Oxidative dehydrogenation of ethane to ethylene over V2O5/Nb2O5 catalysts

V₂O₅/Nb₂O₅ catalysts with various V₂O₅ contents were prepared by impregnation and characterized by various techniques in detail. Oxidative dehydrogenation of ethane was carried out in a fixed bed quartz reactor at 500–600 °C. XPS analysis indicated a clear enrichment of vanadium on the near-surface-region and UV–vis diffuse reflectance spectroscopy revealed the nature of VO_x structures formed. 10 wt.% V₂O₅/Nb₂O₅ catalyst has displayed the best performance (X = 28%, S = 38% at 600 °C) due to enrichment of vanadium in the near-surface-region and formation of optimum amount of monomeric/oligomeric VO_x species.     

Synthesis,structure and photocatalytic hydrogen evolution of a silver-linked hexaniobate Lindqvist chain

By using a combination of hydrothermal and diffusional strategies, a one-dimensional polyoxoniobate K₅[H₂AgNb₆O₁₉]·11H₂O (1) has been synthesized. The structure was characterized by single-crystal X-ray diffraction, UV spectroscopy, TG analysis, PXRD and IR spectrum. 1 crystallizes in the hexagonal P63/mmc space group with a = 9.8171(2) Å, c = 16.5442(6) Å, and V = 1380.84(6) Å³. It is the first Ag-containing polyoxoniobate, which consists of [H₂AgNb₆O₁₉]^5 − polyoxoanion and potassium ions. In addition, 1 exhibits the photocatalytic H₂ evolution activity.     

Synthesis,crystal structure,characterization and magnetic property of a new organophosphonate-based polyoxovanadate

A novel organophosphonate-based polyoxovanadate, Cs_1·5Na_3.5[H{V₃(H₂O)O₃}{O₃PC- (OH)(CH₃)PO₃}₃]·15H₂O (1) has been synthesized and further investigated by single-crystal X-ray diffraction analysis, IR spectrum, UV–vis spectroscopy, X-ray powder diffraction, thermogravimetric analysis and X-ray photoelectron spectroscopy. Single-crystal X-ray analysis reveals that compound 1 crystallizes in the triclinic space group P-1 with a = 9.506(3) Å, b = 15.150(5) Å, c = 17.915(6) Å, V = 2437.9(14) ų and Z = 2. Compound 1 exhibits a ring-shaped cluster with three branches of the 1-hydroxyethane 1, 1-diphosphonic acid [HEDP = H₂O₃P(OH)C(CH₃)PO₃H₂] ligands. Furthermore, the magnetic property of compound 1 has also been studied.     

Inorganic–organic hybrid material containing β-cage: {[H2(en)]Co2(ox)(V4O12)}n

By using an organic ligand, a new inorganic–organic hybrid compound of cobalt oxalate-vanadate, {[H₂(en)]Co₂(ox)(V₄O₁₂)}_n 1, where en = ethylenediamine, ox = oxalic acid, has been synthesized hydrothermally from V₂O₅,CoCl₂·6H₂O,H₂C₂O₄·2H₂O and en. Crystal data 1, orthorhombic, Cmcm space group, a=11.624(2), b=9.968(2), c=14.900(3) Å, R1=0.0298, wR2=0.1172. Compound 1 possesses a three-dimensional open-framework with β-cage and is an antiferromagnetic matter.     

The first example of extended structure constructed from Knoth-type sandwich POMs and coordination fragments

A novel compound [P₂W₁₈M₃O₆₈][Cu(en)₂]₄·7H₂O·2OH^? (M = 0.5W + 0.5Cu) 1 which contains the first example of extended structure constructed from Knoth-type sandwich polyoxoanions and transition metal coordination complexes has been hydrothermally synthesized and characterized by elemental analysis, IR spectrum, UV–Vis spectrum and single-crystal X-ray diffraction analysis. Crystal data for 1: triclinic, space group, P-1, a = 13.2718(7) Å, b = 13.6432(8) Å, c = 25.7307(15) Å, α = 104.7340(10)°, β = 96.7630(10)°, γ = 90.0330(10)°, V = 4472.2(4) Å³, Z = 2. Structure solution and refinement based on 1090 parameters gave R1 (wR2) = 0.0409 (0.0993).     

