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First-Principles Molecular Dynamics Insight into Fe2+ Complexes Adsorbed on Edge Surfaces of Clay Minerals

Published online by Cambridge University Press:  01 January 2024

Xiandong Liu ,
Evert Jan Meijer ,
Xiancai Lu  and
Rucheng Wang
Xiandong Liu*
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 Centre for Multiscale Modelling, University of Amsterdam, Nieuwe Achtergracht 166, 1018 WV, Amsterdam, The Netherlands
Xiancai Lu
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

Using first-principles molecular-dynamics simulations, probable inner-sphere complexes of Fe2+ adsorbed on the edge surfaces of clay minerals were investigated. Ferrous ions are important reductants in natural processes and their properties can be altered significantly by complexation on edge surfaces of clay minerals. However, the microscopic picture of adsorption sites and structures of Fe2+ is difficult to reveal with modern experimental techniques and, therefore, remains unclear. From the results of first-principles molecular-dynamics simulations, evidence has been provided that complexes on ≡Si—O sites were the most stable forms, which should be responsible for the experimentally observed pH-dependent uptake. Such complexation was found to be strong enough to distort the local coordination structures of Si—O tetrahedra in the substrate. Analyses showed that Fe2+—Owater coordination structures were dominated by the solvent with surface groups participating in the complexes via H bonding. The present study provided a microscopic basis for understanding the chemical processes involving surface-complexed Fe2+ ions.

Keywords

ComplexationEdge SurfaceFerrous IonFirst-principles Molecular DynamicsHydration
Type
Article
Information
Clays and Clay Minerals , Volume 60 , Issue 4 , August 2012 , pp. 341 - 347
Copyright
Copyright © Clay Minerals Society 2012

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