X-ray photoelectron spectroscopic study of copper minerals

Nakai, Izumi; Izawa, Mihoko; Sugitani, Yoshinori; Niwa, Yoshio; Nagashima, Kōzō

doi:10.2465/minerj.8.135

Cited by 186 publications

(35 citation statements)

References 6 publications

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“…The S L-edge spectra (solid curves) are aligned to zero by subtracting the XPS S 2p312 BE that is 161.1 eV for chalcopyrite and cubanite, and 161.5 for bornite (Nakai et al 1978). The S K-edge spectra (dash curves) are correlated with the L-edge spectra by the S Kcq XES at 2307.8 eV.…”

Section: Results and Spectral Assignmentsmentioning

confidence: 99%

“…Due to its importance in technology and industry, the bonding and electronic structure of chalcopyrite (CuFeS2) has been extensively studied by qualitative MO/energy band structure calculations (Tossell 1978;Tossell 1980, 1983), a self-consistentcharge discrete-variation Xc~ calculation (Hamajima et al 1981), x-ray photoelectron spectra (XPS) (Nakai et al 1978) and S Ko x-ray emission spectra (XES) (Natbutt 1974). Tossell ef al.…”

Section: Introductionmentioning

confidence: 99%

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S K- and L-edge XANES and electronic structure of some copper sulfide minerals

Bancroft

Kasrai

et al. 1994

Phys Chem Minerals

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Abstract. The S K-and L-edge x-ray absorption nearedge structures (XANES) of low bornite, cubanite, chalcocite, covellite, enargite and tetrahedrite have been measured with synchrotron radiation. The near-edge features are interpreted based on comparison with the S K-and L-edge spectra of chalcopyrite and a MO/energy band structure model. The XANES spectra of these sulfides reflect the DOS of unoccupied S s-, p-and d-like states near and above the Fermi level. In tetrahedral Cu-Fe sulfides, the Fe 3+ 3d crystal field band has much more significant DOS of unoccupied S 3p-and 3 s-like states than the Cu § 3d crystal field band. For Cu sulfides, the Cu § 3d crystal field band has the higher DOS of S 3p-and 3 s-like states in tetrahedral structure than in structures with the triangular CuS3 cluster. The shifts in both S K-and L-edges correlate approximately linearly with the energy gap.

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Section: Results and Spectral Assignmentsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

S K- and L-edge XANES and electronic structure of some copper sulfide minerals

Bancroft

Kasrai

et al. 1994

Phys Chem Minerals

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“…3A) includes a strong singlet peak, but no shakeup satellite contribution between about 940 and 945 eV, indicating that the oxidation state of Cu in bornite is 1+ (McIntyre & Cook 1975, Nakai et al 1977, Deroubaix & Marcus 1992. The Cu 2p 3/2 spectrum is distinctly asymmetric, displaying one intense peak located at about 932.2 eV, and a weak high-binding-energy tail that extends to about 936 eV (Fig.…”

Section: The Cu 2p 3/2 Bulk Signalmentioning

confidence: 99%

“…The BE of the Cu 2p peak is similar to that in other copper and copper-iron sulfi des (McIntyre & Cook 1975, Nakai et al 1977, Deroubaix & Marcus 1992, Harmer et al 2004. The peak's FWHM and G/L contribution was adjusted to fi t the low-binding-energy side of the peak.…”

