Molybdenum dioxide
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Molybdenum dioxide is the chemical compound with the formula MoO2. It is a violet-colored solid and is a metallic conductor. The mineralogical form of this compound is called tugarinovite, and is only very rarely found.
Structure
It crystallizes in a monoclinic cell, and has a distorted rutile, (TiO2) crystal structure. In TiO2 the oxide anions are close packed and titanium atoms occupy half of the octahedral interstices (holes). In MoO2 the octahedra are distorted, the Mo atoms are off-centre, leading to alternating short and long Mo – Mo distances and Mo-Mo bonding. The short Mo – Mo distance is 251 pm which is less than the Mo – Mo distance in the metal, 272.5 pm. The bond length is shorter than would be expected for a single bond. The bonding is complex and involves a delocalisation of some of the Mo electrons in a conductance band accounting for the metallic conductivity.[1]
Preparation
MoO2 can be prepared :
- by reduction of MoO3 with Mo over the course of 70 hours at Script error: No such module "convert".. The tungsten analogue, WO2, is prepared similarly.
- 2 MoO3 + Mo → 3 MoO2
Single crystals are obtained by chemical transport using iodine. Iodine reversibly converts MoO2 into the volatile species MoO2I2.[3]
Uses
Molybdenum dioxide is a constituent of "technical molybdenum trioxide" produced during the industrial processing of MoS2:[4][5]
- 2 MoS2 + 7 O2 → 2 MoO3 + 4 SO2
- MoS2 + 6 MoO3 → 7 MoO2 + 2 SO2
- 2 MoO2 + O2 → 2 MoO3
MoO2 has been reported as catalysing the dehydrogenation of alcohols,[6] the reformation of hydrocarbons[7] and biodiesel.[8] Molybdenum nano-wires have been produced by reducing MoO2 deposited on graphite.[9] Molybdenum dioxide has also been suggested as possible anode material for Li-ion batteries.[10][11]
References
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- ↑ Oxides: Solid state chemistry McCarroll W.H. Encyclopedia of Inorganic Chemistry Ed R. Bruce King, (1994), John Wiley & sons Template:ISBN
- ↑ Script error: No such module "citation/CS1".
- ↑ Conroy, L. E.; Ben-Dor, L. "Molybdenum(IV) Oxide and Tungsten(IV) Oxides Single-Crystals" Inorganic Syntheses 1995, volume 30, pp. 105–107. Template:ISBN
- ↑ Metallurgical furnaces Jorg Grzella, Peter Sturm, Joachim Kruger, Markus A. Reuter, Carina Kogler, Thomas Probst, Ullmans Encyclopedia of Industrial Chemistry
- ↑ "Thermal Analysis and Kinetics of Oxidation of Molybdenum Sulfides" Y. Shigegaki, S.K. Basu, M.Wakihara and M. Taniguchi, J. Therm. Analysis 34 (1988), 1427-1440
- ↑ A. A. Balandin and I. D. Rozhdestvenskaya, Russian Chemical Bulletin, 8, 11, (1959), 1573 Script error: No such module "CS1 identifiers".
- ↑ Molybdenum based catalysts. I. MoO2 as the active species in the reforming of hydrocarbons A. Katrib, P. Leflaive, L. Hilaire and G. Maire Catalysis Letters, 38, 1–2, (1996) Script error: No such module "CS1 identifiers".
- ↑ Catalytic partial oxidation of a biodiesel surrogate over molybdenum dioxide, C.M. Cuba-Torres, et al, Fuel (2015), Script error: No such module "CS1 identifiers".
- ↑ Synthesis of Molybdenum Nanowires with Millimeter-Scale Lengths Using Electrochemical Step Edge Decoration M. P. Zach, K. Inazu, K. H. Ng, J. C. Hemminger, and R. M. Penner Chem. Mater. (2002),14, 3206 Script error: No such module "CS1 identifiers".
- ↑ Script error: No such module "Citation/CS1".
- ↑ Script error: No such module "Citation/CS1".
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