The oxidation state of copper and cobalt in carrollite, CuCo2S4

Richard A D Pattrick; Victoria S. Coker; Carolyn I. Pearce; Neil D. Telling; Gerrit van der Laan

doi:10.3749/canmin.46.5.1317

The oxidation state of copper and cobalt in carrollite, CuCo2S4

Richard A D Pattrick, Victoria S. Coker, Carolyn I. Pearce, Neil D. Telling, Gerrit van der Laan

Dalton Nuclear Institute

Research output: Contribution to journal › Article › peer-review

Abstract

Using X-ray absorption spectroscopy (XAS) at the Cu L2,3 and Co L2,3 edges, we demonstrate that the valence state of copper in the thiospinel carrollite (CUCo2S4) is Cu+ with a d count of Cu d9.8. The Co has a d count of d6.4, so that the highly covalent mineral has an electronic formula of Cu1.2+ (Co2.4+)2 (S1.5-)4. There is half a hole per atom in the S 3p band (per unit formula); the Co L2,3 XAS indicates a covalent low-spin electronic structure. These data dispel the notion of the presence of Cu2+ in carrollite.

Original language	English
Pages (from-to)	1317-1322
Number of pages	5
Journal	Canadian Mineralogist
Volume	46
Issue number	5
DOIs	https://doi.org/10.3749/canmin.46.5.1317
Publication status	Published - Oct 2008

Keywords

Carrollite
L-edge
Low-spin electronic structure
Oxidation state
Thiospinel
X-ray absorption spectroscopy

Research Beacons, Institutes and Platforms

Dalton Nuclear Institute

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10.3749/canmin.46.5.1317

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title = "The oxidation state of copper and cobalt in carrollite, CuCo2S4",

abstract = "Using X-ray absorption spectroscopy (XAS) at the Cu L2,3 and Co L2,3 edges, we demonstrate that the valence state of copper in the thiospinel carrollite (CUCo2S4) is Cu+ with a d count of Cu d9.8. The Co has a d count of d6.4, so that the highly covalent mineral has an electronic formula of Cu1.2+ (Co2.4+)2 (S1.5-)4. There is half a hole per atom in the S 3p band (per unit formula); the Co L2,3 XAS indicates a covalent low-spin electronic structure. These data dispel the notion of the presence of Cu2+ in carrollite.",

keywords = "Carrollite, L-edge, Low-spin electronic structure, Oxidation state, Thiospinel, X-ray absorption spectroscopy",

author = "Pattrick, {Richard A D} and Coker, {Victoria S.} and Pearce, {Carolyn I.} and Telling, {Neil D.} and {van der Laan}, Gerrit",

note = "Pattrick, Richard A. D. Coker, Victoria S. Pearce, Carolyn I. Telling, Neil D. van der Laan, Gerrit 24 MINERALOGICAL ASSOC CANADA OTTAWA Part 5 379SV",

year = "2008",

month = oct,

doi = "10.3749/canmin.46.5.1317",

language = "English",

volume = "46",

pages = "1317--1322",

journal = "Canadian Mineralogist",

issn = "0008-4476",

publisher = "Mineralogical Association of Canada",

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TY - JOUR

T1 - The oxidation state of copper and cobalt in carrollite, CuCo2S4

AU - Pattrick, Richard A D

AU - Coker, Victoria S.

AU - Pearce, Carolyn I.

AU - Telling, Neil D.

AU - van der Laan, Gerrit

N1 - Pattrick, Richard A. D. Coker, Victoria S. Pearce, Carolyn I. Telling, Neil D. van der Laan, Gerrit 24 MINERALOGICAL ASSOC CANADA OTTAWA Part 5 379SV

PY - 2008/10

Y1 - 2008/10

N2 - Using X-ray absorption spectroscopy (XAS) at the Cu L2,3 and Co L2,3 edges, we demonstrate that the valence state of copper in the thiospinel carrollite (CUCo2S4) is Cu+ with a d count of Cu d9.8. The Co has a d count of d6.4, so that the highly covalent mineral has an electronic formula of Cu1.2+ (Co2.4+)2 (S1.5-)4. There is half a hole per atom in the S 3p band (per unit formula); the Co L2,3 XAS indicates a covalent low-spin electronic structure. These data dispel the notion of the presence of Cu2+ in carrollite.

AB - Using X-ray absorption spectroscopy (XAS) at the Cu L2,3 and Co L2,3 edges, we demonstrate that the valence state of copper in the thiospinel carrollite (CUCo2S4) is Cu+ with a d count of Cu d9.8. The Co has a d count of d6.4, so that the highly covalent mineral has an electronic formula of Cu1.2+ (Co2.4+)2 (S1.5-)4. There is half a hole per atom in the S 3p band (per unit formula); the Co L2,3 XAS indicates a covalent low-spin electronic structure. These data dispel the notion of the presence of Cu2+ in carrollite.

KW - Carrollite

KW - L-edge

KW - Low-spin electronic structure

KW - Oxidation state

KW - Thiospinel

KW - X-ray absorption spectroscopy

U2 - 10.3749/canmin.46.5.1317

DO - 10.3749/canmin.46.5.1317

M3 - Article

SN - 0008-4476

VL - 46

SP - 1317

EP - 1322

JO - Canadian Mineralogist

JF - Canadian Mineralogist

IS - 5

ER -

The oxidation state of copper and cobalt in carrollite, CuCo2S4

Abstract

Keywords

Research Beacons, Institutes and Platforms

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