Section: The Cu 2p 3/2 Bulk Signalmentioning

confidence: 99%

Reconstruction of Fracture Surfaces on Bornite

Harmer¹,

Pratt²,

Nesbitt³

et al. 2005

The Canadian Mineralogist

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Synchrotron-radiation X-ray Photoelectron Spectroscopy (SRXPS) and conventional X-ray Photoelectron Spectroscopy (XPS) have been used to study a pristine fracture-surface of bornite (Cu 5 FeS 4 ). Comparisons of these high-resolution spectra reveal, for the fi rst time, four distinct contributions to the S 2p spectra. The main symmetric peak of the S 2p spectra for bornite is located at about 163.51 eV and is derived from bulk S atoms. The broad nature of the bulk contribution, in comparison to other 3d transition-metal sulfi des such as chalcopyrite, is consistent with the presence of eight crystallographically distinct S sites within the structure, these sites being energetically as well as structurally distinct. A second peak located at 160.1 eV is attributed to a surface monomeric species (S 2-) of lower coordination. The presence of a second broad surface-contribution at 162.1 eV likely represents surface polymeric species (S n 2-). The presence of surface sulfur polymers indicates the stabilization of the bornite surface upon fracture through formation of S-S bonds. These data suggest that surface polymers form where polar surfaces are exposed during conchoidal fracture. A high binding-energy tail was observed at about 163 eV and extends to about 166 eV, the origin of which is uncertain. Conventional XPS Cu 2p and Fe 2p spectra collected from a pristine fracture-surface of bornite reveal a Cu 1+ peak centered at about 932.2 eV and a high-spin Fe 3+ peak centered at 708 eV.Keywords: X-ray photoelectron spectroscopy, bornite, sulfi des, iron, copper, surface speciation. SOMMAIRENous avons utilisé la spectroscopie photo-électronique des rayons X en rayonnement synchrotron (SRXPS) et la spectroscopie photo-électronique des rayons X conventionnelle (XPS) pour étudier une surface fracturée très fraiche de la bornite (Cu 5 FeS 4 ). A la suite de comparaisons de ces spectres à résolution élevée, nous démontrons pour la première fois quatre contributions distinctes au spectre de l'atome S 2p. Le pic symétrique principal du spectre de S 2p de la bornite est situé à environ 163.51 eV, et il est dérivé de la masse globale des atomes de S. La nature généralisée de cette contribution globale, par rapport aux autres sulfures de métaux de transition 3d tels la chalcopyrite, concorde avec la présence de huit sites S cristallographiquement distincts dans la structure, tous ces sites étant aussi énergétiquement et structuralement distincts. Un second pic situé à 160.1 eV est attribuable à une espèce de surface monomérique (S

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“…The qualitative assignments of the S near-edge structures of spahlerite are summarized in Table 1. M6ssbauer spectroscopy of 57Fe and 119Sn (Yamanaka and Kato 1976) and x-ray photoelectron spectroscopy (XPS) of Cu (Nakai et al 1978) consistently indicate the configuration Cu2 + 1Fe / + Sn 4 + $42 -for stannite. At present no MO/energy band calculation for stannite is available.…”

Section: Peaksmentioning

confidence: 99%

Sulfur K- and L-edge X-ray absorption spectroscopy of sphalerite, chalcopyrite and stannite

Bancroft

Kasrai

et al. 1994

Phys Chem Minerals

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Abstract. Sulfur K-edge x-ray absorption spectra (XANES and EXAFS) and L-edge XANES of sphalerite (ZnS), chalcopyrite (CuFeS2) and stannite (Cu2FeSnS4) have been recorded using synchrotron radiation. The K-and L-edge XANES features are interpreted using a qualitative MO/energy band structure model. The densities of unoccupied states at the conduction bands of sphalerite, chalcopyrite and stannite are determined using S K-and L-edge XANES features (up to 15 eV above the edge), combined with published metal K-edge XANES. The S K-and L-edge XANES also indicate that, for sphalerite, the Fe 2 § 3 d band at the fundamental gap has little or no bonding hybridization with S 3p and S 3s orbitals; for chalcopyrite, the Cu § 3d and Fe 3+ 3d bands have strong mixing with S 3p and S 3s states, while for stannite the Cu § 3 d band strongly hybridizes with S 3 p and S 3 s orbitals, but the Fe 2 § 3 d band does not. The post-edge XANES features (15-50 eV above the edge) of sphalerite, chalcopyrite and stannite are similar. These features are related to the tetrahedral coordination of sulfur in all these structures, and interpreted by a multiple scattering model. The resonance energies from both the K-edge and L-edge XANES for these minerals are well correlated with reciprocal interatomic distances and lattice spaces. Sulfur K-edge EXAFS analyses using Fourier transform and curve fitting procedures are presented. Comparison of the structural parameters from EXAFS with x-ray structure data shows that the first shell bond distances (BD) from EXAFS are usually accurate to _+ 0.02/~, and that coordination numbers (CN) are generally accurate to + 20 percent. For sphalerite, EXAFS analysis yields the structure parameters for the first three neighbour shells around a sulfur atom; the BD and CN even for the third shell are in close agreement with the x-ray structure, and the Debye-Waller term decreases from the first shell to the third shell. It is shown that sphalerite (ZnS) is a good model compound for EXAFS analysis of sulfur in chalcogenide glasses and metalloproteins.

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X-ray photoelectron spectroscopic study of copper minerals

Cited by 186 publications

References 6 publications

S K- and L-edge XANES and electronic structure of some copper sulfide minerals

S K- and L-edge XANES and electronic structure of some copper sulfide minerals

Reconstruction of Fracture Surfaces on Bornite

Sulfur K- and L-edge X-ray absorption spectroscopy of sphalerite, chalcopyrite and stannite

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