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1.
The hydrothermal reactions of vanadium oxide starting materials with divalent transition metal cations in the presence of nitrogen donor chelating ligands yield the bimetallic cluster complexes with the formulae [{Cd(phen2)2V4O12]·5H2O (1) and [Ni(phen)3]2[V4O12]·17.5H2O (2). Crystal data: C48H52Cd2N8O22V4 (1), triclinic. a=10.3366(10), b=11.320(3), c=13.268(3) Å, =103.888(17)°, β=92.256(15)°, γ=107.444(14)°, Z=1; C72H131N12Ni2O29.5V4 (2), triclinic. a=12.305(3), b=13.172(6), c=15.133(4), =79.05(3)°, β=76.09(2)°, γ=74.66(3)°, Z=1. Data were collected on a Siemens P4 four-circle diffractometer at 293 K in the range 1.59° <θ<26.02° and 2.01°<θ<25.01° using the ω-scan technique, respectively. The structure of 1 consists of a [V4O12]4− cluster covalently attached to two {Cd(phen)2}2+ fragments, in which the [V4O12]4− cluster adopts a chair-like configuration. In the structure of 2, the [V4O12]4− cluster is isolated. And the complex formed a layer structure via hydrogen bonds between the [V4O12]4− unit and crystallization water molecules.  相似文献   

2.
Dense tubular Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCFO) membranes were successfully prepared by the plastic extrusion method. The oxygen permeation flux was determined at different oxygen partial pressures in the shell side and different temperatures between 700 and 900 °C. The oxygen vacancy diffusion coefficients (Dv) at different temperatures were calculated from the dependence of oxygen permeation flux on the oxygen partial pressure term based on the surface current exchange model. No unsteady-state of oxygen permeation flux was observed at the initial stage in our experiments. The reason is the equilibrium time is too short (less than 10 min) to observe the unsteady-state in time. The increase of the helium flow rate can increase the oxygen permeation flux, which is due to the decrease of the oxygen partial pressure in the tube side with increasing of the helium flow rate. The oxygen permeation flux can also be affected by the air flow rate in the shell side when the air flow rate is lower than 150 ml/min. But the oxygen permeation flux is insensitive to the air flow rate when the air flow is higher than 150 ml/min. The membrane tube was operated steadily for 150 h with oxygen permeation flux of 1.12 ml/(cm2 min) at 875 °C. X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS) analysis showed that both the surface exposed to air and the surface exposed to helium of the BSCFO membrane tube after permeation for 150 h are similar to the fresh membrane tube in composition and structure. These results indicated that the membrane tube exhibits high structure stability.  相似文献   

3.
The compound [Zn(H2O)4]2[H2As6V15O42(H2O)]·2H2O (1) has been synthesized and characterized by elemental analysis, IR, ESR, magnetic measurement, third-order nonlinear property study and single crystal X-ray diffraction analysis. The compound 1 crystallizes in trigonal space group R3, a=b=12.0601(17) Å, c=33.970(7) Å, γ=120°, V=4278.8(12) Å3, Z=3 and R1(wR2)=0.0512 (0.1171). The crystal structure is constructed from [H2As6V15O42(H2O)]4− anions and [Zn(H2O)4]2+ cations linked through hydrogen bonds into a network. The [H2As6V15O42(H2O)]6− cluster consists of 15 VO5 square pyramids linked by three As2O5 handle-like units.  相似文献   

