Theoretical study on the adsorption mechanism of PbCl₂/CdCl₂ by kaolinite during municipal solid waste pyrolysis

In the process of municipal solid waste (MSW) pyrolysis, kaolinite possesses an outstanding trapping effect on semi-volatile metal vapors (Pb, Cd) through physical and chemical adsorption. In this paper, the microscopic mechanism of PbCl₂ and CdCl₂ adsorption on the surface of Al rings and Si rings of kaolinite was investigated by combining Monte Carlo method with density functional theory (DFT). The calculations indicate that the continuously enriched pore structure in the process of dehydroxylation indirectly influences the adsorption of PbCl₂/CdCl₂ by kaolinite. Under the non-bond interaction and electron transfer induction, PbCl₂ molecules are more conveniently adsorbed on the Al-(001) surface than CdCl₂, while the adsorption sites of CdCl₂ molecules are more widely distributed on the Si-(001) surface. Moreover, the transform in the Al-coordination and the exposed active oxygen atoms significantly affect the adsorption activity of kaolinite (the capability to gain and lose electrons). Considering the energy barrier and electrophilic nucleophilic sensitivity, it is more feasible for PbCl₂/CdCl₂ to be adsorbed near IV/V-coordinated Al and active O under Van der Waals action. Subsequently, IV/V-coordinated Al will act as an electron acceptor, and the active oxygen atoms after dehydrogenation will serve as an electron donor. Under the induction of the energy difference of frontier orbitals, the electrons transfer will encourage the formation of more stable adsorption states. The results shed new light on strengthening the adsorption activity of kaolinite to PbCl₂/CdCl₂ in the process of MSW pyrolysis.