Natural kaolinite exhibit high affinity for heavy metals while the interaction mechanisms in the presence of heteroatoms remain largely elusive, which are tackled by first principles. In this paper, three common dopants (Mg, Ca, Fe) were employed to construct metal-doped kaolinite(001) (K(001)) surfaces. We found that Mg-doped K(001) was the most stable surface in terms of thermal stability and structural analysis, consistent with the pervasive isomorphic substitution in kaolinite minerals. The interaction of mercury with Mg-doped K(001) surface was investigated in the form of predominant top-site and bridge-site models. The effects of chloride on the interaction were also studied. The results demonstrated that the strongest adsorption occured in the present of dopants and the absence of chloride. The electronic properties revealed a significant charge transfer (up to 1.28 electrons) and chemisorption character at the interfaces when dopants were introduced, which could be ascribed to the overlapping of Hg-5d and Os-2p (surface O) orbitals in the range of -7.5 eV to +0.5 eV. Additionally, the chloride had a profoundly adverse influence on mercury adsorption due to the upward shift of Hg-6s and Hg-6p orbitals. The studies are beneficial to understand the interaction mechanisms of natural minerals toward environmental pollutants in actual applications.
Keywords: Adsorption mechanism; Charge transfer; Doped K(001) surface; Mercury species; PDOS analysis.
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