4.
W.M. Shaheen   《Thermochimica Acta》2008,470(1-2):18-26
The effects of calcination temperature and doping with K2O on solid–solid interactions and physicochemical properties of NiO/Fe2O3 system were investigated using TG, DTA and XRD techniques. The amounts of potassium, expressed as mol% K2O were 0.62, 1.23, 2.44 and 4.26. The pure and variously doped mixed solids were thermally treated at 300, 500, 750, 900 and 1000 °C. The catalytic activity was determined for each solid in H2O2 decomposition reaction at 30–50 °C. The results obtained showed that the doping process much affected the degree of crystallinity of both NiO and Fe2O3 phases detected for all solids calcined at 300 and 500 °C. Fe2O3 interacted readily with NiO at temperature starting from 700 °C producing crystalline NiFe2O4 phase. The degree of reaction propagation increased with increasing calcination temperature. The completion of this reaction required a prolonged heating at temperature >900 °C. K2O-doping stimulates the ferrite formation to an extent proportional to its amount added. The stimulation effect of potassium was evidenced by following up the change in the peak height of certain diffraction lines characteristic NiO, Fe2O3, NiFe2O4 phases located at “d” spacing 2.08, 2.69 and 2.95 Å, respectively. The change of peak height of the diffraction lines at 2.95 Å as a function of firing temperature of pure and doped mixed solids enabled the calculation of the activation energy (ΔE) of the ferrite formation. The computed ΔE values were 120, 80, 49, 36 and 25 kJ mol−1 for pure and variously doped solids, respectively. The decrease in ΔE value of NiFe2O4 formation as a function of dopant added was not only attributed to an effective increase in the mobility of reacting cations but also to the formation of potassium ferrite. The calcination temperature and doping with K2O much affected the catalytic activity of the system under investigation.  相似文献   

5.
Microdifferential thermal analysis (μ-DTA), X-ray diffraction (XRD) and infrared (IR) spectroscopy were used for the first time to investigate the liquidus and solidus relations in the KPO3–Y(PO3)3 system. The only compound observed within the system was KY(PO3)4 melting incongruently at 1033 K. An eutectic appears at 13.5 mol% Y(PO3)3 at 935 K, the peritectic occurs at 1033 K and the phase transition for potassium polyphosphate KPO3 was observed at 725 K. Three monoclinic allotropic phases of the single crystals were obtained. KY(PO3)4 polyphosphate has the P21 space group with lattice parameters: a=7.183(4) Å, b=8.351(6) Å, c=7.983(3) Å, β=91.75(3)° and Z=2 is isostructural with KNd(PO3)4. The second allotropic form of KY(PO3)4 belongs to the P21/n space group with lattice parameters: a=10.835(3) Å, b=9.003(2) Å, c=10.314(1) Å, β=106.09(7)° and Z=4 and is isostructural with TlNd(PO3)4. The IR absorption spectra of the two forms show a chain polyphosphates structure. The last modification of KYP4O12 crystallizes in the C2/c space group with lattice parameters: a=7.825(3) Å, b=12.537(4) Å, c=10.584(2) Å, β=110.22(7)° and Z=4 is isostructural with RbNdP4O12 and contains cyclic anions. The methods of chemical preparations, the determination of crystallographic data and IR spectra for these compounds are reported.  相似文献   

6.
The solid–solid interactions between pure and alumina-doped cobalt and ferric oxides have been investigated using DTA, IR and XRD techniques. Equimolar proportions of basic cobalt carbonate and ferric oxide and different amounts of aluminum nitrate were added as dopant substrate. The amounts of dopant were 0.75, 1.5, 3.0 and 4.5 mol% Al2O3.

The results obtained revealed that solid–solid interaction between Fe2O3 and Co3O4 takes place at temperatures starting from 700°C to produce cobalt ferrite. The degree of propagation of this reaction increases progressively as a function of precalcination temperature and Al2O3-doping of the reacting solids. However, the heating of pure mixed solids at 1000°C for 6 h. was not sufficient to effect the complete conversion of the reacting solids into CoFe2O4, while the addition of a small amount of Al2O3 (1.5 mol%) to ferric/cobalt mixed solids followed by precalcination at 1000°C for 6 h conducted the complete conversion of the reacting solids into cobalt ferrite. The heat treatment of pure and the 0.75 mol%-doped solids at 900 and 1000°C effected the disappearance of most of IR transmission bands of the free oxides with subsequent appearance of new bands characteristic for the CoFe2O4 structure. An increase in the amount of Al2O3 added from 1.5–4.5 mol% to the mixed solids precalcined at 1000°C led to the disappearance of all bands of free oxides and appearance of all bands of cobalt ferrite. The promotion effect of Al2O3 in cobalt ferrite formation was attributed to an effective increase in the mobility of the various reacting cations. The activation energy of formation (ΔE) of CoFe2O4 phase was determined for pure and doped solids. The computed values of ΔE were, respectively, 99.6, 87.8, 71.9, 64.7 and 48.7 kJ mol−1 for the pure solid and those treated with 0.75, 1.5, 3 and 4.5 mol% Al2O3.  相似文献   


