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1.
《Catalysis communications》2007,8(11):1763-1766
Selective hydrogenation of p-chloronitrobenzene to p-chloraniline over ruthenium catalyst was found to be promoted remarkably (Selectivity: from 80.4% to 98.6%; TON: from 0.89 × 10−2 s−1 to 3.20 × 10−2 s−1) by simply adding some water into the solvent of ethanol. The optimized volume percent of water in ethanol was 30%. The promoting effect of water was also found over various supported metal catalysts, such as Fe/SiO2, Co/SiO2, Ni/SiO2, Cu/SiO2, and Ag/SiO2.  相似文献   

2.
《Catalysis communications》2007,8(10):1472-1478
Cobalt oxide (CoOx) prepared by a direct calcination of cobalt nitrate was considerably active for the epoxidation of styrene with air in DMF under mild conditions. A substrate conversion of 75.8 mol% with an epoxide selectivity of 82.1% was achieved at 353 K over 10 mg of cobalt oxide catalyst. Once CoOx was loaded on the support SiO2 through a simple procedure consisting of wet impregnation, drying and calcination, the as-prepared catalyst presented higher catalytic activity and epoxide selectivity than cobalt oxide itself. Over the optimized catalyst CoOx/SiO2 (1.0 wt% Co), 85.7 mol% of styrene was effectively converted at 363 K within 4 h, with a high epoxide selectivity up to 86.0%. The results showed that many factors influenced the performance of the catalyst, such as the Co loading, the support, the temperature and the atmosphere, etc. The leaching of cobalt from the catalyst CoOx/SiO2 was negligible, indicating the applicability of the catalyst CoOx/SiO2 as a true heterogeneous catalyst. The control test and UV–vis spectra revealed a synergic interaction among solvent, oxygen and substrate over CoOx/SiO2.  相似文献   

3.
The present work describes a sensitive procedure for extraction and determination of three sulfonylurea herbicides (metsulfuron-methyl, bensulfuron-methyl and chlorsulfuron) in water samples using supramolecular solvent microextraction. A supramolecular solvent with a nano structure made up of decanoic acid assemblies dispersed in tetrahydrofuran and water was proposed. Also, a supercritical fluid extraction coupled with supramolecular solvent microextraction was applied for extraction and determination of ultra-trace amounts of sulfonylurea herbicides in soil samples. A Taguchi orthogonal array experimental design with an OA16 (45) matrix was employed to optimize the supercritical fluid extraction conditions. In supercritical fluid extraction–supramolecular solvent microextraction procedure, a mixture of decanoic acid and the SFE collecting solvent (tetrahydrofuran) was added to water for supramolecular solvent formation. The effective parameters on the supramolecular solvent microextraction efficiency were studied and optimized using two different optimization methods: one variable at a time and face centered design. Under the optimum conditions, linear dynamic ranges varied within 0.1–5 mg kg−1 (0.9978  R2  0.9987) and 0.5–100 μg L−1 (0.9973  R2  0.9995) for all of the sulfonylurea herbicides in the supercritical fluid extraction–supramolecular solvent microextraction and supramolecular solvent microextraction, respectively. The intraday (n = 5) and interday standard deviations were calculated by extracting the SUHs from water and soil samples through supramolecular solvent microextraction and supercritical fluid extraction–supramolecular solvent microextraction. Interday RSDs% lower than 7.1% and intraday RSDs% lower than 3.8% were obtained. Limits of detection, based on a S/N ratio of 3, were 0.5 μg L−1 and 0.7 mg kg−1 for supramolecular solvent microextraction and supercritical fluid extraction–supramolecular solvent microextraction, respectively.  相似文献   

