Magnetische Eigenschaften von Ti3−xMxO5-Phasen (M = V3+, Cr3+, Nb4+)

Magnetic Properties of Ti_3?xM_xO₅ Phases (M = V³⁺, Cr³⁺, Nb⁴⁺) The magnetic properties of Ti_3?xV_xO₅, Ti_3?xCr_xO₅, and Ti_3?xNb_xO₅ phases are reported. In the case of V³⁺ and Cr³⁺ the magnetic leaping-temperature decreases, however Nb⁴⁺ shift the phase-transition towards higher temperatures. All samples show a “memory-effect” in magnetic properties, i. e. the results of heating- and cooling-cycles are higher susceptibilities of the α-phase of Ti₃O₅. Endowed Ti₃O₅ phases show for the α- and β-Ti_3?xM_xO₅ til the leap Curie-Weiss characteristic in 1/X vs. temperature measurements. Exception is β-Ti_3?xNb_xO₅, its susceptibility is independend of the temperature up to x ? 0.3.     

Une nouvelle structure à tunnels: KxVxMo1−xO3 (x = 0.13)

The crystal structure of the hexagonal phase K_xV_xMo_1?xO₃ (x = 0.13) has been determined by single crystal X-ray analysis. The space group is P6₃. The parameters are a = 10.481 Å and c = 3.701 Å. The structure is formed by triple chains of octahedra sharing corners and parallel to the Oz axis. Each triple chain shares edges with three other chains.Potassium is inserted in the large tunnels. The reliability factor is R = 0.045 on the base of 158 observed reflexions. The Rb_xV_xMo_1?xO₃ and Cs_xV_xMo_1?xO₃ phases (0.12 ? x ? 0.14) are isostructural with K_xV_xMo_1?xO₃.     

Partial Enthalpies of Silicon,Vanadium, Zirconium,Niobium and Molybdenum in Liquid Tin at High Dilution

Abstract

The partial enthalpies of silicon, vanadium, zirconium, niobium and molybdenum in liquid tin at 1173 K were measured at high dilution by direct reaction calorimetry (drop method) with the help of a Tian-Calvet high-temperature calorimeter. When referred to liquid metals we found h _si/kj. mol^?1 = 99.4–263.0 x _si, hv/kj. mol^?1 = 102.8–14.8x _v, h _zr/kJ. mol^?1 = 124.2–18.1x _zr,h _Nb/kJ .mol^?1 = 81.7 + 72.5x _Nb and h _Mo/kJ. mol^?1 = 115.4–159.9x _Mo. The limiting partial enthalpies were deduced by extrapolation at infinite dilution.     

A new square niobium cluster {Nb4(μ4-O)I8}2+. Crystal structure of a [Nb4OI8][Mo6I14]2∞ polymer

A crystal structure of a new layered [Nb₄OI₈][Mo₆I1₄]_2∞ polymer containing a previously unknown niobium cluster {Nb₄(μ₄-O)I₈}²⁺ with a μ₄ oxygen atom is determined. The compound crystallizes in the P$\bar 1$\bar 1 triclinic space group with unit cell parameters a = 10.1842(6) ?, b = 10.1880(6) ?, c = 11.5700(6) ?, α = 78.058(2)°, β = 77.944(2)°, γ = 80.738(2)°, V = 1139.85(11) ?³, Z = 1, R _f = 0.0414. The electronic structure of the [{Nb₄(μ₄-O)I₈}I₄]²⁻ cluster complex is calculated.     

Two novel windmill-like tetrasupporting heteropolyoxometalates: [MoVI7MoVVIV8O40(PO4)][M(phen)2(OH)]2[M(phen)2(OEt)]2 (M=Co,Ni)

Two interesting neutral tetrasupporting heteropolyoxometalates: [Mo^VI₇Mo^VV^IV₈O₄₀(PO₄)][M(phen)₂(OH)]₂[M(phen)₂(OEt)]₂·xH₂O (phen=1,10-phenanthroline, EtOH=ethanol, M=Co, x=7, 1; M=Ni, x=6, 2) were hydrothermally prepared and structurally characterized. The mixed molybdenum–vanadium polyoxoanion [Mo^VI₇Mo^VV^IV₈O₄₀(PO₄)]⁴⁻ exist in both two complexes, which acts as a bridge to covalently link two pairs of transition metal complex fragments, generating neutral windmill-like trimetallic nanocluster polyoxometalates. Variable-temperature magnetic susceptibility measurements of complexes 1 and 2 reveal that antiferromagnetic exchange interaction exists in this type of trimetallic tetrasupporting heteropolyoxometalates.     

