Ion-selective sensors based on molybdenum bronzes

New pH- and sodium ion-sensitive metal-oxide-type sensors have been developed and tested with a direct solid state contact method. Performance was demonstrated at ambient temperature with single crystals of several molybdenum bronzes (i.e. Na_0.9Mo₆O₁₇, Li_0.9Mo₆O₁₇, Li_0.33MoO₃ and K_0.3MoO₃). The pH sensors with Na-molybdenum-oxide bronzes show near ideal Nernstian behavior in the pH range 3–9. The response is not affected by the direction of the pH change. The response time of most molybdenum bronze pH sensors is less than 5 s for 90% response. The sodium molybdenum bronze sensor responded reproducibly and fast to changes of Na⁺ concentration in the range 1–10^–4 mol dm^–3. Cross sensitivity tests to other ions such as H⁺ or K⁺ have shown that the new sodium ion sensor may be used when the concentration of other ions is an order of magnitude smaller than the Na⁺ concentration. pH sensors with single crystals of molybdenum oxide bronzes can be used to follow pH titrations. Electronic Publication     

Exploratory growth in the Li2MoO4-MoO3 system for the next crystal generation of heat-scintillation cryogenic bolometers

In this work, we report on the Czochralski growth of Li₂MoO₄ crystals up to 230 g for heat-scintillation cryogenic bolometers likely to be used in astroparticle physics and neutron spectroscopy. Their transmission properties, radiopurity levels and detector behavior characterizations were carried out in order to validate the crystal growth process. The melting characteristics, the partition coefficients of a broad range of impurities, the thermal expansion (lattice parameters and dilatometry) and specific heat properties of the crystals were measured, over a broad temperature range for the last two, providing new data likely to be used in crystal growth process numerical simulations. We also investigated the crystal growth of Li₄Mo₅O₁₇ and determined its melting behavior and specific heat. The physical properties directly relevant to heat-scintillation cryogenic bolometers of Li₂MoO₄ and Li₄Mo₅O₁₇ are discussed in the context of the current materials developed for such applications.     

Structure determination of low-dimensional conductor sodium molybdenum purple bronze Na0.9Mo6O17

Structure determination of the molybdenum purple bronze Na_0.9Mo₆O₁₇ is carried out by single-crystal X-ray diffraction. The crystal is monoclinic with space group A2 and the lattice constants are a = 12.983(2), b = 5.518(1), c = 9.591(2) Å, β = 89.94(1)°, Z = 2. Full-matrix least-squares refinement gives the final values of R(F) = 0.028 and R_w(F) = 0.040 for 1484 independent reflections, in which the occupancy factor of the sodium atom becomes 0.899(12). The present structure is built up of the linkage of the MoO₄ and MoO₆ polyhedra. There are slabs which consist of four layers of distorted MoO₆ octahedra sharing corners. Both the structure and the molybdenum valence distribution estimated from the MoO bond lengths are considered to lead to the two-dimensional electronic transport. This structure is compared with those of other members of molybdenum purple bronzes, K_0.9Mo₆O₁₇ and Li_0.9Mo₆O₁₇. The difference of the electronic properties among these compounds can be well understood on the basis of their structural characteristics.     

Quasi-two-dimensional electronic properties of the sodium molybdenum bronze,Na0.9Mo6O17

Four probe electrical resistivity measurements between 1.5 and 300 K were made on single crystals of the violet-red bronze Na_0.9Mo₆O₁₇ grown by a temperature gradient flux technique. The temperature variation of the resistivity shows metallic conductivity and highly anisotropic behavior similar to K_0.9Mo₆O₁₇ and Li_0.9Mo₆O₁₇. The room-temperature resistivity, measured in the direction parallel to the plate axis, is 3.0 × 10^?3 Ω cm and perpendicular to that axis it is 0.21 Ω cm. A transition observed at ～88 K is possibly related to the onset of a charge density wave. The temperature variation of the susceptibility show Pauli paramagnetic behavior at high temperature, and highly anomalous behavior in the vicinity of the transition at low temperatures.     

Low-temperature synthetic route based on the amorphous nature of giant species for preparation of lower valence oxides

We examined low-temperature synthetic route based on the amorphous nature of giant species to succeed to prepare Cs blue bronze (Cs_0.3MoO₃), which has never obtained by usual high-temperature methods, at ca. 680 K. Solid solutions (K_1−xRb_x)_0.28MoO₃ and (Li_1−xNa_x)_0.9Mo₆O₁₇ were also obtained at lower temperatures (ca. 670 K). For the latter system consisting of non-isostructural end members, Li_0.9Mo₆O₁₇-structure type solid solution was formed even when 0.25<x<0.70, unlike the case by the usual high-temperature methods. Metastable mixed oxides Ln₂Mo₃O₉ (Ln=La, Gd) were obtained, but not as single phases.     