4.
《Ceramics International》2015,41(4):5484-5491
Porous chitosan–SiO2 membranes were prepared by ultrasonic mixing solution-cast and porogen removal method at different SiO2 weight ratios. To remove SiO2 from chitosan membranes, NaOH solution was used to dissolve SiO2. Porous chitosan:SiO2 membrane with the weight ratio 1:2 produced optimum average pore size (8.5 μm) with an amorphous structure and the highest water uptake (257.1%). Further soaking of this membrane in NH4CH3COO electrolyte solution for two days produced the highest conductivity (3.6×10−3 S cm−1) and optimum breakdown voltage (1.8 V). Fabrication of coin cell proton battery displayed an open circuit potential of 1.5 V for 7 days, maximum power density (6.7 mW cm−2) and small current resistance (0.03 Ω). The specific discharge capacities obtained from discharge profile of 39.7 mA h g−1 (0.5 mA) and 43.8 mA h g−1 (1.0 mA) increased as the discharge currents were increased. These results showed that a porous chitosan–SiO2 membrane is suitable membrane for the proton batteries.  相似文献   

5.
《Ceramics International》2017,43(10):7393-7400
Water vapour corrosion resistance of five rare earth monosilicates Y2SiO5, Gd2SiO5, Er2SiO5, Yb2SiO5, and Lu2SiO5 was investigated during testing at 1350 °C for up to 166 h in static air with 90% water vapour. Four of the RE-silicates showed little weight gain (0.859 mg cm−2) after 166 h of exposure. Prior to testing the microstructure consists of equiaxed grains of 4- 7±0.4 µm. XRD analysis showed that after 50 h exposure to water vapour corrosion Y, Er, Yb and Lu-silicates had both mono and disilicates present on their surfaces as a result of the reaction between monosilicate and water vapour to form disilicate, while Gd-silicate has converted completely to G4.67Si3O13 making it less stable for environmental barrier coating application. The microstructures of corroded Y, Er, Yb and Lu-silicates contain ridges and cracks, while that of Gd-silicate contains rounded grains suggesting melting along with striped contract grains.  相似文献   

6.
《Ceramics International》2017,43(2):1795-1801
Borosilicate glass with different concentrations of vanadium and cobalt of the composition (mol%) 40 Na2B4O7- 40 SiO2- (20–x) V2O5- x Co2O3, with x=0, 1, 3 and 5 mol% were prepared by melt quenching technique at 1373 K and investigated by X-ray diffraction (XRD) and FTIR spectroscopy. Optical properties of the obtained borosilicate glasses in the UV–vis range were also investigated. Urbach theory has been used to analyze the optical data. The dc electrical conductivity was investigated for all samples in the temperature range from 298 K to 700 K. The ac electrical conductivity was measured in the frequency range from 50 Hz to 2 MHz from 298 to 523 K. Guntini's theory has been used to analyze the electrical data. It was found that Urbach energy decreases with the increase of vanadium content, the sample with x=0 shows the highest absorption in the visible and IR region and an electrical conductivity in the order of 10−2 Scm−1. The frequency exponent was calculated. A semiconducting behavior has been assessed for the studied glasses. The sample with x=0 has the highest IR absorption, the highest conductivity, at 323 K at different frequencies, and the lowest activation energy; these features are promising for smart windows applications.  相似文献   

7.
Pine (Pinus silvestris) wood with shaped sample dimensions of 20 mm × 20 mm × 5 mm (axial) was selected as the raw material. Samples were dried and, for a half of the samples, resin extraction from the sample was applied. SiO2 sol was prepared, and samples were impregnated under different vacuum/pressure conditions. Relative impregnation efficiency was calculated for impregnated samples and varied from 95 up to 105% of the theoretical value for different samples and impregnation conditions. Impregnation and drying procedures were repeated up to three times to increase the SiO2 amount introduced in the sample. Impregnated samples were pyrolyzed at 500 °C under oxygen free atmosphere with the subsequent high temperature treatment at 1600 °C in an Ar atmosphere. Biomorphic SiC ceramics and its precursors were investigated using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). An experimental result shows that the optimized vacuum/pressure impregnation technique is highly effective for the introduction of SiO2 in the wood.  相似文献   

