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Probing the site occupancies of Co-, Ni-, and Mn-substituted biogenic magnetite using XAS and XMCD

DOI: 10.2138/am.2008.2681 DOI Help

Authors: John M Charnock (University of Manchester) , Elke Arenholz (Lawrence Berkeley National Laboratory) , Jonathan R Lloyd , Victoria S Coker (University of Manchester) , Richard A.d. Pattrick (University of Manchester) , Carolyn I Pearce (University of Manchester) , Neil Telling (Daresbury Laboratory) , Gerrit Van Der Laan (Diamond Light Source)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: American Mineralogist , VOL 93 (7) , PAGES 1119-1132

State: Published (Approved)
Published: July 2008

Abstract: Ferrimagnetic nanoparticles have many uses in industry including in magnetic recording media and transformers, however these particles are often expensive to synthesize. In this study, the Fe3+-reducing bacteria Geobacter sulfurreducens and Shewanella oneidensis were used to synthesize spinel ferrite nanoparticles of the general chemical formula MxFe3–xO4, where M is either Co, Ni, Mn, Zn, or a combination of Mn and Zn. This was done at ambient temperatures through the dissimilatory reduction of Fe3+-oxyhydroxides containing the appropriate substitutional cations. A combination of L-edge and K-edge X-ray absorption spectroscopy (XAS) and L-edge X-ray magnetic circular dichroism (XMCD) was used to determine the site occupancies, valence, and local structure of the Fe and substitutional cations within the spinels. The Ni and Co ferrites produced using each bacterium were very similar and therefore this study concludes that, despite the difference in reduction mechanism of the bacteria used, the end-product is remarkably unaltered. Nickel ferrites contained only Ni2+, with at least 80% in Oh coordination. Cobalt ferrites contained only Co2+ but with a significant proportion (up to 45%) in Td coordination, showing a slight preference for Td sites. The Mn-ferrites contained Mn2+ only on the Oh sites but a mixture of Mn2+ and Mn3+ on Td sites when the amount of Mn exceeded 3% (compared to the amount of Fe) or some Zn was also present. This study successfully produced a range of nanoparticulate ferrites that could be produced industrially using relatively environmentally benign methodologies.

Journal Keywords: Nanoparticles; Thermoresponsive Polymer; Block Copolymer; Polymer Brushes

Subject Areas: Environment


Instruments: NONE-No attached Diamond beamline