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1.
T. Uma  M. Nogami   《Journal of membrane science》2006,280(1-2):744-751
A new class of proton conducting glass membranes for hydrogen fuel cell applications are being developed using phosphotungstic acid. These glasses are being design to yield high proton conductivities could be potential substitutes for electrolytes in H2/O2 fuel cell. P2O5–SiO2–PWA glasses have been non-crystalline phases confirmed by structural studies. The glass materials showed good mechanical and thermal stability, and also found a maximum proton conductivity of 9.1 × 10−2 S/cm at 90 °C and 30% RH. The average pore size less than 5 nm was determined by Barrett–Joyner–Halenda (BJH) desorption method. The electrochemical activity was investigated by polarization curves and current–voltage profiles. A maximum power density value of 10.2 mW/cm2 was obtained using 0.15 mg/cm2 of Pt/C loaded on electrode and 5P2O5–87SiO2–8PWA glasses at 30 °C and 30% humidity.  相似文献   

2.
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   

3.
Titania–zirconia mixed oxides with various ZrO2 content in TiO2 (10, 50 and 90 wt.%) were prepared by the sol–gel method. High specific surface areas (77–244 m2/g) were obtained. Acidity determined by NH3-TPD and FTIR-pyridine adsorption showed that in mixed oxides the number of acid sites is dramatically increased; it varies from 173 μmol NH3/g for TiO2 to 1226–1456 μmol NH3/g for the mixed oxides. FTIR-pyridine adsorption showed the presence of Lewis sites in the catalysts. Basic sites were identified by FTIR-CO2 adsorption, suggesting the formation of mixed oxides with acid–basic properties. XRD spectra identified anatase in the TiO2 rich region, amorphous material in the mixed oxide 50–50 TiO2–ZrO2 and tetragonal and monoclinic crystalline phases in the ZrO2 rich region. Activity in the isopropanol decomposition showed a good correlation between the acid–basic properties and the selectivity to propene, acetone and isopropyl ether. The latter was found as a product which mainly depends of the acid sites density.  相似文献   

4.
The mechanism of the SO2 + HO2 reaction was studied theoretically for the first time. Three product channels were revealed, namely, O2 + HOSO, O2 + HSO2, and OH + SO3. The O2 + HOSO channel dominates the reaction under combustion conditions. A five-member-ring complex [SO2–HO2] exists at the entrance of the reaction. The structure and binding energy (De and D0) of the SO2–HO2 complex have been calculated. In view of D0 = 21.2 ± 2.0 kJ mol−1, the SO2–HO2 complex should be stable at low temperature. The infrared spectra and frequency shifts were calculated for both SO2–HO2 and SO2–DO2, and compared with the available experimental data.  相似文献   

5.
TiO2/InN (In/(Ti + In) = 6.5:100 mol) was prepared by nitridation of TiO2/In2O3 by NH3 at 580 °C for 8 h. Only the anatase TiO2 phase was detected in the XRD measurements. The highly dispersed InN clusters on the surface of anatase TiO2 nanocrystals were beyond the detection limit of XRD. In order to confirm the existence of InN in the products of nitridation, thermogravimetry–differential scanning calorimetry–mass spectrometry (TG–DSC–MS) coupling techniques were used for a simultaneous characterizing study of the changes of mass, enthalpy and determination of the evolved gases during the thermal decomposition of the InN and the nitrided TiO2/In2O3 samples. Moreover, pulse thermal analysis (PulseTA) was combined with TG–DSC–MS for the quantitative calibration of the evolved nitrogen formed during the thermal decomposition of the InN and the nitrided TiO2/In2O3. The applied technique enabled identification and quantification of the InN in the products of the nitridation of TiO2/In2O3.  相似文献   

