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Book ChapterDOI

Chapter 3 - The Oxide Chemistry of Molybdenum

01 Jan 1994-Studies in Inorganic Chemistry (Elsevier)-Vol. 19, Iss: 42, pp 146-184
About: This article is published in Studies in Inorganic Chemistry.The article was published on 1994-01-01. It has received 19 citations till now. The article focuses on the topics: Molybdenum & Oxide.
Citations
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31 Oct 1956
TL;DR: In this article, a mass spectometric analysis of the vapor in thermodynamic equilibrium with powdered molybdenum trioxide, as sampled from a Knudsen effusion cell, has shown that the vapor phase consists of Mo3O9, Mo4O12 and Mo5O15 molecules.
Abstract: Mass spectometric analysis of the vapor in thermodynamic equilibrium with powdered molybdenum trioxide, as sampled from a Knudsen effusion cell, has shown that the vapor phase consists predominantly of Mo3O9, Mo4O12 and Mo5O15 molecules. Utilizing the Clausius‐Clapeyron equation, individual heats of sublimation have been determined to be 80.5±1.5, 93.6±1.6 and 105.6±3.5 kcal/mole respectively at 850° K. The heats of formation and third law entropies have been evaluated for each of these molecules.

112 citations

Journal ArticleDOI
TL;DR: In this article, the role of 2-aminopyridine (2ampy) in the formation of the different solids under hydrothermal conditions is discussed, and the structures of these materials were established by single-crystal and powder X-ray diffraction techniques.
Abstract: The hydrothermal reaction of an aqueous ammonium heptamolybdate solution with first-row transition metal salts in the presence of 2-aminopyridine at around 180 °C and under autogenous pressure yields several molybdates, such as the 1D chains in (C5N2H7)4Mo8O26 (1), zero-dimensional (C5N2H7)6Mo7O24·3H2O (2), and the first synthesis of Lindgrenite [Cu3Mo2O8(OH)2 (3)] The structures of these materials were established by single-crystal and powder X-ray diffraction techniques. The crystal structures of wolframite-based MnMoO4 (4) and ZnMoO4 (5) were established by powder X-ray diffraction. The role of 2-aminopyridine (2-ampy) in the formation of the different solids under hydrothermal conditions is discussed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

81 citations

Journal ArticleDOI
TL;DR: In this article, a chemical etching method has been developed for restructuring these thermally processed catalysts using a 0.1 M NaOH etchant, where the surface steps, ledges, and terraces are created.
Abstract: Crystalline catalysts of orthorhombic MoO3 have been prepared via a vapor phase deposition method, and their crystallographic structure has been affirmed by XRD and FTIR investigations. A chemical etching method has been developed for restructuring these thermally processed catalysts. Using a 0.1 M NaOH etchant, {001} and {100} plane areas of the catalysts can be significantly increased while surface steps, ledges, and terraces are created. Moreover, alternate crystal plane combinations of either {100} and {010} or the {001} and {010} are observed on crystal edges and rectangular etch pits in the basal planes {010}. Both materials chemistry of MoO3 and etching mechanisms have been studied on the basis of the surface morphological evolution of etching patterns of the catalysts. Technological merits and the processing parameters of this new method have also been identified. Following the findings of the current work, it is believed that the chemically carved surface structures may be crucial for certain MoO...

72 citations

Journal ArticleDOI
TL;DR: In this article, a review of the benefits and methods for interlayer modification of layered transition metal oxides, which include the presence of structural water, solvent cointercalation and exchange, cation exchange, polymers, and small molecules, exfoliation, and exfoliated heterostructures, is presented.
Abstract: Layered transition metal oxides are some of the most important materials for high energy and power density electrochemical energy storage, such as batteries and electrochemical capacitors. These oxides can efficiently store charge via intercalation of ions into the interlayer vacant sites of the bulk material. The interlayer can be tuned to modify the electrochemical environment of the intercalating species to allow improved interfacial charge transfer and/or solid-state diffusion. The ability to fine-tune the solid-state environment for energy storage is highly beneficial for the design of layered oxides for specific mechanisms, including multivalent ion intercalation. This review focuses on the benefits as well as the methods for interlayer modification of layered oxides, which include the presence of structural water, solvent cointercalation and exchange, cation exchange, polymers, and small molecules, exfoliation, and exfoliated heterostructures. These methods are an important design tool for further development of layered oxides for electrochemical energy storage applications.