7.
The effects of doping of Co3O4with MgO (0.4–6 mol%) and V2O5 (0.20–0.75 mol%) on its surface and catalytic properties were investigated using nitrogen adsorption at −196°C and decomposition of H2O2 at 30–50°C. Pure and doped samples were prepared by thermal decomposition in air at 500–900°C, of pure basic cobalt carbonate and basic carbonate treated with different proportions of magnesium nitrate and ammonium vanadate. The results revealed that, V2O5 doping followed by precalcination at 500–900°C did not much modify the specific surface area of the treated Co3O4 solid. Treatment of Co3O4 with MgO at 500–900°C resulted in a significant increase in the specific surface area of cobaltic oxide. The catalytic activity in H2O2 decomposition, of Co3O4 was found to suffer a considerable increase by treatment with MgO. The maximum increase in the catalytic reaction rate constant (k) measured at 40°C on Co3O4 due to doping with 3 mol% MgO attained 218, 590 and 275% for the catalysts precalcined at 500, 700 and 900°C, respectively. V2O5-doping of Co3O4 brought about a significant progressive decrease in its catalytic activity. The maximum decrease in the reaction rate constant measured at 40°C over the 0.75 mol% V2O5-doped Co3O4 solid attained 68 and 93% for the catalyst samples precalcined at 500 and 900°C, respectively. The doping process did not modify the activation energy of the catalyzed reaction but much modified the concentration of catalytically active constituents without changing their energetic nature. MgO-doping increased the concentration of CO3+–CO2+ ion pairs and created Mg2+–CO3+ ion pairs increasing thus the number of active constituents involved in the catalytic decomposition of H2O2. V2O5-doping exerted an opposite effect via decreasing the number of CO3+–CO2+ ion pairs besides the possible formation of cobalt vanadate.  相似文献   

8.
Offwhite pure Fe_2P_2O_7 was synthesized through solid phase reaction using Fe_2O_3 and NH_4H_2PO_4 in argon atmosphere.The reaction products of Fe_2O_3 and NH4_H_2PO_4 at a series of temperatures from 400 to 900℃were characterized by XRD.Comparison and analysis of XRD patterns of resultant products indicated well-crystallized Fe_2P_2O_7 could be obtained over 630℃and Fe_2P_2O_7 prepared at 700℃was triclinic in cell type.Comparison of the cell parameters proved that the as-prepared Fe_2P_2O_7 belonged toβ- Fe_2P_2O_7 in crystal phase and SEM showed its size distribution was 0.5-2μm.  相似文献   

9.
The samples of La0.4Sr0.6Co1−yFeyO3−δ (y = 0.2 and 0.4) were prepared using both conventional ceramic technique and nitrate–citrate precursors technique. The phase identification was made by X-ray diffraction method. The refinement of structural parameters from the XRD and neutron diffraction measurements was performed by full profile Rietveld analysis. Neutron diffraction showed that both samples possess distorted perovskite-type structure. Oxygen nonstoichiometry was measured by chemical analysis and thermogravimetry (TG) analysis in the range 20 ≤ T/°C ≤ 900 and 2E-5 ≤ pO2/atm ≤ 4E-1. TG-experiments indicate a relatively fast and reversible oxygen exchange at pO2 > 1E-2 atm. Mass saturation occurs at T < 300 °C upon cooling. The absolute value of oxygen nonstoichiometry was determined by iodometric titration measurements. It was found that both samples have practically stoichiometric composition at 300 °C in air and δ increases with increasing temperature and decreasing oxygen partial pressure.  相似文献   