Kinetic investigation of propane oxidation on diluted Mo1–V0.3–Te0.23–Nb0.125–Ox mixed-oxide catalysts

Reaction kinetics and proposed mechanism for the oxidation of propane over diluted Mo₁–V_0.3–Te_0.23–Nb_0.125–O _x are described. The kinetic study allowed determination of the orders of propane disappearance, propene formation, CO _x formation, and acids formation. The results show that selective oxidation of propane to propylene over this catalyst follows the Langmuir-Hinshelwood mechanism. Deep oxidation of propane to carbon dioxide is first order with respect to hydrocarbon, and partial order (0.21) with respect to oxygen. The selective oxidation of propane to acrylic acid is half order with respect to hydrocarbon and partial order (0.11) with respect to oxygen, while water does not participate directly in propane transformation. The result also shows that the overall reaction consists of three parallel process channels. One main sequence of consecutive reactions leads to the desired product.     

Formation and properties of the Fe<Subscript>8</Subscript>V<Subscript>10</Subscript>W<Subscript>16–x</Subscript>Mo<Subscript>x</Subscript>O<Subscript>85</Subscript> type solid solution

Solid solution phases of a formula Fe₈V₁₀W_16–xMo_xO₈₅ where 0≤x≤4, have been obtained, possessing a structure of the compound Fe₈V₁₀W₁₆O₈₅. It was found on the base of XRD and DTA investigations that these solution phases melted incongruently, with increasing the value of x, in the temperature range from 1108 (x=0) to 1083 K (x=4) depositing Fe₂WO₆ and WO₃. The increase of the Mo⁶⁺ ions content in the crystal lattice of Fe₈V₁₀W₁₆O₈₅ causes the lattice parameters a=b contraction with cbeing almost constant. IR spectra of the Fe₈V₁₀W_16–xMo_xO₈₅ solid solution phases have been recorded.     

Reactions of Neutral and Charged Molybdenum Oxide Clusters with Low-Molecular-Weight Alcohols in a Gas Phase Studied by Ion Cyclotron Resonance

A set of oxygen-containing molybdenum oxide clusters Mo _x O _y (x = 1–3; y = 1–9) was obtained with the use of a combination of a Knudsen cell and an ion trap cell. The reactions of positively charged clusters with C₁–C₄ alcohols were studied using ion cyclotron resonance. The formation of a number of organometallic ions, the products of initial insertion of molybdenum oxide ions into the C–O and C–H bonds of alcohols, and polycondensation products of methanol and ethanol were found. The reactions of neutral molybdenum oxide clusters Mo _x O _y (x = 1–3; y = 1–9) with protonated C₁–C₄ alcohols and an ammonium ion were studied. The following limits of proton affinity (PA) were found for neutral oxygen-containing molybdenum clusters: (MoO) < 180, (Mo₂O₄, Mo₂O₅, and Mo₃O₈) = 188 ± 8, PA(MoO₂) = 202 ± 5, PA(MoO₃, Mo₂O₆, and Mo₃O₉) > 207 kcal/mol.     

Phase formation in the V<Subscript>2</Subscript>O<Subscript>5</Subscript>-Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>-MoO<Subscript>3</Subscript> system

The solid-phase interaction in the V₂O₅-Nb₂O₅-MoO₃ system has been investigated, and the formation of a solid solution bounded by the compositions MoNb₂V₄O_{18 ? δ}, Mo₂NbV₅O_{21 ? δ}, Mo₂Nb₃V₃O_{21 ? δ}, and Mo₄Nb₉V₉O_{57 ? δ} has been found (δ is nonstoichiometry). In the V₂O₅?Nb₂O₅ system, the formation of three compounds is verified, namely, VNbO₅ (tetragonal structure), VNb₉O₂₅, and V₂Nb₂₃O_62.5. The first two compounds are isostructural and form a continuous solid solution with tetragonal symmetry. A new compound of the composition Mo₃NbVO_{14 ? δ} has been synthesized. This compound is isostructural to the Mo₃Nb₂O₁₄ compound described in the literature and forms a tetragonal solid solution with it. The phase equilibria in the V₂O₅-Nb₂O₅-MoO₃ system in the subsolidus region have been determined.     