Kryometrische Untersuchungen. IV. Lösungen von oxidischen Mo6+- und Cr6+-Verbindungen in geschmolzenem K2Cr2O7 und KNO3

The depression of freezing point of molten K₂Cr₂O₇ and KNO₃ as solvents was measured after addition of small concentrations of the following compounds: to K₂Cr₂O₇: MoO₃, CrO₃, (NH₄)₂CrO₄, K₂MoO₄, Na₂MoO₄, Li₂MoO₄, and Na₂Mo₂O₇, respectively; to KNO₃: CrO₃, (NH₄)₂Cr₂O₇ K₂Cr₂O₇, K₂CrO₄ and MoO₃, (NH₄)₆(Mo₇O₂₄) · 4 H₂O, K₂Mo₂O₇, K₂MoO₄, Na₂MoO₄ and Li₂MoO₄, respectively. It could be concluded from the measured values of the freezing point depression if a reaction between solvent and solute took place.     

HRTEM and neutron diffraction study of LixMo5O17: From the ribbon (x=5) structure to the rock salt (x=12) structure

Structure determination of the fully intercalated phase Li₁₂Mo₅O₁₇ and of the deintercalated oxide Li₅Mo₅O₁₇ has been carried out by electron microscopy and neutron powder diffraction. The reversible topotactic transformation between the ordered rock salt structure of the former and the ribbon structure of the latter (closely related to that of Li₄Mo₅O₁₇) is explained on the following basis: both structures can be described as strips built up as an assembly of infinite ribbons of MoO₆ octahedra that are five octahedra thick, and that differ by slight displacements of the octahedral ribbons. We show that the electrochemical behavior of the Li_xMo₅O₁₇ system is based on two sorts of Li⁺ sites; those that are located within the strips between the ribbons, and those that are located at the border of the strips. The high rate of Li intercalation in this oxide and its reversibility are discussed in terms of its peculiar structure.     

Non-stoichiometric molybdenum oxides as cathodes for lithium cells: Part I. Primary batteries

Some non-stoichiometric Mo oxides have been tested as cathodes for primary Li cells. Their performance has been evaluated as a function of current density, electrolyte, temperature, cathode porosity and formulation. Specific capacities exceeding 0.4·Ah g^?1 could be reached at low rates. As found with MoO₃, these oxides give rise to the formation of ternary phases of the type Li_myMo_mO_3m?1. Li⁺ insertion in the lattices allows structure retention for Li/Mo ratios lower than 0.7–0.8, whereas higher Li⁺ contents result in the appearance of new phases.     

On magnetic properties of some molybdenum oxides

The temperature dependence of the magnetic susceptibility for the microcrystalline compounds MoO₂, η-Mo₄O₁₁, γ-Mo₄O₁₁, Mo₁₇O₄₇, Mo₈O₂₃, Mo₉O₂₆, and Mo₁₈O₂₆, respectively, has been investigated between 77 and 550 K at various external fields. The susceptibility increases slightly with temperature for all solids. At low temperatures the changes are more pronounced for η-Mo₄O₁₁, γ-Mo₄O₁₁, Mo₁₇O₄₇, and Mo₁₈O₅₂. The deviations from stoichiometry and the related changes in the concentration of charge carrier have a large influence on the values of the susceptibility. Furthermore, some indications of anistotropy were found.     

Phase relations in the cupric molybdates-cuprous molybdates system

It has been found that the mechanism of oxidation of cuprous molybdates and reduction of cupric molybdates is different in different temperature ranges. Below 460°C Cu₃Mo₂O₉ is reduced by hydrogen directly to Cu₆Mo₄O₁₅, and CuMoO₄ disproportionates to a mixture of Cu₆Mo₄O₁₅ and Cu₂Mo₃O₁₀, metallic copper and MoO₂ being the common final products in both cases. Oxidation of Cu₂Mo₃O₁₀, Cu_4?xMo₃O₁₂, and Cu₆Mo₄O₁₅ results in formation of CuMoO₄ in the mixture with MoO₃ or CuO, depending on the stoichiometry of the initial salt. The consecutive reaction 2CuMoO₄ + CuO → Cu₃Mo₂O₉ proceeds only at higher temperatures. Above 460°C liquid phases appear in the system. The final products of cupric molybdate reduction in this range are the same (MoO₂ and Cu) but “intermediary products” appear (Cu_4?xMo₃O₁₂ for Cu₃Mo₂O₉ and mixtures of Cu₂Mo₃O₁₀ with Cu₃Mo₂O₉ and Cu₆Mo₄O₁₅ for CuMoO₄) resulting from crystallization equilibria frozen on cooling. Thermal decomposition (with simultaneous melting) of Cu₃Mo₂O₉ and CuMoO₄ begins under 10^?1 Torr O₂ at about 690°C leading (if cooled) to the same products as that of mild reduction with hydrogen in the upper temperature range. The equilibrium in the univariant system solid Cu₃Mo₂O₉-liquid Cu₆Mo₄O₁₅-gaseous O₂ is described in the temperature range 700–855°C by the equation . The more complex mechanism of thermal decomposition of CuMoO₄ is also described.     