8.
The extent of reaction between magnesium oxide (MgO) and silica fume (SiO2) is normally limited and mixes require high water contents to give suitable rheology. The use of considerably lower water contents and the formation of magnesium silicate hydrate (M-S-H) gel as a binding phase is made possible by adding sodium hexametaphosphate (Na-HMP) to the mix water prior to the addition of MgO and SiO2. This results in the formation of extensive reaction products and cured samples with high compressive strength and low porosity. In this work, the effect of Na-HMP on the hydration of MgO/SiO2 mixes is investigated using high water to solids ratio samples to allow monitoring of pH and the solution chemistry during hydration. It is shown that a relatively small amount of Na-HMP inhibits the formation of Mg(OH)2 when MgO is hydrolyzed. It is proposed that this is due to adsorption of phosphate species on the MgO which inhibits the nucleation of the Mg(OH)2. This gives rise to high Mg2 + species in solution and elevated pH (> 12) conditions relative to when Mg(OH)2 forms. In contrast, the phosphate does not suppress formation of M-S-H gel. In combination with the enhanced dissolution rate of SiO2 at high pH, M-S-H gel can form quickly without competition for Mg2 + ions by Mg(OH)2 precipitation. Incorporating the optimum concentration of Na-HMP into the mix water therefore transforms the properties of cement paste and mortar samples formed by reacting MgO and SiO2.  相似文献   

9.
Nanoscale crednerite (CuMnO2) was prepared in the system MnO·CuO·SiO2, using glass–ceramics technique for the first time. Based on obtained data from differential thermal analysis (DTA), the prepared samples were heat-treated at 700 and 800 °C for 2 h. The presence of crystalline phases after and before heat treatment was investigated by X-ray diffraction analysis. Crystallization of crednerite (CuMnO2), manganese silicate (Mn2SiO4) and traces of cuprite (Cu2O) and cristobalite (SiO2) phases were recognized. Transmission electron microscopy showed nanoscale crystals in the range 5–10 nm. The prepared glass–ceramics showed ferrimagnetic properties with wide range coercivity from 53 to 2217 Hci and magnetization saturation from 0.21708 to 1.2 emu/g. From IR reflection data; the reflection intensity of the light is high in the range of orange–red color and violet–blue colors and low in the range of green color.  相似文献   

10.
Lignin has been gasified with a Ni/Al2O3–SiO2 catalyst in sub/supercritical water (SCW) to produce gaseous fuels. XRD pattern at 6θ angle shows characteristic peaks of crystalline NiO, NiSi, and AlNi3, suggesting that Al2O3–SiO2 not only offers high surface area (122 m2 g) for Ni, but also changes the crystal morphology of the metal. 9 mmol/g of H2 and 3.5 mmol/g of CH4 were produced at the conditions that 5.0 wt% alkaline lignin plus 1 g/g Ni/Al2O3–SiO2 operating for 30 min at 550 °C. A kinetic model was also developed, and the activation energies of gas and char formation were calculated to be 36.68 ± 0.22 and 9.0 ± 2.4 kJ/mol, respectively. Although the loss of activity surface area during reuse caused slight activity reduction in Ni/Al2O3–SiO2, the catalyst system still possessed high catalytic activity in generating H2 and CH4. It is noted that sulfur linkage could be hydrolyzed to hydrogen sulfide in the gasification process of alkaline lignin. The stable chemical states of Ni/Al2O3–SiO2 grants its insensitivity to sulfur, suggesting that Ni/Al2O3–SiO2 should be economically promising for sub/supercritical water gasification of biomass in the presence of sulfur.  相似文献   

