Understanding the Heterogeneous Nucleation of Heavy Metal Phyllosilicates on Clay Edges with First-Principles Molecular Dynamics.

The nucleation and precipitation of heavy metal phyllosilicates can occur in the course of sorption onto clay edges, which will provide a long-term stabilization of heavy metal pollutants. However, a quantitative understanding of their reaction mechanisms is still lacking. Taking Ni2+ as the model cation, we characterized the atomic scale structures and thermodynamics of the early stage of nucleation by carrying out systematic first-principles molecular dynamics (FPMD) simulations, and the microscopic nucleation mechanisms were revealed. Two possible nucleation pathways were examined: a stepwise pathway (denoted as Path1) and a synchronous pathway (denoted as Path2). In Path1, Ni(OH)2 forms first and then transforms to Ni phyllosilicate via silicification; in Path2, Ni phyllosilicate forms on clay edges directly. The computed free energies of complexation and condensation reactions indicate that Path2 is much more thermodynamically favorable than Path1, meaning that, given that the solution contains dissolved Si initially, heavy metal phyllosilicates will nucleate on clay edges through Path2. By comparing these free energies with their counterpart values of the reaction in bulk solution, the effect of the surface has been uncovered. These findings provide valuable insights for an improved understanding of the stabilization and transformation of heavy metal elements in nature. The derived results form a quantitative basis for future studies on the heterogenous nucleation and precipitation of heavy metal cations.