New nonstoichiometric molybdate,tungstate, and vanadate catalysts with the scheelite-type structure

Phases of the formula A_1?xфxMO₄ with the scheelite-type structure are described where ф represents a vacancy at the A cation site and M is Mo⁶⁺, W⁶⁺, and/or V⁵⁺. Many different univalent, divalent, and trivalent A cations were used in this study. The phases with no defects, i.e., x = 0, were known except for those of the type A¹⁺_.5A³⁺_.5MO₄ where A¹⁺ is Ag or Tl and M is Mo⁶⁺ or W⁶⁺. Phases with x > 0 are generally new and were prepared for catalytic studies. An excellent correlation between catalytic properties and defect concentration has been observed.     

Synthesis and crystal structure of Mo6−x Nb x I11 (x = 1–1.5)

A solid solution Mo_{6 ? x} Nb _x I₁₁ (x = 1.1–1.5) containing cluster cores {Mo₅NbI₈} is obtained by the high-temperature reaction of molybdenum, niobium, and iodine (550°C, 70 h, quartz ampule). According to the X-ray diffraction data, heating at 800°C in a molybdenum container results in the decomposition of the solution to Mo₆I₁₂ and Nb₆I₁₁. According to the X-ray structure analysis data, the compounds are isostructural to the high-spin modification Nb₆I₁₁ (space group Pccn). The presence of Nb atoms in the structure changes the structural type from the layered (Mo₆I₁₂) to framework structure, noticeably increases the metalmetal distances (2.661–2.716 Å, 2.695 Å) Mo₆ octahedron with the retention of the distance from the metal (M) to the μ₃-“capped” I atoms, and strongly elongates the M₆-I-M₆ bridges almost to the value observed in Nb₆I₁₁.     

Heteropoly Complexes Na0.5Cs2 ? x[H0.5 ? xM

Crystals of novel heterepoly complexes (HPC) Na_0.5Cs_{2 − x} [H_{0.5 − x} M _x ^II X^III(OH)₆Mo₆O₁₈] · 7−8H₂O (M^II = Fe, Mn; X^III = Cr, Al) are synthesized. Crystal structures of the complexes Na_0.5Cs_{2 − x} [H_{0.5 − x} Fe_xCr(OH)₆Mo₆O₁₈] · 7H₂O (I) (x = 0.19) and Na_0.5Cs_{2 − x} [H_{0.5 − x} Mn_xAl(OH)₆Mo₆O₁₈] · 8H₂O (II) (x = 0.22) are determined (space group Pbcn, Z = 8, a = 23.023(4) Å, b = 22.064(4) Å, c = 11.606(3) Å, V = 5895.66 ų for I and a = 22.972(9) Å, b = 22.002(8) Å, c = 11.543(5) Å, V = 5834.18 ų for II, respectively). The [X^III(OH)₆Mo₆O₁₈]³⁻ ligands were found to be coordinated in monodentate fashion to M atoms due to the participation of a terminal O atom of the cis-MoO₂ group in coordination with the Fe and Mn atoms, which was confirmed by IR data. __________ Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 9, 2005, pp. 663–676. Original Russian Text Copyright ? 2005 by Gavrilova, Molchanov.     

