic molecules, the intercalation of alcohols and a cationic surfactant was investigated in separate studies. Clay-water-alcohol systems of eight alcohols were characterized experimentally by XRD as well as by molecular dynamics simulations, using different combinations of classical force fields for the clay (ClayFF, ClayFFMod, INTERFACE) and for the alcohols (CGenFF, GAFF, OPLS). It was found that the optimal force field combination varied with the fitting approach. A brute force sensitivity analysis indicated that the comparison with the experimental XRD data was more dependent on the relative interlayer loading than the positions of the atoms, an important result for future similar benchmarking studies.By intercalating and adsorbing a cationic surfactant (CTAB) to Montmorillonite at increasing concentrations, the effects of solvent polarity and the CTAB interlayer content on the Montmorillonite interlayer swelling was investigated. It was found that moderately polar solvents such as DMSO, in combination with CTAB in a planar bilayer configuration resulted in the greatest adsorption of the lipophilic solute alizarin.