Influence of Fe(II), Fe(III) and Al(III) isomorphic substitutions on acid-base properties of edge surfaces of cis-vacant montmorillonite: Insights from first-principles molecular dynamics simulations and surface complexation modeling

摘要: Knowing the influence of isomorphic substitutions on the acid-base properties of smectite edge surfaces is an important aspect of the detailed understanding of clay minerals’ interfacial properties with implications in the modeling of adsorption processes. We investigated the intrinsic acidity constants of Fe(II)/Fe(III) and Al(III) substituted edge surface sites of montmorillonite with a cis-vacant structure, which includes four crystallographic orientations perpendicular to [010], [010], [110], and [110], using the first-principles molecular dynamics (FPMD) based vertical energy gap method. Fe(II) and Fe(III) substitutions resulted, respectively, in a significant increase and decrease in pKa values of amphoteric groups directly associated with Fe octahedra. In addition, Fe(II) substitution increased the pKa values of the neighboring silanol sites, while Fe(III) substitution had a weak influence on these sites. The Al-substituted …