11.
The effect of ceria on the partial oxidation of methanol to formaldehyde over VOx/CeO2/SiO2 catalysts was investigated. A two-dimensional layer of ceria on silica was prepared by grafting cerium (IV) t-butoxide (Ce(OC4H9)4) onto high surface area, mesoporous silica, SBA-15, and then calcining the resulting product in air at 773 K. Ce surface concentrations obtained this way ranged from 0.2 to 0.9 Ce nm?2. Next, V was introduced by grafting VO(OiPr)3 onto CeO2/SiO2 in order to achieve a surface concentration of 0.6 V nm?2. XANES spectra indicate that all of the V is in the 5+ oxidation state and Raman spectra show that vanadia exist as pseudo-tetrahedra bonded to either silica or ceria. Data from Raman spectroscopy and temperature-programmed desorption of adsorbed methanol indicate that with increasing Ce surface density, most of the V becomes associated with the deposited ceria. The turnover frequency for methanol oxidation is nearly two orders of magnitude higher for VOx/CeO2/SiO2 than for VOx/SiO2, whereas the apparent activation energy and apparent first-order pre-exponential factor are 17 kcal/mol and 1.4 × 106 mol CH2O (mol V atm s)?1, respectively, for VOx/CeO2/SiO2 and 23 kcal/mol and 2.3 × 107 mol CH2O (mol V atm s)?1, respectively, for VOx/SiO2.  相似文献   

12.
The deactivation of Co/SiO2 catalyst for Fischer–Tropsch synthesis (FTS) at different H2 / CO ratios was investigated by XRD, FTIR, BET, XPS, TPR and H2 chemisorption. It was found that the deactivation rate of the catalyst increased with the rise of the H2 / CO ratio. The generation of silicates and/or hydrosilicates species was evidenced by TPR and XPS, and their amounts were monotonously enhanced with increasing H2 / CO ratio, which suggested that the deactivation was caused by the transformation of metallic cobalt into inactive silicates and the high partial pressure of H2 facilitated the formation of the silicates. Moreover, the percentage loss of the surface cobalt was larger than that of bulk cobalt, suggesting that the cobalt silicates and/or hydrosilicates species were formed mainly on the surface of the catalyst or in the small crystallites. For the catalyst run at H2 / CO ratio of 1, it was observed that the sintering also contributed to the catalyst deactivation, but it was a less important factor for the deactivation.  相似文献   

13.
To improve the thermal conductivity of Si3N4 ceramics, elimination of grain-boundary glassy phase by post-sintering heat-treatment was examined. Si3N4 ceramics containing SiO2–MgO–Y2O3-additives were sintered at 2123 K for 2 h under a nitrogen gas pressure of 1.0 MPa. After sintering, the SiO2 and MgO could be eliminated from the ceramics by vaporization during post-sintering heat-treatment at 2223 K for 8 h under a nitrogen gas pressure of 1.0 MPa. Thermal conductivity of 3 mass% SiO2, 3 mass% MgO and 1 mass% Y2O3-added Si3N4 ceramics increases from 44 to 89 Wm−1 K−1 by the decrease in glassy phase and lattice oxygen after the heat-treatment. Relatively higher fracture toughness (3.8 MPa m1/2) and bending strength (675 MPa) with high hardness (19.2 GPa) after the heat-treatment were achieved in this specimen. Effects of heat-treatment on microstructure and chemical composition were also observed, and compared with those of Y2O3–SiO2-added and Y2O3–Al2O3-added Si3N4 ceramics.  相似文献   