6.
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   

7.
This work presents chemical modeling of solubilities of metal sulfates in aqueous solutions of sulfuric acid at high temperatures. Calculations were compared with experimental solubility measurements of hematite (Fe2O3) in aqueous ternary and quaternary systems of H2SO4, MgSO4 and Al2(SO4)3 at high temperatures. A hybrid model of ion-association and electrolyte non-random two liquid (ENRTL) theory was employed to fit solubility data in three ternary systems H2SO4–MgSO4–H2O, H2SO4–Al2(SO4)3–H2O at 235–270 °C and H2SO4–Fe2(SO4)3–H2O at 150–270 °C. Employing the Aspen Plus™ property program, the electrolyte NRTL local composition model was used for calculating activity coefficients of the ions Al3+, Mg2+ Fe3+ and SO42−, HSO4, OH, H3O+, respectively, as well as molecular species. The solid phases were hydronium alunite (H3O)Al3(SO4)2(OH)6, hematite Fe2O3 and magnesium sulfate monohydrate (MgSO4)·H2O which were employed as constraint precipitation solids in calculating the metal sulfate solubilities. A correlation for the equilibrium constants of the association reactions of complex species versus temperature was implemented. Based on the maximum-likelihood principle, the binary interaction energy parameters for the ionic species as well as the coefficients for equilibrium constants of the reactions were obtained simultaneously using the solubility data of the ternary systems. Following that, the solubilities of metal sulfates in the quaternary systems H2SO4–Fe2(SO4)3–MgSO4–H2O, H2SO4–Fe2(SO4)3–Al2(SO4)3–H2O at 250 °C and H2SO4–Al2(SO4)3–MgSO4–H2O at 230–270 °C were predicted. The calculated results were in excellent agreement with the experimental data.  相似文献   

8.
The drying and sintering processes of SiO2–ZrO2 alkoxide-derived gels have been studied by means of DSC technique. In the drying process, most part of water and alcohols are removed from the gels. For the SiO2 gel such elimination occurs at the end of the drying process, however for the ZrO2 gel this elimination occurs during the whole drying time. An intermediate behavior is observed for the binary system SiO2–ZrO2 gels. In the sintering process, the DSC technique allows to determine the elimination of water and alcohols retained within the structure (open or close pores) and the well-known hydroxyl condensation of silica gel between 700° and 800°C is also observed. The ZrO2 gel shows the final hydroxyl condensation at the heating temperature of 600°C. For the binary SiO2–ZrO2 gels, the hydroxyl condensation has been associated to the activation energy needed for the dissociation of silica hydroxyls. This energy decreases with the ZrO2 concentration in the gel resulting in a sintering treatment of 500°C leading to the entire hydroxyl condensation for the gel with 75% ZrO2–25% SiO2.

By studying the temperature of the DSC peaks, it is possible to know the temperature at which most part of water and alcohols are leaving the gel, and these results can be used in order to select the corresponding drying or sintering schedules for obtaining a well-fabricated material.  相似文献   


9.
Physico-chemical properties of the binary system NaHSO4–KHSO4 were studied by calorimetry and conductivity. The enthalpy of mixing has been measured at 505 K in the full composition range and the phase diagram calculated. The phase diagram has also been constructed from phase transition temperatures obtained by conductivity for 10 different compositions and by differential thermal analysis. The phase diagram is of the simple eutectic type, where the eutectic is found to have the composition X(KHSO4) = 0.44 (melting point ≈ 406 K). The conductivities in the liquid region have been fitted to polynomials of the form κ(X) = A(X) + B(X)(T − Tm) + C(X)(T − Tm)2, where Tm is the intermediate temperature of the measured temperature range and X, the mole fraction of KHSO4. The possible role of this binary system as a catalyst solvent is also discussed.  相似文献   

10.
The solid–liquid equilibria of the ternary system H2O–Fe(NO3)3–Co(NO3)2 were studied by using a synthetic method based on conductivity measurements.

