On the synthesis and structure of the copper-molybdenum oxide bronzes: Monoclinic Cu2Mo10O30 and orthorhombic CuMo9O26

M. Ørndrup Nielsen; P. Brilner Lund; V. McKee; D. B. Ravnsbæk; T. E. Warner; C. Wegeberg

doi:10.1016/j.jssc.2020.121259

On the synthesis and structure of the copper-molybdenum oxide bronzes: Monoclinic Cu₂Mo₁₀O₃₀ and orthorhombic CuMo₉O₂₆

M. Ørndrup Nielsen
, P. Brilner Lund
, V. McKee
, D. B. Ravnsbæk
, T. E. Warner^*
, C. Wegeberg

^*Kontaktforfatter

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › peer review

Abstract

Cu₂Mo₁₀O₃₀ was prepared as a monophasic material comprising dark blue platy crystals by reacting Cu with MoO₃ under argon at 550 °C. Single-crystal X-ray diffractometry showed that Cu₂Mo₁₀O₃₀ is a stoichiometric compound that crystallizes with a monoclinic (C2/c) cell: a = 16.6359(6); b = 9.3112(3); c = 27.1597(9) Å; β = 102.621(3)° (Z = 8). Electron paramagnetic resonance spectroscopy revealed that Cu₂Mo₁₀O₃₀ displays mixed-valency; (Cu^I _2−xCu^II _x)(Mo^V _2+xMo^VI _8−x)O₃₀ (0 ≪ x ≤ 2). Differential scanning calorimetry and in situ high-temperature powder X-ray diffractometry showed that Cu₂Mo₁₀O₃₀ decomposes ≳550 °C under an inert atmosphere. Dark blue acicular crystals of CuMo₉O₂₆ were discovered as a side-product in materials prepared inside evacuated glass ampoules at 500 °C. Single-crystal X-ray diffractometry showed these to crystallize with an orthorhombic (Pmmn) cell: a = 3.74190(10); b = 26.4941(4); c = 9.15300(10) Å; (Z = 2). Rietveld refinement of the powder X-ray diffraction data for these materials revealed Cu₂Mo₁₀O₃₀ with minor CuMo₉O₂₆ and ‘Cu_0.1MoO₃’.

Originalsprog	Engelsk
Artikelnummer	121259
Tidsskrift	Journal of Solid State Chemistry
Vol/bind	285
Antal sider	8
ISSN	0022-4596
DOI	https://doi.org/10.1016/j.jssc.2020.121259
Status	Udgivet - maj 2020

Finansiering

The authors are grateful to Frederik W. Lund for technical assistance with the HT-PXRD, Christine McKenzie for single-crystal XRD data collection, and to Torben H. Jensen and Danny Kyrping for technical assistance with the furnace. The authors also thank Eivind Skou for reading and commenting on the manuscript. We thank the Independent Research Fund Denmark (grant 4184-00143A) for funding the research. We also thank the Carlsberg Foundation, Denmark, (grant CF17-0823) for funding to DRB and towards the single crystal X-ray diffractometer (grant CF15-0675).

Dokumenter og links

10.1016/j.jssc.2020.121259

SDU link

Tjek adgangen til materialet i Syddansk Universitetsbiblioteks søgemaskine

Citationsformater

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title = "On the synthesis and structure of the copper-molybdenum oxide bronzes: Monoclinic Cu2Mo10O30 and orthorhombic CuMo9O26",

abstract = "Cu2Mo10O30 was prepared as a monophasic material comprising dark blue platy crystals by reacting Cu with MoO3 under argon at 550 °C. Single-crystal X-ray diffractometry showed that Cu2Mo10O30 is a stoichiometric compound that crystallizes with a monoclinic (C2/c) cell: a = 16.6359(6); b = 9.3112(3); c = 27.1597(9) {\AA}; β = 102.621(3)° (Z = 8). Electron paramagnetic resonance spectroscopy revealed that Cu2Mo10O30 displays mixed-valency; (CuI 2−xCuII x)(MoV 2+xMoVI 8−x)O30 (0 ≪ x ≤ 2). Differential scanning calorimetry and in situ high-temperature powder X-ray diffractometry showed that Cu2Mo10O30 decomposes ≳550 °C under an inert atmosphere. Dark blue acicular crystals of CuMo9O26 were discovered as a side-product in materials prepared inside evacuated glass ampoules at 500 °C. Single-crystal X-ray diffractometry showed these to crystallize with an orthorhombic (Pmmn) cell: a = 3.74190(10); b = 26.4941(4); c = 9.15300(10) {\AA}; (Z = 2). Rietveld refinement of the powder X-ray diffraction data for these materials revealed Cu2Mo10O30 with minor CuMo9O26 and {\textquoteleft}Cu0.1MoO3{\textquoteright}.",