14.
《Ceramics International》2017,43(12):9084-9091
This paper reports the preparation of Eu3+ doped Gadolinium oxyorthosilicate (Gd2SiO5:Eu3+) phosphor with different concentration of Eu3+(0.1–2.5 mol%) using the modified solid state reaction method. The synthesis procedure of the Gd2SiO5:Eu3+phosphor using inorganic materials such as Gd2O3, silicon dioxide (SiO2), europium oxide (Eu2O3) and boric acid (H3BO3) as flux is discussed in detail. The prepared phosphor samples were characterized by using X-Ray Diffraction (XRD), Field Emission Gun Scanning Electron Microscopy (FEGSEM), Transmission Electron Microscopy (TEM), Fourier Transform Infrared Spectroscopy (FTIR), Photoluminescence (PL) and Thermoluminescence (TL). The Commission Internationale de l′Eclairage(CIE) coordinates were also calculated. The PL emission was observed in the 350–630 nm range for the Gd2SiO5:Eu3+ phosphor. PL excitation peaks were observed at 266, 275, 312 and 395 nm while the emission peaks were observed at 380, 416, 437, 545, 579, 589, 607, 615 and 628 nm. The emission peak at 615 nm was the most intense peak for all the different Eu3+ concentration samples. From the XRD data, using the Scherrer's formula, the average crystallite size of the Gd2SiO5:Eu3+ phosphor was calculated to be 33 nm. TL was carried out for the phosphor after both UV and gamma irradiation. The TL response of the Gd2SiO5:Eu3+ phosphor for the two different radiations was compared and studied in detail. It was found that the present phosphor can acts as a single host for red emission (1.5 mol%) for display devices and light emitting diode (LED) and white light emission for Eu3+(0.1 mol%) and it might be used as a TL dosimetric material for gamma dose detection.  相似文献   

15.
Phosphorous-modified MoO3/SiO2 catalysts with various P/Mo molar ratios (MoPxO/SiO2, x = 0.3  3.0) were prepared by co-impregnation and compared with MoO3/SiO2 in the oxidation of dibenzothiophene by cumene hydroperoxide. The addition of P significantly enhanced the catalytic performance, and MoP1.0O/SiO2 exhibited the highest oxidation activity. XRD characterization indicated that the active phase of MoP1.0O/SiO2 was amorphous, whereas 31P-NMR measurements revealed that MoP1.0O/SiO2 had a similar connectivity of Mo-O-P to H3PMo12O40. The total sulfur of a hydrotreated diesel was reduced from 298 to 5 ppmw by oxidation with CHP and subsequent dimethylformamide extraction.  相似文献   

16.
Y2SiO5 is a promising candidate for oxidation-resistant or environmental/thermal barrier coatings (ETBC) due to its excellent high-temperature stability, low elastic modulus and low oxygen permeability. In this paper, we investigated the thermal properties of Y2SiO5 comprehensively, including thermal expansion, thermal diffusivity, heat capacity and thermal conductivity. It is interesting that Y2SiO5 has a very low thermal conductivity (~1.40 W/m K) but a relatively high linear thermal expansion coefficient ((8.36 ± 0.5) × 10?6 K?1), suggesting compatible thermal and mechanical properties to some non-oxide ceramics and nickel superalloys as ETBC layer. Y2SiO5 is also an ideal EBC on YSZ TBC layer due to their close thermal expansion coefficients. As a continuous source of Y3+, it is predicted that Y2SiO5 EBC may prolong the lifetime of zirconia-based TBC by stopping the degradation aroused by the loss of Y stabilizer.  相似文献   

17.
New transparent and high infrared reflection films having the sandwich structure of SiO2/Al:ZnO(AZO)/SiO2 were deposited on the soda-lime silicate glass at room temperature by radio frequency (R.F.) magnetron sputtering. The optical and electrical properties of SiO2 (110 nm)/AZO (860 nm)/SiO2 (110 nm) sandwich films were compared with those of single layer AZO (860 nm) films and double layer SiO2 (110 nm)/AZO (860 nm) films. The results show that these sandwich films exhibit high transmittance of over 85% in the visible light range (380–760 nm), and low reflection rate of below 4.5% in the wavelength range of 350–525 nm, which is not shown in the conventional single layer AZO (860 nm) films and double layer SiO2 (110 nm)/AZO (860 nm) films. Further these sandwich films display a low sheet resistance of 20 Ω/sq by sheet resistance formula and high infrared reflection rate of above 80% in the wavelength range of 15–25 μm. In addition, the infrared reflection property of these sandwich films is determined mainly by the AZO film. The outer SiO2 film can diminish the interference coloring and increase transparency; the inner SiO2 film improves the adhesion of the coating to the glass substrate and prevents Ca2+ and Na+ in the glass substrate from entering the AZO film.  相似文献   

