First-Principles Study on Ligand Binding and Positional Disorder in Pentlandite

Calum N. Waterson, Julien O. Sindt, Jun Cheng, Peter A. Tasker, Carole A. Morrison*

*Corresponding author for this work

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

Density functional theory, in conjunction with a cluster expansion model, has been used to study the structure and stability of the positionally disordered iron-nickel sulfide mineral pentlandite (Pn), (Fe,Ni)9S8, with results indicating heterogeneous nearest neighbor metal contacts are more energetically favorable than homogeneous contacts. The virtual crystal approximation was also explored as a means to address positional disorder, but while reliable results could be obtained for the bulk model, the same was not true for the surface, as local distortions which affected the surface model energies could not be reproduced. We also address the binding of ethyl xanthate (CH3CH2OCS2 -), water, and hydroxide to the [111] Pn surface to understand the mode of action of industrial xanthate flotation agents better. In order to model anionic ligands bound to a periodic boundary condition surface we propose applying a correction derived from the surface work function to remove the additional charge introduced by the ligand. The results obtained from the ligand binding studies indicate that while ethyl xanthate could readily displace up to a full monolayer of water per unit cell it is likely that Fe-enriched surfaces will bind xanthate in competition with the hydroxide anion, while a Ni-enriched surface will preferentially bind hydroxide anions over xanthate.

Original languageEnglish
Pages (from-to)25457-25468
Number of pages12
JournalThe Journal of Physical Chemistry C
Volume119
Issue number45
DOIs
Publication statusPublished - 14 Oct 2015

Fingerprint

Ligands
disorders
ligands
hydroxides
Anions
Flotation agents
Negative ions
anions
Sulfide minerals
flotation
Water
pentlandite
water
Density functional theory
sulfides
electric contacts
Monolayers
Iron
Metals
Nickel

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Waterson, C. N., Sindt, J. O., Cheng, J., Tasker, P. A., & Morrison, C. A. (2015). First-Principles Study on Ligand Binding and Positional Disorder in Pentlandite. The Journal of Physical Chemistry C, 119(45), 25457-25468. https://doi.org/10.1021/acs.jpcc.5b08649

First-Principles Study on Ligand Binding and Positional Disorder in Pentlandite. / Waterson, Calum N.; Sindt, Julien O.; Cheng, Jun; Tasker, Peter A.; Morrison, Carole A.

In: The Journal of Physical Chemistry C, Vol. 119, No. 45, 14.10.2015, p. 25457-25468.

Research output: Contribution to journalArticle

Waterson, CN, Sindt, JO, Cheng, J, Tasker, PA & Morrison, CA 2015, 'First-Principles Study on Ligand Binding and Positional Disorder in Pentlandite', The Journal of Physical Chemistry C, vol. 119, no. 45, pp. 25457-25468. https://doi.org/10.1021/acs.jpcc.5b08649
Waterson, Calum N. ; Sindt, Julien O. ; Cheng, Jun ; Tasker, Peter A. ; Morrison, Carole A. / First-Principles Study on Ligand Binding and Positional Disorder in Pentlandite. In: The Journal of Physical Chemistry C. 2015 ; Vol. 119, No. 45. pp. 25457-25468.
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abstract = "Density functional theory, in conjunction with a cluster expansion model, has been used to study the structure and stability of the positionally disordered iron-nickel sulfide mineral pentlandite (Pn), (Fe,Ni)9S8, with results indicating heterogeneous nearest neighbor metal contacts are more energetically favorable than homogeneous contacts. The virtual crystal approximation was also explored as a means to address positional disorder, but while reliable results could be obtained for the bulk model, the same was not true for the surface, as local distortions which affected the surface model energies could not be reproduced. We also address the binding of ethyl xanthate (CH3CH2OCS2 -), water, and hydroxide to the [111] Pn surface to understand the mode of action of industrial xanthate flotation agents better. In order to model anionic ligands bound to a periodic boundary condition surface we propose applying a correction derived from the surface work function to remove the additional charge introduced by the ligand. The results obtained from the ligand binding studies indicate that while ethyl xanthate could readily displace up to a full monolayer of water per unit cell it is likely that Fe-enriched surfaces will bind xanthate in competition with the hydroxide anion, while a Ni-enriched surface will preferentially bind hydroxide anions over xanthate.",
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