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1.
The effect of manganese on the dispersion, reduction behavior and active states of surface of supported copper oxide catalysts have been investigated by XRD, temperature‐programmed reduction and XPS. The activity of methanol synthesis from CO2/H2 was also investigated. The catalytic activity over CuO‐MnOx/γ‐Al2O3 catalyst for CO2 hydrogenation is higher than that of CuO/γ‐Al2O3. The adding of manganese is beneficial in enhancing the dispersion of the supported copper oxide and make the TPR peak of the CuO‐MnKx/γ‐Al2O3 catalyst different from the individual supported copper and manganese oxide catalysts, which indicates that there exists strong interaction between the copper and manganese oxide. For the CuO/γ‐Al2O3 catalyst there are two reducible copper oxide species; α and β peaks are attributed to the reduction of highly dispersed copper oxide species and bulk CuO species, respectively. For the CuO‐MnOx/γ‐Al2O3 catalyst, four reduction peaks are observed, α peak is attributed to the dispersed copper oxide species; β peak is ascribed to the bulk CuO; γ peak is attributed to the reduction of high dispersed CuO interacting with manganese; δ peak may be the reduction of the manganese oxide interacting with copper oxide. XPS results show that Cu+ mostly existed on the working surface of the Cu‐Mn/γ‐Al2O3 catalysts. The activity was promoted by Cu with positive charge which was formed by means of long path exchange function between Cu? O? Mn. These results indicate that there is synergistic interaction between the copper and manganese oxide, which is responsible for the high activity of CO2 hydrogenation.  相似文献   

2.
Catalytic direct dehydrogenation of methanol to formaldehyde was carried out over Ag‐SiO2‐MgO‐Al2O3 catalysts prepared by sol‐gel method. The optimal preparation mass fractions were determined as 8.3% MgO, 16.5% Al2O3 and 20% silver loading. Using this optimum catalyst, excellent activity and selectivity were obtained. The conversion of methanol and the selectivity to formaldehyde both reached 100%, which were much higher than other previously reported silver supported catalysts. Based on combined characterizations, such as X‐ray diffraction (XRD), scanning electronic microscopy (SEM), diffuse reflectance ultraviolet‐visible spectroscopy (UV‐Vis, DRS), nitrogen adsorption at low temperature, temperature programmed desorption of ammonia (NH3‐TPD), desorption of CO2 (CO2‐TPD), etc., the correlation of the catalytic performance to the structural properties of the Ag‐SiO2‐ MgO‐Al2O3 catalyst was discussed in detail. This perfect catalytic performance in the direct dehydrogenation of methanol to formaldehyde without any side‐products is attributed to its unique flower‐like structure with a surface area less than 1 m2/g, and the strong interactions between neutralized support and the nano‐sized Ag particles as active centers.  相似文献   

3.
A series of metal‐Al2O3 catalysts were prepared simply by the conventional impregnation with Al2O3 and metal chlorides, which were applied to the dehydration of fructose to 5‐hydroxymethylfurfural (HMF). An agreeable HMF yield of 93.1% was achieved from fructose at mild conditions (100°C and 40 min) when employing Cr(III)‐Al2O3 as catalyst in 1‐butyl‐3‐methylimidazolium chloride ([Bmim]Cl). The Cr(III)‐Al2O3 catalyst was characterized via XRD, DRS and Raman spectra and the results clarified the interaction between the Cr(III) and the alumina support. Meanwhile, the reaction solvents ([Bmim]Cl) collected after 1st reaction run and 5th reaction run were analyzed by ICP‐OES and LC‐ITMS and the results confirmed that no Cr(III) ion was dropped off from the alumina support during the fructose dehydration. Notably, Cr(III)‐Al2O3 catalyst had an excellent catalytic performance for glucose and sucrose and the HMF yields were reached to 73.7% and 84.1% at 120°C for 60 min, respectively. Furthermore, the system of Cr(III)‐Al2O3 and [Bmim]Cl exhibited a constant stability and activity at 100°C for 40 min and a favorable HMF yield was maintained after ten recycles.  相似文献   

4.
Nano n‐propylsulfonated γ‐Al2O3 is easily prepared by the reaction of nano γ‐Al2O3 with 1,3‐propanesultone. This reagent can be used as an efficient catalyst for the synthesis of spiro [indoline‐3,4‐pyrazolo[3,4‐e][1,4]thiazepine]diones in aqueous media. This new method consistently has the advantages of excellent yields and short reaction times. Further, the catalyst can be reused and recovered several times. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