Koexistenzbeziehungen,Darstellung und Eigenschaften ternärer Phasen im System Cu/Mo/O

Coexistence Relations, Preparation and Properties of Ternary Compounds in the System Cu/Mo/O The phase diagram of the ternary system Cu/Mo/O is presented at 773 K. The compounds CuMoO₄, Cu₃Mo₂O₉, Cu₄Mo₅O₁₇, Cu₆Mo₅O₁₈, Cu_4–xMo₃O₁₂, and Cu_xMoO₃ are found to be thermodynamical stable. The homogeneity range of Cu_4–xMo₃O₁₂ runs to x = 0.1–0.2. Single crystals of CuMoO₄ and Cu₃Mo₂O₉ were grown by chemical transport reactions with TeCl₄, Cl₂, HCl, and Br₂ as transport agent. The results were compared with thermochemical calculations. The decomposition of CuMoO₄ and Cu₃Mo₂O₉ was investigated with thermal analysis and decompositon pressure measurements.     

Characterization and Physical Properties of PbO-As2O3 Glasses Containing Molybdenum Ions

PbO-As₂O₃ glasses containing different concentrations of MoO₃ ranging from 0 to 1 mol% (in steps of 0.2) were prepared. The samples were characterized by X-ray diffraction, differential thermal analysis and scanning electron microscopy. A number of studies, viz., optical absorption, magnetic susceptibilities, ESR spectra, IR spectra, elastic properties (Young's modulus E, shear modulus G and microhardness H) and dielectric properties (constant ε, loss tan δ, a.c. conductivity σ_ac over a range of frequency and temperature and breakdown strength), have been carried out on these glasses. Optical absorption, ESR and magnetic susceptibility measurements suggest that when MoO₃ concentration is greater than 0.4 mol% in the glass matrix, molybdenum ions exist in Mo⁵⁺ state with Mo(V)O⁻₃ complexes that act as modifiers in addition to Mo⁶⁺ state with MoO₄ and MoO₆ structural groups. The studies on elastic and dielectric properties indicate that the mechanical and insulating strengths of the glass are considerably high when the content of MoO₃ is about 0.4 mol% in the glass matrix.     

Crystal growth and electrical properties of lithium,rubidium, and cesium molybdenum oxide bronzes

Crystals of Li_0.33 MoO₃ (blue), Rb_0.23MoO₃ (blue) and Cs_0.31MoO₃ (red) were grown by electrolysis from MoO₃M₂MoO₄ melts (M =alkali metal) with composition 70–77 mole% MoO₃. Melts richer in M₂MoO₄ produced MoO₂ only. Correlation is made between bronze formation and the coordination of Mo in the melt and in the equilibrium solid phase M₂Mo₄O₁₃. Li_0.33MoO₃ and Cs_0.31MoO₃ are semiconductors with high-temperature-range activation energies 0.16 and 0.12 eV. Rb_0.23MoO₃ has an electrical behavior similar to that of blue K_xMoO₃ with a semiconductor-metal transition at (170 ± 5) K. ESR spectra observed in Li_0.33MoO₃ and Rb_0.23MoO₃ single crystals at 4.2 K show extensive delocalization of the 4d¹ electron associated with Mo(V) centers. Attempts to grow molybdenum bronzes containing Ca or Y were unsuccessful.     

Zur Kenntnis eines neuen Kupfermolybdats: Cu4Mo5O17

About a New Copper Molybdate: Cu₄Mo₅O₁₇ Single crystals of Cu₄Mo₅O₁₇ were prepared by solid state reaction of Cu₂O and MoO₃ in the absence of oxygen. Single crystal X-ray investigations lead to triclinic symmetry (space group P1, a = 6.782, b = 9.573, c = 10.948 Å; α = 107.03, β = 88.40, γ = 111.02°, Z = 2). Cu₄Mo₅O₁₇ shows crystal chemical differences in respect to the Cu^II-oxomolybdates. The differences concern the coordination of Mo⁶⁺. Cu⁺ formes not a linear O? Cu? O group but is surrounded by oxygen tetrahedrally and octahedrally. The crystal structure is described and discussed.     