10.
The reaction between transition metal alkoxides and benzyl alcohol provides a novel soft chemistry route to metal oxide nanoparticles. The method allows the preparation of nanocrystals of two important transition metal oxides, namely V2O3 and Nb2O5. Although the reaction temperatures of 200–220 °C are comparably low, the obtained particles are highly crystalline. According to TEM investigations, the V2O3 crystals exhibit particle sizes between 20 and 50 nm, and the Nb2O5 crystals display platelet-like particle shapes with sizes of 50–80 nm, without any indications of amorphous character.  相似文献   

11.
The arsenic oxide pressure of As2O5 has been studied using mass spectrometry and a transportation method. Mass spectrometry revealed the presence of the species As4O+6, As4O+7, and As4O+8 in the vapour. The existence of volatile species up to As4O10(g) as a result of the reaction As4O10(g) As4O(10−y) (g) +1/2yO2(g) has been assumed.

The oxygen pressure of this equilibrium builds up very slowly. The equilibrium pressure can be expressed by log(pO2/atm) (880−952 K) = −(13940±930)/T + (14.53 ± 1.01)

A stationary arsenic oxide pressure has been measured using the transportation method. Since the oxygen pressure in the transportation gas did not influence the arsenic oxide pressure, it is assumed that only the As4O10(g) pressure has been measured. The results can be expressed by the linear function log(pAs4O10/atm) (865−1009 K) = −(15741 ± 410)/T + (13.87 ± 0.42).  相似文献   


12.
The effect of replacement of R4Sn by germanium and silicon derivatives as the promoter for the catalyst system Re2O7/SiO2-Al2O3 in the metathesis of hex-1-ene, and the system Re2O7/B2O3/SiO2-Al2O3 in the metathesis of methyl oleate, was studied. The new promoters react slowly with the rhenium oxide. An activation time of about 15 min at temperatures varying from 50 to 75 °C is required for obtaining a good catalytic activity. These promoters can replace the toxic tin compounds, although they give rise to lower turnover numbers in the metathesis of methyl oleate.  相似文献   

13.
Ferrites have continued to attract attention over years. As magnetic materials, ferrites cannot be replaced by any other magnetic material because they are relatively inexpensive, stable and have a wide range of technological applications in transformer core, high quality filters, high frequency circuits and operating devices. Nanocrystallite sizes of Cu0.5 Zn0.5Fe2O4 with 25 nm have been obtained by hydrothermal route. Cu0.5Zn0.5Fe2O4 powder was isothermally reduced in H2 flow at 400–600 °C. The reduction behavior of the produced powder as well as the influence of reduction temperature on the structural characteristics of the products was extensively studied. Microstructure of partially and completely reduced samples was investigated and the activation energy values were calculated from Arrhenius equation. The activation energy for nanocrystallite Cu0.5 Zn0.5Fe2O4 reduced at the initial stage was found to be 37.4 kJ/mole, while that at the final stage is 14 kJ/mole. The approved mathematical formulations for the different crystallite sizes gas solid reaction were applied and it was found that at the final stages the reaction is controlled by the gaseous diffusion while the combined gaseous diffusion and interfacial chemical reaction is the rate controlling mechanisms at the initial stages. The reduction process produce nanoparticles metallic phases of iron, copper and zinc, which have ball and fibers shapes.  相似文献   