5.
A simple, efficient and eco‐friendly procedure has been developed using Cu(II) immobilized on guanidinated epibromohydrin‐functionalized γ‐Fe2O3@TiO2 (γ‐Fe2O3@TiO2‐EG‐Cu(II)) for the synthesis of 2,4,5‐trisubstituted and 1,2,4,5‐tetrasubstituted imidazoles, via the condensation reactions of various aldehydes with benzil and ammonium acetate or ammonium acetate and amines, under solvent‐free conditions. High‐resolution transmission electron microscopy analysis of this catalyst clearly affirmed the formation of a γ‐Fe2O3 core and a TiO2 shell, with mean sizes of about 10–20 and 5–10 nm, respectively. These data were in very good agreement with X‐ray crystallographic measurements (13 and 7 nm). Moreover, magnetization measurements revealed that both γ‐Fe2O3@TiO2 and γ‐Fe2O3@TiO2‐EG‐Cu(II) had superparamagnetic behaviour with saturation magnetization of 23.79 and 22.12 emu g?1, respectively. γ‐Fe2O3@TiO2‐EG‐Cu(II) was found to be a green and highly efficient nanocatalyst, which could be easily handled, recovered and reused several times without significant loss of its activity. The scope of the presented methodology is quite broad; a variety of aldehydes as well as amines have been shown to be viable substrates. A mechanism for the cyclocondensation reaction has also been proposed.  相似文献   

6.
A novel magnetic binary‐metal‐oxide‐coated nanocataly composing of a hollow Fe3O4 core and CeO2‐La2O3 shells with Au nanoparticles encapsulated has been created in this work. The structural features of catalysts were characterized by several techniques, including SEM, TEM, UV‐vis, FTIR, XRD, XPS and TGA analyses. After the coating of CeO2‐La2O3 layer, CeO2‐La2O3/Au/C/Fe3O4 microspheres showed a superior thermal stability and catalytic reactivity compared with a pure CeO2 or La2O3 layer. Accompanied by the burning of carbon layer, the specific surface could be increased by the formation of double‐shelled structure. Besides, the desired samples could be separated by magnet, implying the superior recycle performance. Using the reduction of 4‐nitrophenol by NaBH4 as a model reaction, the microspheres exhibited highly reusability, superior catalytic activity, thermal stability, which are attributed to the unique double‐shelled structure of the support, uniform distribution of Au nanoparticles, the highly thermal stability of CeO2‐La2O3 layer and mixed oxide synergistic effect. As a consequence, the unique nanocatalyst will open a promising way in the fabrication of the double‐shelled hollow binary‐metal‐oxide materials for future research and has great potential in other applications.  相似文献   

7.
A facile strategy is reported for the fabrication of Pt‐loaded core–shell nanocomposite ellipsoids (Fe2O3‐Pt@DSL) consisting of ellipsoidal Fe2O3 cores, double‐layered La2O3 shells and deposited Pt nanoparticles (NPs). The formation of the doubled‐shelled structure uses Fe2O3‐Pt@mSiO2 as template sacrificial agent and it involves the re‐deposition of silica and self‐assembly of metal oxide units. The preparation methods of double‐shelled metal oxides avoid repeated coating and etching and could be utilized to fabricate other shaped double‐shelled composites. Characterization results indicated that the Fe2O3‐Pt@DSL nanocomposites possessed mesoporous structure and tunable shell thickness. Moreover, due to the formation of Fe2O3 and La2O3 composites, Pt NPs can also be stabilized via deposition on chemically active oxides with a synergistic effect. Therefore, as a catalyst for the reduction of 4‐nitrophenol, Fe2O3‐Pt@DSL showed superior catalytic activity and reusability due to structural superiority and enhanced composite synergy. Finally, well‐dispersed Pt NPs were encapsulated into the void between the shell layers to construct the Fe2O3‐Pt@DSL‐Pt catalyst.  相似文献   

