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Title: Molecular Dynamics Simulation Study of the Early Stages of Nucleation of Iron Oxyhydroxide Nanoparticles in Aqueous Solutions

Abstract

Nucleation is a fundamental step in crystal growth. Of environmental and materials relevance are reactions that lead to nucleation of iron oxyhydroxides in aqueous solutions. These reactions are difficult to study experimentally due to their rapid kinetics. Here, we used classical molecular dynamics simulations to investigate nucleation of iron hydroxide/oxyhydroxide nanoparticles in aqueous solutions. Results show that in a solution containing ferric ions and hydroxyl groups, iron-hydroxyl molecular clusters form by merging ferric monomers, dimers, and other oligomers, driven by strong affinity of ferric ions to hydroxyls. When deprotonation reactions are not considered in the simulations, these clusters aggregate to form small iron hydroxide nanocrystals with a six-membered ring-like layered structure allomeric to gibbsite. By comparison, in a solution containing iron chloride and sodium hydroxide, the presence of chlorine drives cluster assembly along a different direction to form long molecular chains (rather than rings) composed of Fe-O octahedra linked by edge sharing. Further, in chlorine-free solutions, when deprotonation reactions are considered, the simulations predict ultimate formation of amorphous iron oxyhydroxide nanoparticles with local atomic structure similar to that of ferrihydrite nanoparticles. Overall, our simulation results reveal that nucleation of iron oxyhydroxide nanoparticles proceeds via a cluster aggregation-based nonclassical pathway.

Authors:
 [1];  [2];  [3]
  1. Department of Earth and Planetary Science, University of California, Berkeley, California 94720, United States
  2. Earth Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
  3. Department of Earth and Planetary Science, University of California, Berkeley, California 94720, United States, Earth Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1209165
Alternate Identifier(s):
OSTI ID: 1214161; OSTI ID: 1512232
Grant/Contract Number:  
AC02-05CH11231; NSF CHE-1213835
Resource Type:
Published Article
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Name: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry Journal Volume: 119 Journal Issue: 33; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhang, Hengzhong, Waychunas, Glenn A., and Banfield, Jillian F. Molecular Dynamics Simulation Study of the Early Stages of Nucleation of Iron Oxyhydroxide Nanoparticles in Aqueous Solutions. United States: N. p., 2015. Web. doi:10.1021/acs.jpcb.5b03801.
Zhang, Hengzhong, Waychunas, Glenn A., & Banfield, Jillian F. Molecular Dynamics Simulation Study of the Early Stages of Nucleation of Iron Oxyhydroxide Nanoparticles in Aqueous Solutions. United States. https://doi.org/10.1021/acs.jpcb.5b03801
Zhang, Hengzhong, Waychunas, Glenn A., and Banfield, Jillian F. Thu . "Molecular Dynamics Simulation Study of the Early Stages of Nucleation of Iron Oxyhydroxide Nanoparticles in Aqueous Solutions". United States. https://doi.org/10.1021/acs.jpcb.5b03801.
@article{osti_1209165,
title = {Molecular Dynamics Simulation Study of the Early Stages of Nucleation of Iron Oxyhydroxide Nanoparticles in Aqueous Solutions},
author = {Zhang, Hengzhong and Waychunas, Glenn A. and Banfield, Jillian F.},
abstractNote = {Nucleation is a fundamental step in crystal growth. Of environmental and materials relevance are reactions that lead to nucleation of iron oxyhydroxides in aqueous solutions. These reactions are difficult to study experimentally due to their rapid kinetics. Here, we used classical molecular dynamics simulations to investigate nucleation of iron hydroxide/oxyhydroxide nanoparticles in aqueous solutions. Results show that in a solution containing ferric ions and hydroxyl groups, iron-hydroxyl molecular clusters form by merging ferric monomers, dimers, and other oligomers, driven by strong affinity of ferric ions to hydroxyls. When deprotonation reactions are not considered in the simulations, these clusters aggregate to form small iron hydroxide nanocrystals with a six-membered ring-like layered structure allomeric to gibbsite. By comparison, in a solution containing iron chloride and sodium hydroxide, the presence of chlorine drives cluster assembly along a different direction to form long molecular chains (rather than rings) composed of Fe-O octahedra linked by edge sharing. Further, in chlorine-free solutions, when deprotonation reactions are considered, the simulations predict ultimate formation of amorphous iron oxyhydroxide nanoparticles with local atomic structure similar to that of ferrihydrite nanoparticles. Overall, our simulation results reveal that nucleation of iron oxyhydroxide nanoparticles proceeds via a cluster aggregation-based nonclassical pathway.},
doi = {10.1021/acs.jpcb.5b03801},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 33,
volume = 119,
place = {United States},
year = {Thu Aug 06 00:00:00 EDT 2015},
month = {Thu Aug 06 00:00:00 EDT 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpcb.5b03801

Citation Metrics:
Cited by: 28 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: (a) Snapshot of an 8.5 M NaOH aqueous solution at MD time 500 ps: red, O; gray, H; violet, Na. (b) Radial distribution functions (g) and accumulated coordination numbers of atoms (CN) of hydroxyl oxygen (“OH”) and water oxygen (“OW”) around a sodium cation.

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