14.
One-dimensional Co(dien)2(VO3)3·(H2O) was prepared from the hydrothermal reaction of NH4VO3, Co2O3, diethylenetriamine (dien) and H2O at 130 °C. The compound crystallizes in the monoclinic system, space group P21/c with a=16.1581(6) Å, b=8.7006(3) Å, c=13.9893(4) Å, β=103.1483(11)°, V=1915.13(11) Å3, Z=4, and R1=0.0268 for 3060 observed reflections. Single crystal X-ray diffraction revealed that the structure is composed of infinite one-dimensional chains formed by corner-sharing VO4 tetrahedra with Co(dien)3+ complex cations and crystallization water molecules occupying the interchain positions, which are held together to a three-dimensional network via extensive hydrogen-bonding interactions. The compound, with a new zig-zag conformation of metavanadate chains, is the first example of vanadium oxides incorporating trivalent transition metal coordination groups. Other characterizations by elemental analysis, IR and thermal analysis are also described.  相似文献   

15.
The oxygen separation membrane having perovskite structure for the partial oxidation of methane to synthesis gas was prepared. La0.7Sr0.3Ga0.6Fe0.4O3−δ (LSGF) perovskite membrane coated with La0.6Sr0.4CoO3−δ (LSC) (M1), and the one side of M1 membrane coated with NiO (M2) was prepared to examine the partial oxidation of methane. The single oxygen permeations of the LSC + LSGF (M1) membrane and NiO coated membrane (M2) were measured. The oxygen permeation flux in M1 membrane was higher than that of M1 membrane at 850 °C.

The partial oxidation experiment of methane using the prepared membranes was examined at 850 °C. The value of CH4 conversion and CO selectivity of M2 membrane was higher than that of M1 membrane.

NiO/NiAl2O4 catalyst was used to improve the methane conversion, and the partial oxidation experiment of methane with M1 membrane was examined at 850 °C. The CH4 conversion was 88%, and CO selectivity was 100%.  相似文献   


16.
The crystal and magnetic structure of Sr2ErRuO6 has been studied by means of neutron powder diffraction as well as magnetization and susceptibility measurements. Neutron diffraction profile measured at 50 K shows that the Ru5+ and Er3+ are ordered in the B-sites of the perovskite-type structure, while the Sr atoms occupy the A-site. This compound crystallizes with a monoclinic unit cell, space group P21/n and lattice parameters are approximately √2ap × √2ap × 2ap. Magnetic susceptibility measurements reveal the existence of antiferromagnetic interactions in which Ru5+ and Er3+ sublattices are involved. The field dependence of the magnetization indicates the presence of a weak ferromagnetic component at the transition temperature, arising from the spin canting of the antiferromagnetically ordered Ru5+ and Er3+ moments. Thermal evolution of the neutron diffraction patterns indicate that the Nèel temperature is 36 K and the magnetic reflections can be indexed on the basis of a propagation vector k = [0, 0, 0]. The spin arrangement is described by the AxAz magnetic modes where the Ru5+ and Er3+ moments are mainly aligned along the c-axis of the structure, forming an angle of 6° with the c-axis in the case of the Er3+ sublattice and 15° for the Ru5+ moment.  相似文献   

17.
The syntheses and structural determination of NdIII and ErIII complexes with nitrilotriacetic acid (nta) were reported in this paper. Their crystal and molecular structures and compositions were determined by single-crystal X-ray structure analyses and elemental analyses, respectively. The crystal of K3[NdIII(nta)2(H2O)]·6H2O complex belongs to monoclinic crystal system and C2/c space group. The crystal data are as follows: a=1.5490(11) nm, b=1.3028(9) nm, c=2.6237(18) nm, β=96.803(10)°, V=5.257(6) nm3, Z=8, M=763.89, Dc=1.930 g cm−3, μ=2.535 mm−1 and F(000)=3048. The final R1 and wR1 are 0.0390 and 0.0703 for 4501 (I>2σ(I)) unique reflections, R2 and wR2 are 0.0758 and 0.0783 for all 10474 reflections, respectively. The NdIIIN2O7 part in the [NdIII(nta)2(H2O)]3− complex anion has a pseudo-monocapped square antiprismatic nine-coordinate structure in which the eight coordinate atoms (two N and six O) are from the two nta ligands and a water molecule coordinate to the central NdIII ion directly. The crystal of the K3[ErIII(nta)2(H2O)]·5H2O complex also belongs to monoclinic crystal system and C2/c space group. The crystal data are as follows: a=1.5343(5) nm, b=1.2880(4) nm, c=2.6154(8) nm, b=96.033(5)°, V=5.140(3) nm3, Z=8, M=768.89, Dc=1.987 g cm−3, μ=3.833 mm−1 and F(000)=3032. The final R1 and wR1 are 0.0321 and 0.0671 for 4445 (I>2σ(I)) unique reflections, R2 and wR2 are 0.0432 and 0.0699 for all 10207 reflections, respectively. The ErIIIN2O7 part in the [ErIII(nta)2(H2O)]3− complex anion has the same structure as NdIIIN2O7 part in which the eight coordinate atoms (two N and six O) are from the two nta ligands and a water molecule coordinate to the central NdIII ion directly.  相似文献   