66 citations

Journal ArticleDOI
TL;DR: In this article, the structural aspects of the crystallographic shear planes and the resulting thermoelectric properties of transition metal oxides with adaptive structures have been investigated with respect to their thermal properties.
Abstract: Thermoelectric devices can help to tackle future challenges in the energy sector through the conversion of waste heat directly into usable electric energy. For a wide applicability low-cost materials with reasonable thermoelectric performances and cost-efficient preparation techniques are required. In this context metal oxides are an interesting class of materials because of their inherent high-temperature stability and relative high sustainability. Their thermoelectric performance, however, needs to be improved for wide application. Compounds with adaptive structures are a very interesting class of materials. A slight reduction of early transition metal oxides generates electrons as charge carriers and crystallographic shear planes as structure motif. The crystallographic shear planes lead to a reduction of intrinsic thermal conductivity. At the same time, the electronic transport properties can be tuned by the degree of reduction. So far only a few transition metal oxides with adaptive structures have been investigated with respect to their thermoelectric properties, leaving much room for improvement. This review gives an overview of thermoelectric oxides, highlights the structural aspects of the crystallographic shear planes and the resulting thermoelectric properties.

50 citations

References
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Journal ArticleDOI
TL;DR: In this article, an x-ray photoelectron and optical investigation of three thin-film transition metal oxides, namely, WO3, MoO3 and V2O5 are reported.
Abstract: Qualitative results of an x‐ray photoelectron and optical investigation of three thin‐film transition‐metal oxides, namely, WO3, MoO3, and V2O5 are reported. Data were obtained on films that were not colored and colored by an electrochromic process. The particular electrochromic coloration process used is electrolytic in nature and employs a sandwich‐structure electrochromic cell and electrolyte pool. The optical spectra show increased absorption in the visible (red) and near‐infrared spectral regions upon coloration. The photoelectron spectra for colored films exhibit a small band near the Fermi level and asymmetric band shapes for metal core‐level bands which are absent in films that are not colored. The new band and the asymmetric band shapes are attributed to the presence of a reduced‐state species caused by the presence of trapped electrons and metal bronze formation. Results from coloration with different electrolyte pools, i.e., H+, Li+, Na+, K+, Cs+, and Mg2+ electrolytes, are reported.

337 citations

Journal ArticleDOI
TL;DR: In this paper, room-temperature lithium insertion into the title framework structures can be represented as Fe 3+ 2 (Mo 6+ O 4 ) 3 → 2n-BuLi Li 2 Fe 2+ 2(Mo 6+, O 4 ), 3 → 6n- BuLi [Li + 12 Fe 0 2 (W 4+O 4 ), 4+

269 citations

Journal ArticleDOI
TL;DR: In this paper, the topochemical lithiation of rutile related MO 2 with n-BuLi and in nonaqueous lithium electrochemical cells is reported, which illustrates the importance of electronic conductivity and cell volume to substantial lithium incorporation.

