Density Functional Theory and Molecular Dynamics insights into the site-dependent adsorption of hydrogen fluoride on kaolinite.

The removal of fluoride from water using adsorption on a low-cost mineral such as kaolinite is an important research topic. The present communication uses Density Functional Theory (DFT) and Molecular Dynamics (MD) based simulations to comprehensively investigate the adsorption behaviour of HF, one of the most predominant species of fluoride in the aqueous solutions, on the (0 0 1) surface of kaolinite. The optimum geometric configurations of adsorption of HF on different possible sites on the mineral surface have been established, and the corresponding adsorption energies, bond distances, Partial Density of States (PDOS), Mulliken charges and electron density difference plots have been analyzed to understand the interaction at each site. To explore the site-dependent adsorption behaviour, the interaction of HF has been investigated on different sites such as aluminium centres, surface oxygen atoms (both lying and upright) and cavity site (void space encircled by six aluminium centres). The analysis shows that the F atom has a strong tendency to form hydrogen bonds with the surface H atom on kaolinite. Among the three aforementioned types of adsorption sites considered, the "cavity" site is found to offer the greatest adsorption strength. Further, MD simulations have been undertaken to explain the effect of water on the adsorption and substantiate the bonding mechanism. • Adsorption of HF on the kaolinite (0 0 1) surface was investigated by DFT-D simulation. • Optimum adsorption configurations of HF on different possible sites are established. • MD simulations reveal effect of solvent on the behaviour of HF adsorption. • Complex structure, preferred adsorption position and adsorption bonding pattern were solved. • Among all the adsorption sites considered, the "cavity" site is found to offer the greatest adsorption strength. [ABSTRACT FROM AUTHOR]