Correlation between infrared,THz and microwave dielectric properties of vanadium doped antiferroelectric BiNbO4

Terahertz (THz) transmissivity and infrared (IR) reflectivity spectra of orthorhombic microwave (MW) ceramics Bi(Nb_1−xV_x)O₄ (0.002 < x < 0.032) were measured between 4 and 3000 cm⁻¹ (0.09–90 THz) at room temperature. A well underdamped mode, presumably the ferroelectric soft mode, was observed at 25 cm⁻¹. Complex permittivity spectra obtained from the fits to our data were extrapolated down to the MW range and compared with the dielectric data near 5 GHz. The linear extrapolation of dielectric losses from THz down to the MW range is in agreement with the experimental MW losses. Addition of 3.2% of vanadium reduces the sintering temperature to 850 °C and the dielectric properties (ɛ′ = 42.2, Q·f = 14,000 GHz, τ_f = +10 ppm/°C) remain at a level satisfactory for MW applications. Somewhat lower MW losses were observed in a sample sintered in the N₂ atmosphere.     

Organic–inorganic hybrid oxides: Structure and magnetic properties of [{Cu(terpy)}2Mo6O17(H2O)(O3PCH2NH2CH2PO3)2] · H2O,a bimetallic oxide constructed from novel {Mo6O17(H2O)(O3PCH2NH2CH2PO3)2}4− clusters

The hydrothermal reaction of MoO₃, CuSO₄ · 5H₂O, 2,2′:6′:2″-terpyridine (terpy) and bis-N,N-(methylphosphonic acid) amine (H₂O₃PCH₂NHCH₂PO₃H₂) provided blue crystals of the bimetallic oxide [{Cu(terpy)}₂Mo₆O₁₇(H₂O)(O₃PCH₂NH₂CH₂PO₃)₂] · H₂O (1 · H₂O). The three-dimensional structure of 1 is constructed from {Mo₆O₁₇(H₂O)(O₃PCH₂NH₂CH₂PO₃)₂}⁴⁻ clusters linked through {Cu(terpy)}²⁺ subunits. The cluster consists of three pairs of edge-sharing {MoO₆} octahedra linked through corner-sharing interactions into a {Mo₆O₆} ring. One phosphonate ligand spans the diameter of the ring, bridging four molybdenum sites and leaving at a pendant {PO} group at each terminus. The second diphosphonate ligand exploits one {–PO₃} unit to cap the hexamolybdate ring and bridge all six molybdenum sites while the second {–PO₃} terminus bridges two molybdenum sites, leaving a pendant {PO} unit. Crystal data: C₃₄H₄₅Cu₂Mo₆N₈O₃₅P₄: monoclinic, P2₁/n, a = 11.9431(7) Å, b = 17.382(1) Å, c = 27.524(2) Å, β = 90.429(1)°, V = 5713.7(6) Å³, Z = 4, D_calc = 2.270 g cm⁻³, R₁ = 0.0466.     

Effect of Li2O–V2O5 on the low temperature sintering and microwave dielectric properties of Li1.0Nb0.6Ti0.5O3 ceramics

Li₂O–Nb₂O₅–TiO₂ based ceramic systems have been the candidate materials for LTCC application, due to their high dielectric constant and Q × f value and controllable temperature coefficient in the microwave region. However, the sintering temperature was relatively higher (above 1100 °C) for practical application. In this study, dielectric properties of Li_(1+x−y)Nb_(1−x−3y)Ti_(x+4y)O₃ solid solution were studied with different x and y contents and among them, the Li_1.0Nb_0.6Ti_0.5O₃ composition (x = 0.1, y = 0.1) was selected, due to its reasonable dielectric properties to determine the possibility of low temperature sintering. The effects of 0.17Li₂O–0.83V₂O₅, as a sintering agent, on sinterability and microwave dielectric properties of Li_1.0Nb_0.6Ti_0.5O₃ ceramics were investigated as a function of the sintering agent content and sintering temperature. With addition of 0.17Li₂O–0.83V₂O₅ above 0.5 wt%, the specimens were well densified at a relatively lower temperature of 850 °C. Only slight decrease in apparent density was observed with increasing 0.17Li₂O–0.83V₂O₅ content above 0.75 wt%. In the case of 0.5 wt% 0.17Li₂O–0.83V₂O₅ addition, the values of dielectric constant and Q × f reached maximum. Further addition caused inferior microstructure, resulting in degraded dielectric properties. For the specimens with 0.5 wt% 0.17Li₂O–0.83V₂O₅ sintered at 850 °C, dielectric constant, Q × f and TCF values were 64.7, 5933 GHz and 9.4 ppm per °C, respectively.     

