Adsorption behavior of NH 4 + and Mg 2+ at kaolinite surfaces: Effect of the ion concentration, NH 4 + /Mg 2+ mixing ratio, and layer charge

The adsorption behavior of NH 4 + and Mg 2+ at kaolinite surfaces was investigated by using molecular dynamics (MD) simulations, considering the factors such as ion concentration, NH 4 + /Mg 2+ mixing ratio, and layer charge of kaolinite. The results showed that the increase in ion concentration did not affect the adsorption modes of NH 4 + and Mg 2+ ions but promote the increase in the adsorption capacity. The total adsorption capacities of Mg 2+ and NH 4 + were 3.25 × 10 −6 and 2.85 × 10 −6 μmol·mm −2 at the ion concentration of 1.5 mol·L −1 , respectively. When NH 4 + and Mg 2+ were co‐adsorbed, they could inhibit the adsorption of each other at the surface of kaolinite, except that the inner‐sphere (IS) adsorption of NH 4 + at aluminum hydroxyl (Al–OH) surface could be enhanced by the presence of Mg 2+ . Both NH 4 + and Mg 2+ tended to adsorb at the siloxane (Si–O) surface of kaolinite rather than Al–OH surface. When layer charge occurred in kaolinite, a small number of Mg 2+ began to adsorb in the IS complexes at 1.7 and 2.3 Å above the Al and O atoms of the lattice‐substituted tetrahedra of the Si–O surface, and at 1.7 Å above the hexahedra of the Al–OH surface. However, most of NH 4 + were adsorbed in IS complexes at 1.7 Å above the center of the oxygen six‐membered ring of the Si–O surface and above the hexahedron of the Al–OH surface. The adsorption capacity of Mg 2+ changed little with the increase of layer charge density, while the IS and total adsorption capacity of NH 4 + increased significantly.