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Magnetic spectroscopy of nanoparticulate greigite, Fe3S4

Published online by Cambridge University Press:  02 January 2018

Richard A. D. Pattrick ,
Victoria S. Coker ,
Masood Akhtar ,
M. Azad Malik ,
Edward Lewis ,
Sarah Haigh ,
Paul O'Brien ,
Padraic C. Shafer  and
Gerrit van der Laan
Richard A. D. Pattrick*
Affiliation:
School of Earth, Atmospheric and Environmental Sciences and Williamson Research Centre, The University of Manchester, Manchester M13 9PL, UK
Victoria S. Coker
Affiliation:
School of Earth, Atmospheric and Environmental Sciences and Williamson Research Centre, The University of Manchester, Manchester M13 9PL, UK
Masood Akhtar
Affiliation:
School of Chemistry, The University of Manchester, Manchester M13 9PL, UK
M. Azad Malik
Affiliation:
School of Chemistry, The University of Manchester, Manchester M13 9PL, UK
Edward Lewis
Affiliation:
School of Chemistry, The University of Manchester, Manchester M13 9PL, UK
Sarah Haigh
Affiliation:
School of Chemistry, The University of Manchester, Manchester M13 9PL, UK
Paul O'Brien
Affiliation:
School of Chemistry, The University of Manchester, Manchester M13 9PL, UK
Padraic C. Shafer
Affiliation:
Advanced Light Source, Lawrence Berkeley National Labs, Berkeley, CA, USA
Gerrit van der Laan
Affiliation:
School of Earth, Atmospheric and Environmental Sciences and Williamson Research Centre, The University of Manchester, Manchester M13 9PL, UK Magnetic Spectroscopy Group, Diamond Light Source, Didcot OX11 0DE, UK
*
*E-mail: richard.pattrick@manchester.ac.uk
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Abstract

Synthesis of Ni and Zn substituted nano-greigite, Fe3S4, is achieved from single source diethyldithiocarbamato precursor compounds, producing particles typically 50–100 nm in diameter with plate-like pseudohexagonal morphologies. Up to 12 wt.% Ni is incorporated into the greigite structure, and there is evidence that Zn is also incorporated but Co is not substituted into the lattice. The Fe L3 X-ray absorption spectra for these materials have a narrow single peak at 707.7 eV and the resulting main X-ray magnetic circular dichroism (XMCD) has the same sign at 708.75 eV. All XMCD spectra also have a broad positive feature at 711 eV, a characteristic of covalent mixing. The greigite XMCD spectra contrast with the three clearly defined XMCD site specific peaks found in the ferrite spinel, magnetite. The Fe L2,3X-ray absorption spectra and XMCD spectra of the greigite reflect and reveal the high conductivity of greigite and the very strong covalency of the Fe–S bonding. The electron hopping between Fe3+ and Fe2+ on octahedral sites results in an intermediate oxidation state of the Fe in the Oh site of Fe2.5+ producing an effective formula of [Fe3+ ↑]A-site[2Fe2.5+ ↓]B-siteS42–]. The Ni L2,3 X-ray absorption spectra and XMCD reveal substitution on the Oh site with a strongly covalent character and an oxidation state <Ni1.5+ in a representative formula [Fe3+ ↑]A[[(2 – x)Fe2.5+ ↓][Nix1.5+]]BS42–.

Keywords

ferrimagneticthiospinelmagnetic spectroscopynanoparticulate greigiteX-ray absorption spectroscopy
Type
Research Article
Information
Mineralogical Magazine , Volume 81 , Issue 4 , August 2017 , pp. 857 - 872
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2017

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