Reaction sequence and electrochemical properties of lithium vanadium oxide cathode materials synthesized via a hydrothermal reaction

Lithium vanadium oxide (Li_1+xV₃O₈) cathode materials were synthesized via a simple hydrothermal reaction followed by heat treatment at 300 or 400 °C. From both XRD and TG/DTA analyses, a detailed comprehensive reaction sequence for the formation of single-phase LiV₃O₈ is proposed. Li_1+xV₃O₈ (x=0.2) materials with different thermal histories show clear differences in morphologies and sizes, although they maintained an impurity-free single phase regardless of thermal treatment. Samples that were heat treated at 300 °C show an agglomerated particle shape with many nanorod-like Li_1+xV₃O₈ particles over the surface that enhance the surface area of the particles. In contrast, samples treated at 400 °C have a bi-modal particle size distribution with improved crystallinity. Such differences in morphologies clearly influence the electrochemical properties. LiV₃O₈ cathode materials that were treated at 300 and 400 °C showed initial discharge capacacities of 346.52 and 261.23 mA h/g, respectively, and discharge capacities of 78.66 and 157.35 mA h/g, respectively, after 100 cycles. The improved cyclability of LiV₃O₈ cathode materials that were heat treated at 400 °C is due to their increased crystallinity and structural stability.     

A novel paradodecatungstate-B compound decorated by transition metal copper,Na2Cu5(H2O)24(OH)2[H2W12O42]·10H2O: Synthesis,structure and antitumor activities

A new paradodecatungstate-B compound decorated by transition metal copper, Na₂Cu₅(H₂O)₂₄(OH)₂[H₂W₁₂O₄₂]·10H₂O (1), has been synthesized by convenient aqueous solution method and structurally characterized by single-crystal X-ray diffraction, IR spectrum, elemental analysis and TGA. The compound crystallizes in the triclinic P-1 space group with a = 10.7140(8) Å, b = 12.9476(9) Å, c = 13.6696(10) Å, α = 73.56°, β = 75.73°, γ = 67.69°, V = 1661.8(2) ų and Z = 1. In compound 1, polyanion of [H₂W₁₂O₄₂]^10 − acts as a dodecadentate ligand that links copper and sodium cations, forming a remarkable three-dimensional framework. The experiment of antitumor activities in vitro shows that the title compound exhibits remarkable inhibitory actions on human cervical carcinoma HeLa cells, ovarian carcinoma SKOV-3 cells, hepatoma HepG2 cells and neuroblastoma SHY5Y cells.     

High-temperature hot corrosion behavior of gadolinium zirconate by vanadium pentoxide and sodium sulfate in air

Gadolinium zirconate (Gd₂Zr₂O₇) prepared by solid state reaction exhibited a defect fluorite-type structure. Reactions between Gd₂Zr₂O₇ ceramic and vanadium pentoxide (V₂O₅), sodium sulfate (Na₂SO₄), and V₂O₅ + Na₂SO₄ mixture were investigated from 700 to 1000 °C in air using an X-ray diffractometer (XRD), scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS). V₂O₅ reacts with Gd₂Zr₂O₇ to form gadolinium vanadate (GdVO₄) and monoclinic zirconia (m-ZrO₂) at 900 and 1000 °C in air. However, no chemical reaction product between Na₂SO₄ and Gd₂Zr₂O₇ is found at 900 and 1000 °C in air. V₂O₅ reacts with equal molar Na₂SO₄ to form sodium vanadate (NaVO₃) at 610 °C. In the temperature range of 700–1000 °C, Na₂SO₄ + V₂O₅ mixture reacts with Gd₂Zr₂O₇ in air to form the final reaction products of GdVO₄ and m-ZrO₂.     