264 citations

Journal ArticleDOI
TL;DR: In this article, the molybdenum chlorides of MoCl4, α-MoCl3 and MoCl2 (≙Mo6Cl12) in reiner, kristallisierter form were found.
Abstract: Die Molybdanchloride wurden einer erneuten chemischen und physikalischen Untersuchung unterworfen. Die Synthese im Temperaturgefalle lieferte die Verbindungen MoCl4, α-MoCl3 und MoCl2 (≙Mo6Cl12) in reiner, kristallisierter Form. Auf gleichem Wege wurde die neue Verbindung MoCl3,08 („β-MoCl3”) gefunden. Das im festen Zustande dimere MoCl5 verdampft monomolekular (Massenspektrometer). Der thermische Zerfall (Thermogravimetrie, Massenspektrometer) von MoCl3 erfolgt nach wahrend MoCl2 nach . Kristallstrukturuntersuchungen lieferten folgende Informationen: MoCl4 kristallisiert trigonal in einem Schichtengitter mit hexagonal dichter Cl-Packung. Die Mo-Atome besetzen 75% der Metallplatze einer Trichloridstruktur, wobei im Mikrobereich Ordnungszustande auftreten. α-MoCl3 und β-MoCl3 kristallisieren monoklin in Schichtengittern mit kubisch (α) bzw. hexagonal (β) dichter Cl-Packung. Die Mo-Atome sind paarweise als Mo2-Gruppen aneinander gebunden (MoMo = 2,76 A). Mo6Cl12(MoCl2) kristallisiert orthorhombisch. Die Struktur enthalt [Mo6Cl8]-Gruppen, die 2-dimensional unendlich miteinander verknupft sind: {[Mo6Cl8]Cl2}Cl4/2. Die Bindungsabstande MoMo innerhalb der regularen Mo6-Oktaeder betragen 2,61 A. Der Vergleich der Vergleich der Raumbeanspruchung („pro Cl”) zeigt, das diese beim Ubergang von den hoheren Molybdanchloriden zum Mo6Cl12 wegen dessen sperrigen Aufbaus sprunghaft groser wird. Magnetische Messungen liefern fur MoCl5 und MoCl4 nahezu den reinen Spinwert, wahrend die fur α-MoCl3, β-MoCl3 und Mo6Cl12 gemessenen Werte wegen der MoMo-Wechselwirkungen sehr viel kleiner sing. Mo6Br12, Mo6J12, W6Cl12, W6Br12 und W6J12 sind mit Mo6Cl12 isotyp. Chemical and physical properties of the molybdenum chlorides have been reinvestigated. By synthesis in a temperature gradient crystalline samples of MoCl4, α-MoCl3 and MoCl2 (≙Mo6Cl12) were prepared. The new compound MoCl3,08 (“β-MoCl3”) was found in the same way. MoCl5, being dimeric in the solid state, is monomeric in the vapour (mass spectrum). Thermal dissociation (TGA, mass spectrum) of MoCl3 proceeds according to 2 MoCl3 MoCl2 + MoCl4,g; P(MoCl4, 800°C) = 12 atm, whereas MoCl2 decomposes according to 2 MoCl2 Mo + MoCl4,g; P(MoCl4, 860°C) = 0,4 atm. Crystal structure analyses submitted the following informations: MoCl4 (trigonal) forms a layer structure with a hexagonal closepacked Cl sequence. Three quarters of the metal positions of a corresponding trichloride structure are randomly occupied by Mo atoms. α-MoCl3 and β-MoCl3 (both monoclinic) have layer structures with cubic (α) and hexagonal (β) close Cl arrangements and with certain adjacent octahedral holes occupied by molybdenum forming Mo2 pairs (MoMo = 2,76 A). Mo6Cl12 (MoCl2) (orthorhombic) is built up by [Mo6Cl8] clusters, linked to a 2-dimensional arrangement: {[Mo6Cl8]Cl2}Cl4/2. The MoMo distance in the regular octahedral Me6 group is 2,61 A. Comparing the volumes per one Cl atom, it can be seen, that these are abruptly increased on going from the molybdenum chlorides of higher oxidation state to Mo6Cl12 with its cumbersome structure. The magnetic moments of MoCl5 and MoCl4 nearly correspond to the spin-only values, whereas the moments of α-MoCl3, β-MoCl3, and Mo6Cl12 are much smaller, caused by MoMo interaction. Mo6Br12, Mo6I12, W6Cl12, W6Br12, and W6J12 are isotypic with Mo6Cl12.

225 citations