8.
Millimeter size γ‐Al2O3 beads were prepared by alginate assisted sol–gel method and grafting organic groups with propyl sulfonic acid and alkyl groups as functionalized γ‐Al2O3 bead catalysts for fructose dehydration to 5‐hydroxymethylfurfural (5‐HMF). Experiment results showed that the porous structure of γ‐Al2O3 beads was favorable to the loading and dispersion of active components, and had an obvious effect on the properties of the catalyst. The lower calcination temperature of γ‐Al2O3 beads increased the specific surface area, the hydrophobicity and the activity of catalysts. Competition between the reaction of alkyl groups and ‐SH groups with surface hydroxyl during the preparation process of the catalyst influenced greatly the acid site densities, hydrophobic properties and activity of the catalyst. With an increase in the alkyl group chain, the hydrophobicity of catalysts increased obviously and the activity of the catalyst was enhanced. The most hydrophobic catalyst C16‐SO3H‐γ‐Al2O3–650°C exhibited the highest yield of 5‐HMF (84%) under the following reaction conditions: reaction medium of dimethylsulfoxide/H2O (V/V, 4:1), catalyst amount of 30 mg, temperature of 110°C and reaction time of 4 hr.  相似文献   

9.
The activities of a MnO/γ‐Al2O3 catalyst for the selective reduction of methyl benzoate to benzaldehyde have been studied in a continuous flow reactor. Characterization of the catalyst has been conducted by XRD, XPS, NH3‐TPD and TPD‐IR. XRD and XPS results revealed that the steady state catalyst is mainly MnO2/γ‐AlO3 before reduction and MnO/γ‐Al2O3 after reduction. Monolayer dispersion capacity obtained by XPS method is about w (Mn)11.3% TPD‐IR results revealed that there are only L acidic centers on the catalytic surface. NH3‐TPD determinations have verified that the catalyst with a certain number of moderate strength acidic sites is advantageous to hydrogenation of methyl benzoate to benzaldehyde.  相似文献   

10.
Several TiO2 and γ‐Al2O3 supported catalyst systems were prepared by a novel way and characterized by X‐ray diffraction, Raman spectroscopy and BET surface area measurement. The results show: (1) all the samples, including MoO3/TiO2, WO3/TiO2, V2O5/TiO2, FeSO4/γ‐Al2O3, Al2 (SO4)3/γ‐Al2O3, K2CO3/‐Al2O3 and so on, prepared by impregnating TiO2·H2O or pseudo‐boehmite AlO(OH) with the active components then calcining at a high temperature exhibit much larger surface areas than that of pure TiO2 or γ‐Al2O3 calcined at the same temperature; (2) the surface area of the sample increases with the increase in the coverage of active component on the surface of the support; (3) when the content of active component reaches its utmost monolayer dispersion capacity, the surface area of the sample is the largest, and then decreases when the content of active component exceeds its dispersion threshold.  相似文献   

11.
Hydrolysis reaction of Fe(NO3)3 at a high temperature in the presence of urea as the homogeneous precipitant was studied. With the prepared ceramic filter balls loaded with α-Fe2O3 after high temperature calcination, the loading of α-Fe2O3 on the porous ceramic filter balls from Fe(NO3)3 solutions of different concentrations and mechanical stability of the loaded α-Fe2O3 were studied. The product was characterized using XRD and SEM. Adsorption experiments were conducted to evaluate the performance of the product in adsorbing NH3-N. It turned out that the specific surface area of the ceramic filter balls loaded with α-Fe2O3 had increased to 36.5387 m2/g from original 4.6127 m2/g. When the concentration of Fe(NO3)3 was 0.40 mol/L, the loading of α-Fe2O3 on the ceramic filter balls accounted for 8.4% of the total mass of the adsorbent and α-Fe2O3 was adsorbed on the filter balls very well. The adsorption isotherm of NH3-N on the ceramic filter ball adsorbent loaded with α-Fe2O3 was of Langmuir type. The saturated adsorption capacity was 3.33 mg/L, and the adsorption constant K was 0.1873. NH3-N was adsorbed by α-Fe2O3 more easily, which was a kind of specific adsorption.  相似文献   

12.
A series of KF/Al2O3 catalyzed Michael-addition reactions between malononitrile and α,β-unsaturated cycloketones in DMF solution were studied. At room temperature, 2-cyano-3-aryl-3-(1,2,3,4-tetrahydronaphthalen-1-one-2-yl) propionitrile derivatives were synthesized by the reaction between 2-arylmethylidene-1,2,3,4-tetra-hydronaphthalen-1-one and malononitrile. However, if the temperature was increased to 80℃, 2-amino-3-cyano-4-aryl-4H-benzo[h]chromene derivatives were obtained in high yields. When the α,β-unsaturated ketones were replaced by 2,6-biarylmethylidenecyclohexanone or 2,5-biarylmethylidenecyclopentanone, another series of 2-amino-3-cyano-4H-pyran derivatives was isolated successfully. The structures of the products were confirmed by X-ray diffraction analysis.  相似文献   