Hydrothermal synthesis,crystal structure and magnetic properties of a novel nickel carboxylate–phosphonate with a layered structure

Hydrothermal reactions of N-(phosphonomethyl)proline (H₃L) with nickel sulfate hexahydrate resulted in a novel nickel carboxylate–phosphonate: |H₂O|[Ni₃(O₃PCH₂–NC₄H₇–CO₂)₂(H₂O)₄] (complex 1). Single-crystal X-ray diffraction analysis revealed that complex 1 crystallizes in the triclinic space group P-1 (No. 2), with lattice parameters of a = 10.0167(5) Å, b = 10.3882(5) Å, c = 11.9528(5) Å, α = 90.132(3)°, β = 107.246(3)°, γ = 111.158(3)°, V = 1099.39(9) Å³, and Z = 2. Complex 1 features a 2D layered structure. The structure contains alternating Ni-centered octahedra (Ni(1)O₆, Ni(2)O₅N and Ni(3)O₅N) and O₃PC tetrahedra linked to construct a layer with rhombohedral 12-MRs holes. The cyclopentylamine moieties of H₃L were grafted onto the layer through coordination of CPO₃, CO₂ and (CH₂)₂NCH₂ with central nickel atoms. These layers are stacked in an AA sequence, which results in a one-dimensional channel in the [001] direction. Water molecules are located in these channels. Magnetic studies showed that complex 1 exhibits predominantly paramagnetic behavior.     

A wet-chemical method for the synthesis of in-doped CaZrO3 ceramic powders

Both CaZr_0·9In_0·1O_3-α ceramics and ceramic nano-powders are synthesized starting from a co-precipate formed using a wet-chemical co-precipitation method. The XRD-results confirm that CaZrO₃ and CaIn₂O₄ phases exist after the co-precipitates are calcined at 1273 K for 3 h in air. The CaIn₂O₄ phase disappears after calcining the powder twice at 1823 K for 10 h in air with the formation of the CaZr_0·9In_0·1O_3-α phase. The XRD pattern of the ceramic powders is the same as that of sintered CaZr_0·9In_0·1O_3-α ceramics (1823 K for 10 h in air). Scanning electron microscopy shows that the ceramic powders calcined at 1273 K for 3 h are nano-sized powders. After sintering at 1823 K for 10 h, the grain-size increases dramatically. EDX results indicate that the Ca:Zr: In ratio in the co-precipitates is close to the theoretical value. The ratio of Ca:In decreases with increasing calcining or sintering temperature. ©     

An organic–inorganic hybrid nickel-substituted arsenotungstate consisting of three types of polyoxotungstate units

A new organic–inorganic hybrid nickel-substituted arsenotungstate [Na(H₂O)₃]₂[Ni(H₂O)₆]₂[Ni(H₂O)₅]{[Ni₃(dap)(H₂O)₂]₂(H₂W₄O₁₆)}{(α-H₂AsW₆O₂₆)[Ni₆(OH)₂(H₂O)(dap)₂](B-α-HAsW₉O₃₄)}₂·7H₂O (1) (dap = 1,2-diaminopropane) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Crystal data for 1: C₁₈H₁₄₄As₄N₁₂Na₂Ni₂₁O₁₇₆W₃₄, Mr = 11174.92, triclinic, space group P-1, a = 15.004(4) Å, b = 16.357(5) Å, c = 22.070(6) Å, α = 80.458(5)°, β = 79.291(5)°, γ = 72.074(5)°, V = 5030(3) Å³, Z = 1, GOOF = 1.007, R₁ = 0.0703, wR₂ = 0.1670. The skeleton of 1 is a centric nanoscale cluster and is composed of two asymmetric sandwich-type clusters {(α-H₂AsW₆O₂₆)[Ni₆(OH)₂(H₂O)(dap)₂](B-α-AsW₉O₃₄)}^7? linked by a symmetric cluster {[Ni₃(dap)(H₂O)₂]₂(H₂W₄O₁₆)}⁶⁺. Notably, 1 is an interesting polyoxometalate containing the trivacant Keggin [B-α-AsW₉O₃₄]^9?, hexavacant Keggin [α-AsW₆O₂₆]^11? and tetrameric [W₄O₁₆]^8? units. Magnetic measurements indicate that 1 shows the ferromagnetic interactions within Ni^II centers.     