碳纳米管促进的Co-Mo-K硫化物基催化剂用于合成气制低碳混合醇

 以自行制备的多壁碳纳米管(CNT)作为添加剂,制备共沉淀型CNT促进的Co-Mo-K硫化物基催化剂. 实验发现,与未添加CNT的催化剂相比,添加少量CNT可显著提高CO的加氢转化活性和生成低碳醇的选择性. 在5.0 MPa, 623 K, V(CO)∶V(H2)∶V(N2)=45∶45∶10, GHSV=3600 ml/(g·h)的反应条件下, Co1Mo1K0.3-10%CNT催化剂上CO的转化率达21.6%, 相应的总醇(C1～4醇)时空产率为241.5 mg/(g·h), 产物中C2+醇/C1醇=1.39 (C基选择性比). 添加少量CNT并不会导致Co1Mo1K0.3硫化物基催化剂上CO加氢反应表观活化能发生明显变化,但却导致工作态催化剂表面催化活性Mo物种(Mo4+)的摩尔百分率有所提高; 另一方面, CNT促进的催化剂对H2有更强的吸附活化能力,并能在相当大程度上抑制水煤气变换副反应的发生. 这些因素有利于提高催化剂的活性和选择性.     

Reduction potential and oxidation catalysis of vanadium-containing H6+x P2Mo18−x V x O62 Wells-Dawson heteropolyacid (HPA) catalysts

Vanadium-containing H_6+x P₂Mo_18?x V _x O₆₂ (x=0?3) Wells-Dawson heteropolyacid (HPA) catalysts were prepared. The successful formation of the Wells-Dawson HPAs was confirmed by FT-IR and ICP-AES analyses. The reduction potential of the H_6+x P₂Mo_18?x V _x O₆₂ (x=0?3) catalysts was determined by temperature-programmed reduction measurements. The Wells-Dawson HPA catalysts were applied to the vapor-phase oxidation of methacrolein and benzyl alcohol. The reduction potential, conversion of methacrolein, and conversion of benzyl alcohol showed volcano-shaped curves with respect to vanadium substitution, and decreased in the order of H₈P₂Mo₁₆V₂O₆₂>H₇P₂Mo₁₇V₁O₆₂>H₉P₂Mo₁₅V₃O₆₂>H₆P₂Mo₁₈O₆₂. A correlation between reduction potential and catalytic activity clearly showed that the conversion was monotonically increased with increasing reduction potential of the HPA catalyst in both oxidation reactions.     

Structure and electrical conductivity of multicomponent metal oxides having scheelite structure

The investigated bismuth vanadate, BiVO₄, bismuth vanadomolybdate, Bi_0.85V_0.55Mo_0.45O₄, and pure bismuth molybdate, Bi₂Mo₃O₁₂, oxides prepared by novel spray drying technique having the scheelite structure were found to be monoclinic in the case of BiVO₄ and Bi₂Mo₃O₁₂, whereas Bi_0.85V_0.55Mo_0.45O₄ is body-centered tetragonal. The distribution of intergranular porosity across polycrystalline samples is inhomogeneous, being larger parallel to the flat compression of the powder samples. The high polarizability of Bi³⁺ cations with their lone-pair electrons influences stability of the disordered oxygen sublattice. All as-prepared systems undergo a slight structural change of the oxygen arrangement during the sample heating in the temperature region of 340–390°C, probably due to an order ⇆ disorder transition, resulting in a decrease of lattice oxygen ion mobility and decrease of electrical conductivity. The total bulk electrical conductivity of both vanadate systems is essentially ionic at low temperatures and high oxygen partial pressures. Diffusion of the lattice oxygen ions in the Bi_1−x/3V_1−x Mo _x O₄ scheelite structure is indirectly related to the introduction of cation vacancies. The highest conductivity was observed in the multicomponent oxide Bi_0.85V_0.55Mo_0.45O₄, both as-prepared and thermally treated. Above 350°C the conductivity of BiVO₄ and partially also Bi_0.85V_0.55Mo_0.45O₄ oxides is affected by the n-type electron contribution. Published in Russian in Elektrokhimiya, 2009, Vol. 45, No. 6, pp. 659–667. The article is published in the original. Published by report at IX Conference “Fundamental Problems of Solid State Ionics”, Chernogolovka, 2008.     