18.
With a hydrothermal technique, a layered titanium phosphate with the formula Ti2(H2PO4)(HPO4)(PO4)2 · 0.5C6N2H16 (denoted TP-J2) has been prepared by treating the Ti/H3PO4/H2O/1-methylpiperazine system directly. The as-synthesized products were characterized by powder X-ray diffraction, CP-MAS solid-state 31P NMR spectroscopy, thermogravimetric and differential thermal analyses (TG-DTA). The structure was solved by single-crystal X-ray diffraction analysis and it presents an extended γ-phase intercalated with organic amine. Crystal data: triclinic, , a = 8.106 (2) Å, b = 8.197 (2) Å, c = 11.658 (2) Å.  = 78.32 (3)°, β = 80.85 (3)°, γ = 77.90 (3)°, Z = 2. Additionally, the intercalation behavior of TP-J2 with n-alkyl monoamine (n = 2, 3, 4, 6, 8, 10 and 12) was investigated. Owing to the strong brønsted base, N,N′-dimethylpiperazine, resides in the interlayer, it presented unusual features of TP-J2 in contrast with that of γ-Tip.  相似文献   

19.
The thermal decomposition of CaOsO3 by differential thermal analyses, thermogravimetry and X-ray powder diffraction has been studied. In nitrogen CaOsO3 decomposes at 880 ± 10°C into CaO, osmium metal and oxygen due to the reaction CaOsO3 → CaO + Os + O2. In static air the decomposition occurs in three stages: 2CaOsO3 + 1/2O2 → Ca2Os2O7 (in region 775–808°C), Ca2Os2O7 → Ca2Os2O6,5 + 1/4O2 (at a temperature interval of 850–1000°C) and in the third stage Ca2Os2O6,5 → 2CaO + OsO4 ÷ 1/4 O2 (at 1005 ± 5°C). The first intermediate Ca2Os2O7 is isostructural with orthorhombic Ca2Nb2O7 and its cell parameters are: a0 = 3.745 Å, b0 = 25.1 Å, c0 = 5.492 Å, Z = 4, space group Cmcm or Cmc2. Ca2Os2O7 exhibits metallic conductivity and its electrical resistivity is 4.6 × 10−2 ohm-cm at 296K.  相似文献   

20.
Irena Szczygiel   《Thermochimica Acta》2001,370(1-2):125-128
The phase diagram of the system CePO4–K3PO4 has been determined based on investigations by differential thermal analysis, X-ray powder diffraction, IR spectroscopy and optical microscopy. The system contains only one intermediate compound K3Ce(PO4)2, which melts incongruently at (1500±20)°C. This compound is stable down to room temperature and exhibits a polymorphic transition at 1180°C. It was confirmed that the low-temperature form β-K3Ce(PO4)2 crystallizes in a monoclinic system, space group P21/m with unit cell parameters a=9.579 (5), b=5.634 (6), c=7.468 (5) Å; =γ=90°, β=90.81 (3)°; V=403.083 Å3.  相似文献   

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