keywords = "Chemical synthesis, Crystal structure, Differential scanning calorimetry (DSC), Electron paramagnetic resonance spectroscopy, Oxides, X-ray diffraction",

author = "Nielsen, \{M. {\O}rndrup\} and Lund, \{P. Brilner\} and V. McKee and Ravnsb{\ae}k, \{D. B.\} and Warner, \{T. E.\} and C. Wegeberg",

year = "2020",

month = may,

doi = "10.1016/j.jssc.2020.121259",

language = "English",

volume = "285",

journal = "Journal of Solid State Chemistry",

issn = "0022-4596",

publisher = "Academic Press",

}

TY - JOUR

T1 - On the synthesis and structure of the copper-molybdenum oxide bronzes

T2 - Monoclinic Cu2Mo10O30 and orthorhombic CuMo9O26

AU - Nielsen, M. Ørndrup

AU - Lund, P. Brilner

AU - McKee, V.

AU - Ravnsbæk, D. B.

AU - Warner, T. E.

AU - Wegeberg, C.

PY - 2020/5

Y1 - 2020/5

N2 - Cu2Mo10O30 was prepared as a monophasic material comprising dark blue platy crystals by reacting Cu with MoO3 under argon at 550 °C. Single-crystal X-ray diffractometry showed that Cu2Mo10O30 is a stoichiometric compound that crystallizes with a monoclinic (C2/c) cell: a = 16.6359(6); b = 9.3112(3); c = 27.1597(9) Å; β = 102.621(3)° (Z = 8). Electron paramagnetic resonance spectroscopy revealed that Cu2Mo10O30 displays mixed-valency; (CuI 2−xCuII x)(MoV 2+xMoVI 8−x)O30 (0 ≪ x ≤ 2). Differential scanning calorimetry and in situ high-temperature powder X-ray diffractometry showed that Cu2Mo10O30 decomposes ≳550 °C under an inert atmosphere. Dark blue acicular crystals of CuMo9O26 were discovered as a side-product in materials prepared inside evacuated glass ampoules at 500 °C. Single-crystal X-ray diffractometry showed these to crystallize with an orthorhombic (Pmmn) cell: a = 3.74190(10); b = 26.4941(4); c = 9.15300(10) Å; (Z = 2). Rietveld refinement of the powder X-ray diffraction data for these materials revealed Cu2Mo10O30 with minor CuMo9O26 and ‘Cu0.1MoO3’.

AB - Cu2Mo10O30 was prepared as a monophasic material comprising dark blue platy crystals by reacting Cu with MoO3 under argon at 550 °C. Single-crystal X-ray diffractometry showed that Cu2Mo10O30 is a stoichiometric compound that crystallizes with a monoclinic (C2/c) cell: a = 16.6359(6); b = 9.3112(3); c = 27.1597(9) Å; β = 102.621(3)° (Z = 8). Electron paramagnetic resonance spectroscopy revealed that Cu2Mo10O30 displays mixed-valency; (CuI 2−xCuII x)(MoV 2+xMoVI 8−x)O30 (0 ≪ x ≤ 2). Differential scanning calorimetry and in situ high-temperature powder X-ray diffractometry showed that Cu2Mo10O30 decomposes ≳550 °C under an inert atmosphere. Dark blue acicular crystals of CuMo9O26 were discovered as a side-product in materials prepared inside evacuated glass ampoules at 500 °C. Single-crystal X-ray diffractometry showed these to crystallize with an orthorhombic (Pmmn) cell: a = 3.74190(10); b = 26.4941(4); c = 9.15300(10) Å; (Z = 2). Rietveld refinement of the powder X-ray diffraction data for these materials revealed Cu2Mo10O30 with minor CuMo9O26 and ‘Cu0.1MoO3’.

KW - Chemical synthesis

KW - Crystal structure

KW - Differential scanning calorimetry (DSC)

KW - Electron paramagnetic resonance spectroscopy

KW - Oxides

KW - X-ray diffraction

U2 - 10.1016/j.jssc.2020.121259

DO - 10.1016/j.jssc.2020.121259

M3 - Journal article

AN - SCOPUS:85079610987

SN - 0022-4596

VL - 285

JO - Journal of Solid State Chemistry

JF - Journal of Solid State Chemistry

M1 - 121259

ER -