Correlation between reduction potential of vanadium-containing heteropolyacid (HPA) catalysts and their oxidation activity for cyclohexanol dehydrogenation

Vanadium-containing H_6+xP₂Mo_18−xV_xO₆₂ (x = 0, 1, 2 and 3) Wells-Dawson heteropolyacid (HPA) and H_3+xPMo_12−xV_xO₄₀ (x = 0, 1, 2 and 3) Keggin HPA catalysts were applied to the vapor-phase dehydrogenation of cyclohexanol. The catalytic oxidation activity showed a volcano-shaped curve with respect to vanadium substitution for both families of HPA catalysts. The Wells-Dawson HPA showed a better catalytic oxidation performance than the Keggin HPA at the same level of vanadium substitution.     

Structure and properties of solid solutions based on bismuth niobate Bi<Subscript>3</Subscript>NbO<Subscript>7</Subscript>

Solid solutions Bi₃Nb_1–yW_yO_{7 ± δ}, Bi₃Nb_1–yV_yO_{7 ± δ}, Bi₃Nb_1–yFe_yO_{7 ± δ} (y = 0.1–0.5; Δy = 0.1), and Bi_3–xY_xNb_1–yW_yO_{7 ± δ} (x = 0.05, 0.1; y = 0–0.3; Δy = 0.1) have been studied. The homogeneity ranges of the solid solutions and crystal-chemical parameters have been determined by means of X-ray powder diffraction. The electrical conductivity of sintered samples has been studied by impedance spectroscopy. The joint introduction of yttrium and tungsten into the niobium sublattice does not lead to an increase in the conductivity of solid solutions, and the change of the dopant type has no noticeable effect on this conductivity.     

Low-alkali metal content in β-vanadium mixed bronzes: The crystal structures of β-Kx(V,Mo)6O15 (x=0.23 and 0.32) by single-crystal X-ray diffraction

The vanadium-molybdenum mixed oxide bronzes of composition K_0.23(V_5.35Mo_0.65)O₁₅ and K_0.32(V_5.48Mo_0.52)O₁₅ have a monoclinic structure with s.g. C2/m, Z=2, and unit-cell dimensions a=15.436(2), b=3.6527(5), c=10.150(1) Å, β=108.604(3)° and a=15.452(2), b=3.6502(5), c=10.142(1) Å, β=109.168(3)°, respectively, as determined by single-crystal X-ray diffraction. These compounds show the β-Na_xV₆O₁₅ tunnel structure, which is isostructural with bannermanite, natural sodium-potassium vanadate. Structure refinements from diffracted intensities collected in the 2-38°θ range converged to final R=5.58% and 7.48% for the two crystals, respectively. The V atoms are distributed on three different crystallographic sites. Partial substitution of V with Mo occurs in only one of these positions. Oxygen atoms involved in vanadyl groups point toward the tunnels. The K ions in the tunnels are coordinated by seven oxygen atoms. The alkali metal content in these crystals is much lower than the solubility limit found for the analogous Na containing compound.     

Stoichiometry and physical properties of ternary molybdenum chalcogenides MxMo6X8 (X = S,Se; M = Li,Sn, Pb)

Chemical and electrochemical insertion of Li at room temperature, as well as insertion of lead and tin at moderate temperatures (500°C), into the binary phase Mo₆X₈ forms ternary molybdenum chalcogenides M_xMo₆X₈ (X = S, Se). Crystallographic parameters, superconducting properties, and magnetic susceptibility are reported. The stoichiometry x for lead and tin is shown not to exceed x = 1, while for Li, x can reach approximately 4.0. For the lead and tin sulfide series, the hexagonal lattice parameters and superconducting critical temperatures (T_c) are invariant to changes in the nominal composition of 0.8 < x < 1.2, while both an increase in T_c and a small decrease in c_h is observed for the selenides; a narrow homogeneity range exists near x = 1 below 500°C for both these sulfides and selenides, the single-phase region being somewhat larger in the selenides. In contrast, several single-phase regions and large unit cell changes are observed in Li_xMo₆X₈ (0 < x < 3.2). Magnetic susceptibility measurements of the lithiated compounds at x ～ 3.2 reveals a structural phase transition at 140 and 185 K for the sulfide and selenide, respectively; but neither superconducts down to 1.5 K. At lower lithium concentration near x ～ 1.0, the T_c of the sulfide is raised from that of Mo₆S₈ (1.8 K) to 5.2 K but the T_c of Mo₆Se₈ (6.5 K) is depressed to 3.9 K.