Synthesis,crystal structure,and optical property of a one-dimensional selenidostannate: [AEPPH2]2[Sn5Se12] (AEPP = N-aminoethylpiperazine)

A one-dimensional (1-D) selenidostannate, [AEPPH₂]₂[Sn₅Se₁₂] (AEPP = N-aminoethylpiperazine) (1), has been prepared under solvothermal condition and characterized. Single crystal X-ray analysis reveals that compound 1 crystallizes in the triclinic space group P-1, a = 10.6351(7) Å, b = 10.6850(7) Å, c = 10.7771(7) Å, α = 61.3440(10)°, β = 62.4420(10)°, γ = 67.4680(10). With distinct linkage modes between SnSe₄ tetrahedrons and SnSe₆ octahedrons, a secondary building unit (SBU) [Sn₅Se₁₄] is formed. Compound 1 contains infinite bead-like chains built up by the [Sn₅Se₁₄] SBUs, and the protonated [AEPPH₂]^2 + cations are located between the chain spaces. A pseudo 3-D network is formed through C–H···Se and N–H···Se hydrogen bonds between adjacent chains. Its optical property and theoretical band structure and density of state (DOS) calculations have also been studied.     

An inorganic–organic hybrid material with a novel oxometallic framework: Hydrothermal synthesis and characterization of [Zn3O3(C13H14N2)3]V6O15

A new hybrid material [Zn₃O₃(C₁₃H₁₄N₂)₃]V₆O₁₅ (1) with extended framework structure has been synthesized hydrothermally and characterized by vibrational spectroscopy, thermogravimetry and complete single crystal X-ray diffraction analysis. The compound has a complex three-dimensional covalent framework structure. It exhibits a fully oxidized novel oxometallic framework containing 10-membered {V₄ZnO₅} oxometalate rings and 4,4′-trimethylene dipyridine ligands (C₁₃H₁₄N₂) that connect pairs of crystallographically equivalent zinc atoms. The extended structure of 1 may also be viewed as containing a framework of corner-sharing {VO₄} and {ZnO₂N₂} polyhedra together with 4,4’-trimethylene dipyridine ligands linking zinc centers. The hybrid material is thermally stable up to 323 °C. It contains metal centers and coordination geometry that make it a potentially attractive model compound for investigating the structures of metallo-organic biomolecules by use of solid state NMR spectroscopic techniques. Crystal data for C₃₉H₄₂N₆O₁₈V₆Zn₃: monoclinicic P2₁, a = 10.9894(9) Å, b = 18.1493 (15) Å, c = 13.0903 (11) Å, β = 109.8880(10)°, V = 2455.1(4) Å³, Z = 2, D_calc. = 1.873 Mg/m³.     

Microstructure and electrical characteristics of ZnO–B2O3–PbO–V2O5–MnO2 ceramics prepared from ZnO nanopowders

A peculiar kind of ZnO–B₂O₃–PbO–V₂O₅–MnO₂ ceramics was produced from the ZnO nanopowders directly co-doped with the oxides instead of lead zinc borate frit in this investigation. The 8 wt.% (PbO+B₂O₃) co-doped ceramics sintered at 950 °C for 2 h displayed the optimum electrical properties, that is, leakage current density J_L=6.2×10⁻⁶ A/cm², nonlinear coefficient α=22.8 and breakdown voltage V_BK=331 V/mm. The co-doping of 8 wt.% (PbO+B₂O₃) resulted in an increase in nonlinear coefficient and a decrease in leakage current density of the ZnO–V₂O₅ varistors while the sintering temperature showed no evident influence on nonlinear coefficient and leakage current density at the range of 800–950 °C.     

Microwave dielectric properties of tungstenbronze type like (Ba1−αSrα)6−3xR8+2xTi18O54 (R = Sm,Nd) solid solutions

Tungstenbronze type like Ba_6−3xR_8+2xTi₁₈O₅₄ (R = Sm or Nd) dielectric ceramics reveal high quality factor Q·f as well as high dielectric constant ɛ_r. We have investigated the effect of Sr substitution for Ba ions on the microwave dielectric properties of the compounds. (Ba_1−αSr_α)_6−3xR_8+2xTi₁₈O₅₄ (R = Sm or Nd) ceramics were prepared in the composition ranges of x = 0–0.2 and α = 0–0.312 and the microwave dielectric properties were investigated. (Ba_1−αSr_α)_6−3xSm_8+2xTi₁₈O₅₄, where x = 0.1 and α = 0.298, and (Ba_1−αSr_α)_6−3xNd_8+2xTi₁₈O₅₄, where x = 0.2, α = 0.296 revealed remarkably higher Q·f value among the solid solutions, indicating that Q·f increased with substituting Sr ions into Ba ions at the rhombic A1-site. This fact suggests that relaxation of local distortions at the A1-sites is closely related to improvement of Q·f.