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Cadmium(II) Complexes Adsorbed on Clay Edge Surfaces: Insight from First Principles Molecular Dynamics Simulation

Published online by Cambridge University Press:  01 January 2024

Chi Zhang,
Xiandong Liu,
Xiancai Lu,
Evert Jan Meijer,
Kai Wang,
Mengjia He and
Rucheng Wang
Chi Zhang
Affiliation:
State Key Laboratory for Mineral Deposits Research, School of Earth Sciences and Engineering, Nanjing University, Nanjing 210093, P.R. China
Xiandong Liu*
Affiliation:
State Key Laboratory for Mineral Deposits Research, School of Earth Sciences and Engineering, Nanjing University, Nanjing 210093, P.R. China
Xiancai Lu
Affiliation:
State Key Laboratory for Mineral Deposits Research, School of Earth Sciences and Engineering, Nanjing University, Nanjing 210093, P.R. China
Evert Jan Meijer
Affiliation:
Van’t Hoff Institute for Molecular Sciences and Amsterdam Center for Multiscale Modeling, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands
Kai Wang
Affiliation:
State Key Laboratory for Mineral Deposits Research, School of Earth Sciences and Engineering, Nanjing University, Nanjing 210093, P.R. China
Mengjia He
Affiliation:
State Key Laboratory for Mineral Deposits Research, School of Earth Sciences and Engineering, Nanjing University, Nanjing 210093, P.R. China
Rucheng Wang
Affiliation:
State Key Laboratory for Mineral Deposits Research, School of Earth Sciences and Engineering, Nanjing University, Nanjing 210093, P.R. China
*
*E-mail address of corresponding author: xiandongliu@nju.edu.cn
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Abstract

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Aiming to identify the complexing mechanisms of heavy metal cations on edge surfaces of 2:1-type clay minerals, systemic first-principles molecular dynamics (FPMD) simulations were conducted and the microscopic structures and complex free energies were obtained. Taking Cd(II) as a model cation, the structures on both (010) and (110) edges of the complexes were derived for the three possible binding sites (≡SiO, ≡Al(OH)2/≡AlOH≡AlSiO, and vacant sites). The stable complexes adsorbed on the three binding sites on both terminations had similar structures. The free energies of the complexes on (010) edges were calculated by using the constrained FPMD method. The free energies of complexes on the ≡SiO and ≡Al(OH)2 sites were similar and they were both significantly lower than the free energy of the complex on the octahedral vacant site. In association with the concept of high energy site (HES) and low energy site (LES) in the 2 Site Protolysis Non Electrostatic Surface Complexation and Cation Exchange (2SPNE SC/CE) sorption model, the vacant site was assigned to HES and the other two sites to LES, respectively.

Keywords

Binding SiteCadmium CationComplexationEdge SurfaceFirst-Principles Molecular DynamicsFree Energy

Information

Type
Article
Information
Clays and Clay Minerals , Volume 64 , Issue 4 , August 2016, pp. 337 - 347
Copyright
Copyright © The Clay Minerals Society 2016

Footnotes

This paper is published as part of a special issue on the subject of ‘Computational Molecular Modeling’. Some of the papers were presented during the 2015 Clay Minerals Society-Euroclay Conference held in Edinburgh, UK.

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