The phase diagram of V<Subscript>2</Subscript>O<Subscript>5</Subscript>-MoO<Subscript>3</Subscript>-Ag<Subscript>2</Subscript>O system

The results concerning the synthesis, structure and thermal properties of V₂O₅-MoO₃-Ag₂O samples in the molybdenum rich region of ternary system are presented in the form of quasi-binary systems: β-AgVO₃-β-Ag₂MoO₄, AgVMoO₆-MoO₃, AgVMoO₆-Ag₂Mo₄O₁₃, AgVMoO₆-Ag₂Mo₂O₇, AgVMoO₆-β-Ag₂MoO₄ and also of the system in which at V₂O₅/MoO₃ molar ratio 3:7 the content of Ag₂O was variable. The ternary phase AgVMoO₆ was not described earlier in the literature.     

Achieving high-performance Li2ZnTi3O8 anode for advanced Li-ion batteries by molybdenum doping

The Li₂ZnTi_3-xMo_xO₈ (x = 0, 0.05, 0.1 and 0.15) anode materials are successfully synthesized through a simple solid-state method, and few Li₂MoO₄ phase can be found in Li₂ZnTi_3-xMo_xO₈ (x = 0.1 and 0.15). All samples are composed of nanocrystalline particles and irregular micron-sized particles with a relatively uniform particle size of 100–200 nm Li₂ZnTi_2.9Mo_0.1O₈ shows the best electrochemical properties among all samples. The Li₂ZnTi_2.9Mo_0.1O₈ delivers a charge/discharge capacity of 188.1/188.2 mA h/g at 1 A/g after 400 cycles, but the corresponding capacity of pristine Li₂ZnTi₃O₈ is only 104.5 (102.2) mA h/g. The Mo⁶⁺ doping enhances the reversible capacity, rate performance, and cycling stability of Li₂ZnTi₃O₈, especially at large current densities. The improved electrochemical performance of Li₂ZnTi_3-xMo_xO₈ can be ascribed to the enhanced electrical conductivity, improved intercalation/de-intercalation reversibility of Li ions, increased lithium-ion diffusion coefficients, and reduced charge-transfer resistance. This work provides an effective strategy to construct high-performance anode materials for advanced lithium-ion battery; this effective design strategy may be used to enhance the reversible specific capacity, and rate the performance and cycle stability of other insertion-host anode materials.     

Cryoscopic studies in molten salts. Dissociation state of some alkali isopolymolybdates and some related molybdenum(VI) compounds in molten K2Cr2O7and KNO3

The dissociation state of the solutes M₂MoO₄, M₂Mo₃O₁₀, M₂Mo₄O₁₃, M₂Mo₅O₁₆ (MRb or Cs), Na₂CrO₄·MoO₃, K₂CrO₄·2 MoO₃, Cr₂Mo₃O₁₂ and V₂MoO₈ was studied cryoscopically in molten K₂ Cr₂O₇ and KNO₃ solvents. The freezing point depression, ΔT, of the solvents was obtained by measuring the cooling curves of the binary salt mixtures over unlimited range of solute concentration. The number of foreign ions obtained ν, showed that the solutes were either simply dissociated in the melt into the probable stable species (MoO₄)^2?, (Mo₃O₁₀)^2?, (Mo₄O₁₃)^2? and (Mo₅O₁₆)^2? or, in some cases after reactions and rearrangements, into (CrMo₂O₁₀)^2? heteropolyions. The solute V₂MoO₈, on the other hand, was found to dissolve without any apparent dissociation. An agreement between the experimental and calculated values of activity, a, based on the Temkin and Random Mixing models and that of Van't Hoff's equation support the proposed simple dissocia- tion scheme for K₂Cr₂O₇Cs₂MoO₄ system.     

Tree of phases of the quinary reciprocal system Li,K || F,Br, MoO<Subscript>4</Subscript>, WO<Subscript>4</Subscript> and study of the stable tetrahedron LiF–KBr–Li<Subscript>2</Subscript>MoO<Subscript>4</Subscript>–Li<Subscript>2</Subscript>WO<Subscript>4</Subscript>

The quinary reciprocal system Li, K || F, Br, MoO₄, WO₄ was partitioned into simplexes using graph theory by writing an adjacency matrix and solving a logical expression. A tree of phases of the system was constructed. The tree of phases has a linear structure and consists of four stable partitioning tetrahedra, two stable pentatopes, and three stable hexatopes. In the quinary reciprocal system Li, K || F, Br, MoO₄, WO₄, crystallizing phases were predicted. The stable tetrahedron LiF–KBr–Li₂MoO₄–Li₂WO₄ of the quinary reciprocal system Li, K || F, Br, MoO₄, WO₄ was studied by differential thermal analysis and X-ray powder diffraction. There are no invariant equilibrium points in the tetrahedron. Continuous series of solid solutions Li₂Mo_xW_1–xO₄ do not decompose.