18.
(Na0.5Bi0.5)0.94Ba0.06TiO3 thin films were deposited on Pt/Ti/SiO2/Si (1 1 1) and LaNiO3/Pt/Ti/SiO2/Si (1 1 1) substrates by a sol–gel process. The phase structure and ferroelectric properties were investigated. The X-ray diffraction pattern indicated that the (Na0.5Bi0.5)0.94Ba0.06TiO3 thin film deposited on Pt/Ti/SiO2/Si (1 1 1) substrates is polycrystalline structure without any preferred orientation. But the thin film deposited on LaNiO3/Pt/Ti/SiO2/Si substrates shows highly (1 0 0) orientation (f  81%). The leakage current density for the two thin films is about 6 × 10?3 A/cm2 at 250 kV/cm, and thin film deposited on LaNiO3/Pt/Ti/SiO2/Si substrates possessed a much lower leakage current under high electric field. The hysteresis loops at an applied electric field of 300 kV/cm and 10 kHz were acquired for the thin films. The thin films deposited on LaNiO3/Pt/Ti/SiO2/Si substrates showed improved ferroelectricity.  相似文献   

19.
An unprecedented mixed valence cobalt(III)/cobalt(II) ion-pair complex, [CoCO3(bipy)2]2[Co(DCA)2]⋅16H2O (1) [bipy = 2,2′-bipyridine, DCA = demethylcantharidate, exo-1,4-epoxy-cyclohexyl-2,3-dicarboxylate group, (C8H8O5)2 ], has been synthesized and characterized by elemental analysis, IR, UV–vis, Thermogravimetric analysis (TGA) and single crystal X-ray diffraction. The crystal structure of 1 consists of three independent molecular moieties: [CoCO3(bipy)2]+, [Co(DCA)2]2–, and water molecules of crystallization. Interestingly, two novel water tapes, one comprises of alternate cyclic water tetramer and octamer, the other is constructed by alternate cyclic water hexamer and carboxylate–water hybrid octamer [(H2O)2(COO)2]2 , have been detected for the first time in the host framework of 1. The two novel water tapes are linked together by the DCA and carbonate ligands via hydrogen bonds into a 2D water layer, and then the water layers assemble complex ions ([CoCO3(bipy)2]+ and [Co(DCA)2]2 ) through hydrogen bonds, π–π interactions and electrostatic interactions to form the overall 3D metal–organic framework structure.  相似文献   

20.
Subcritical water extraction (SWE) of antioxidants from Coriandrum sativum seeds (CSS) was optimized by simultaneous maximization of the total phenolics (TP) and total flavonoids (TF) yield and antioxidant activity, using IC50 value. Box–Behnken experimental design (BBD) on three levels and three variables was used for optimization together with response surface methodology (RSM). Influence of temperature (100–200 °C), pressure (30–90 bar) and extraction time (10–30 min) on each response was investigated. Experimentally obtained values were fitted to a second-order polynomial model and multiple regression. Analysis of variance (ANOVA) was used to evaluate model fitness and determine optimal conditions. Moreover, three-dimensional surface plots were generated from employed mathematical model. The optimal SWE conditions obtained in simultaneous optimization were temperature of 200 °C, pressure of 30 bar and extraction time of 28.3 min, while obtained values of TP and TF yields and IC50 value at this experimental point would be 2.5452 g GAE/100 g CSS, 0.6311 g CE/100 g CSS and 0.01372 mg/ml, respectively. Moreover, good and moderate linear correlation was observed between antioxidant activity (IC50 value) and total phenolics content (R2 = 0.965), and total flavonoids content (R2 = 0.709) which indicated that these groups of compounds are responsible for antioxidant activity of C. sativum extracts.  相似文献   

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