Two isotherms were established at 0 and 15 °C, and the stable solid phases which appear are the iron nitrate nonahydrate (Fe(NO3)3·9H2O), the iron nitrate hexahydrate (Fe(NO3)3·6H2O), the cobalt nitrate hexahydrate (Co(NO3)2·6H2O) and the cobalt nitrate trihydrate (Co(NO3)2·3H2O).  相似文献   


11.
An overview on the variation of the thermal expansion, the electrical conductivity as well as non-stoichiometry of the oxide content as a function of composition within the quasi-ternary system La0.8Sr0.2MnO3−δ–La0.8Sr0.2CoO3−δ–La0.8Sr0.2FeO3−δ in air is presented. The various powders were synthesized under identical conditions. The DC electrical conductivity values of the compositions at 800 °C in air vary in a wide range from 15 to 1338 S cm−1. The magnitude of electrical conductivity of the perovskites is mainly determined by the percentage of cobalt in the compositions. A similar behaviour was observed for the measured thermal expansion coefficients between room temperature and 1000 °C in air, increasing from 10.9 to 19.4 × 10−6 K−1 as a function of cobalt content. Changes in the oxygen stoichiometry of the materials were characterized by temperature-programmed oxidation measurements.  相似文献   

12.
Al2O3–ZrO2 mixed supports have been synthesised using a colloidal solution of ZrO(OH)2 or a Zr(IV) propoxide solution in organic medium. Zirconia content in these samples was about 10% (36% of the theoretic monolayer). The hydrothermal stability (alumina→boehmite transformation at 230 °C, about 10 bar pressure, in the presence of water vapour) of these supports was then investigated by XRD. The presence of the zirconia over the alumina decrease the quantity of boehmite formed after the hydrothermal treatment. The dispersion of zirconia and the stability in hydrothermal conditions of the final support are function of the preparation method.  相似文献   

13.
The details of weak C–Hπ interactions that control several inter and intramolecular structures have been studied experimentally and theoretically for the 1:1 C2H2–CHCl3 adduct. The adduct was generated by depositing acetylene and chloroform in an argon matrix and a 1:1 complex of these species was identified using infrared spectroscopy. Formation of the adduct was evidenced by shifts in the vibrational frequencies compared to C2H2 and CHCl3 species. The molecular structure, vibrational frequencies and stabilization energies of the complex were predicted at the MP2/6-311+G(d,p) and B3LYP/6-311+G(d,p) levels. Both the computational and experimental data indicate that the C2H2–CHCl3 complex has a weak hydrogen bond involving a C–Hπ interaction, where the C2H2 acts as a proton acceptor and the CHCl3 as the proton donor. In addition, there also appears to be a secondary interaction between one of the chlorine atoms of CHCl3 and a hydrogen in C2H2. The combination of the C–Hπ interaction and the secondary ClH interaction determines the structure and the energetics of the C2H2–CHCl3 complex. In addition to the vibrational assignments for the C2H2–CHCl3 complex we have also observed and assigned features owing to the proton accepting C2H2 submolecule in the acetylene dimer.  相似文献   

14.
We reported on the preparation of a thin BaTiO3-coated layer (2.27 nm) on the surface of TiO2 and its further application in the dye-sensitized solar cells (DSCs). The as-prepared BaTiO3–TiO2 films were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscope (TEM). The performances of the DSCs with and without BaTiO3 coating were analyzed by cyclic voltammograms (CVs), electrochemical impedance spectroscopy (EIS), and current–voltage measurements. It was found that the BaTiO3–TiO2 films with about 12 μm thickness increased the dye adsorption, resulting in increased Jsc. In the meantime, the BaTiO3 modification on the TiO2 surface is beneficial to the formation of an energy barrier against the electron transfer from TiO2 to I3, providing the increase of Voc due to the increased electron density in the TiO2 that is caused by the increased electron lifetime.  相似文献   

