Toward Modeling Clay Mineral Nanoparticles: The Edge Surfaces of Pyrophyllite and Their Interaction with Water

Abstract

The basal surfaces of phyllosilicate minerals have been widely studied, whereas the edge surfaces have received little attention. However, in order to simulate complete clay particles at the atomic level, the modeling of edge surfaces becomes crucially important, and such surfaces are likely to be far more active. We used a combination of quantum and potential based techniques to evaluate the structure of the edge surfaces of pyrophyllite and their interaction in an aqueous environment. These include {110}, {100}, {010}, {1̅10}, {130}, and {1̅30}. We found that the CLAYFF force field is an effective model for reproducing the DFT results. Furthermore, the results show that, for this notorious natural hydrophobic clay, all edge surfaces show hydrophilic behavior and that the precise structure of water above these surfaces is influenced by both the presence of hydroxyl groups and under-coordinated surface Al atoms; this will impact both geological processes where natural clays are involved and processes where such clays act as primary retention barriers to the dispersion of contaminants.