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The oxidation state of copper and cobalt in carrollite, CuCo2S4

DOI: 10.3749/canmin.46.5.1317 DOI Help

Authors: V.s. Coker (University of Manchester) , R.a.d. Pattrick (University of Manchester) , C.i. Pearce (University of Manchester) , Neil Telling (Keele University) , Gerrit Van Der Laan (Diamond Light Source)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Canadian Mineralogist , VOL 46 , PAGES 1317-22

State: Published (Approved)
Published: October 2008

Abstract: Using X-ray absorption spectroscopy (XAS) at the Cu L(2,3) and Co L(2,3) edges, we demonstrate that the valence state of copper in the thiospinel carrollite (CuCo(2)S(4)) is Cu(+) with a d count of Cu d(9.8). The Co has a d count of d(6.4), so that the highly covalent mineral has an electronic formula of Cu(1.2+)(Co(2.4+))(2)(S(1.5-))(4). There is half a hole per atom in the S 3p band (per unit formula); the Co L(2,3) XAS indicates a covalent low-spin electronic structure. These data dispel the notion of the presence of Cu(2+) in carrollite.

Subject Areas: Physics

Instruments: NONE-No attached Diamond beamline