15.
Aerosol flame pyrolysis deposition method was applied to deposit the oxide glass electrolyte film and LiCoO2 cathode for thin film type Li-ion secondary battery. The thicknesses of as-deposited porous LiCoO2 and Li2O–B2O3–P2O5 electrolyte film were about 6 μm and 15 μm, respectively. The deposited LiCoO2 was sintered for 2 min at 700 °C to make partially densified cathode layer, and the deposited Li2O–P2O5–B2O3 glass film completely densified by the sintering at 700 °C for 1 h. After solid state sintering process the thicknesses were reduced to approximately 4 μm and 6 μm, respectively. The cathode and electrolyte layers were deposited by continuous deposition process and integrated into a layer by co-sintering. It was demonstrated that Aerosol flame deposition is one of the good candidates for the fabrication of thin film battery.  相似文献   

16.
Two series of nano-sized N-containing MOx–ZnO (M: Fe, W) composite powders were synthesized by spray pyrolysis. The nitrogen content was controlled from 500 to 2100 ppm by changing the powder ingredients and spray pyrolysis temperature. Ultraviolet-visible (UV-Vis) spectra indicated that the N-containing MOx–ZnO powders absorbed not only ultraviolet light (λ<387 nm) like pure ZnO powder, but also part of visible light (λ<650 nm). Acetaldehyde decomposition was used as a probe reaction to evaluate the photocatalysis of these composite powders. The photocatalytic activity of the N-containing ZnO powder was pronouncedly enhanced by the WO3 addition under both UV and visible-light irradiation. However, that of the N-containing ZnO powder was suppressed by the Fe2O3 addition. A model of the semiconductor energy-band structure is proposed to explain the enhancement and suppression of photocatalytic activity.  相似文献   

17.
Application of atmospheric pressure plasma as an alternative technology for the destruction of toluene is demonstrated in this study. Used TiO2 colloidal solution was obtained by an improved sol–gel method, and coated on glass beads to prepare decomposition of toluene. The physical property of synthesized TiO2 catalyst film was analyzed by XRD and SEM spectroscopy. From these results, it was identified that the catalyst film exhibited anatase structure with particle size of about 50–100 nm after calcination at 500 °C for 1 h. The decomposition of toluene in TiO2/O2 plasma system was investigated. Amounts of the catalyst and toluene concentration were fixed as 3 wt.% and 1000 ppm, respectively. The analyses for performance of toluene decomposition and intermediates in reaction were done by the in situ method using the mass spectroscopy and gas chromatography. The toluene of 40% was decomposed at pulse voltage of 13 kV in the only O2 plasma condition without TiO2 catalyst. Furthermore, the conversion enhanced remarkably in the TiO2/O2 plasma system, and it reached 70% at pulse voltage of 13 kV after 120 min. This result was very notable compared with that in photocatalytic system, with below 40% after 120 min reaction.  相似文献   

18.
Electrocatalytic water oxidation to evolve O2 was studied on a Nafion–RuO2–Ru(bpy)32+ composite electrode. The O2 evolution current efficiency was largely improved for the multi-component electrode over the Nafion–RuO2 and Nafion–Ru(bpy)32+ individuals. The redox mediation through the Ru(bpy)32+ was found to dominate over the RuO2 catalytic effect in the water oxidation mechanism. The specific surface area of the RuO2, which was prepared at different temperatures (300–700°C), used in fabricating the composite electrode also played an important role in the overall water oxidation mechanism. Both the reaction and electrode parameters were optimized to get effective electrocatalytic current values in this study.  相似文献   

19.
To develop porous alumina supported MF ZrO2 membranes, ZrO2–Al2O3 composite intermediate layers are considered in order to decrease stress creation during the processing and avoid cracks formation. The relation between distortion stress and sintering shrinkage was experimentally studied. And the cracks formation mechanism was qualitatively evaluated and discussed. Finally, crack-free YSZ membrane with pore size of 0.16 μm on the two ZrO2–Al2O3 intermediate layers possessing a gradient composition was successfully prepared and characterized.  相似文献   

20.
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