13.
Coordination polymers are a thriving class of functional solid‐state materials and there have been noticeable efforts and progress toward designing periodic functional structures with desired geometrical attributes and chemical properties for targeted applications. Self‐assembly of metal ions and organic ligands is one of the most efficient and widely utilized methods for the construction of CPs under hydro(solvo)thermal conditions. 2‐(Pyridin‐3‐yl)‐1H‐imidazole‐4,5‐dicarboxylate (HPIDC2−) has been proven to be an excellent multidentate ligand due to its multiple deprotonation and coordination modes. Crystals of poly[aquabis[μ3‐5‐carboxy‐2‐(pyridin‐3‐yl)‐1H‐imidazole‐4‐carboxylato‐κ5N1,O5:N3,O4:N2]copper(II)dicopper(I)], [CuIICuI2(C10H5N3O4)2(H2O)]n, (I), were obtained from 2‐(pyridin‐3‐yl)‐1H‐imidazole‐4,5‐dicarboxylic acid (H3PIDC) and copper(II) chloride under hydrothermal conditions. The asymmetric unit consists of one independent CuII ion, two CuI ions, two HPIDC2− ligands and one coordinated water molecule. The CuII centre displays a square‐pyramidal geometry (CuN2O3), with two N,O‐chelating HPIDC2− ligands occupying the basal plane in a trans geometry and one O atom from a coordinated water molecule in the axial position. The CuI atoms adopt three‐coordinated Y‐shaped coordinations. In each [CuN2O] unit, deprotonated HPIDC2− acts as an N,O‐chelating ligand, and a symmetry‐equivalent HPIDC2− ligand acts as an N‐atom donor via the pyridine group. The HPIDC2− ligands in the polymer serve as T‐shaped 3‐connectors and adopt a μ3‐κ2N,O2N′,O′:κN′′‐coordination mode, linking one CuII and two CuI cations. The Cu cations are arranged in one‐dimensional –Cu1–Cu2–Cu3– chains along the [001] direction. Further crosslinking of these chains by HPIDC2− ligands along the b axis in a –Cu2–HPIDC2−–Cu3–HPIDC2−–Cu1– sequence results in a two‐dimensional polymer in the (100) plane. The resulting (2,3)‐connected net has a (123)2(12)3 topology. Powder X‐ray diffraction confirmed the phase purity for (I), and susceptibilty measurements indicated a very weak ferromagnetic behaviour. A thermogravimetric analysis shows the loss of the apical aqua ligand before decomposition of the title compound.  相似文献   

14.
Al2O3 insulator layers were deposited step by step by the physical vapor deposition (PVD) method onto gallium nitride in the wurtzite form, n‐type and (0001)‐oriented. The substrate surface and the early stages of Al2O3/n‐GaN(0001) interface formation were characterized in situ under ultra‐high vacuum conditions by X‐ray and ultraviolet photoelectron spectroscopy (XPS, UPS). The electron affinity (EA) of the substrate cleaned by annealing was 3.6 eV. Binding energies of the Al 2p (76.0 eV) and the O 1s (532.9 eV) confirmed the creation of the Al2O3 compound in the deposited film for which the EA was 1.6 eV. The Al2O3 film was found to be amorphous with a bandgap of 6.9 eV determined from the O 1s loss feature. As a result, the calculated Al2O3/n‐GaN(0001) valence band offset (VBO) is ?1.3 eV and the corresponding conduction band offset (CBO) 2.2 eV.  相似文献   

15.
In order to enhance dielectric properties and energy storage density of poly(vinylidene fluoride‐hexafluoro propylene) (PVDF‐HFP), surface charged gas‐phase Al2O3 nanoparticles (GP‐Al2O3, with positive surface charges, ε’ ≈ 10) are selected as fillers to fabricate PVDF‐HFP‐based composites via simple physical blending and hot‐molding techniques. The results show that GP‐Al2O3 are dispersed homogeneously in the PVDF‐HFP matrix and the existence of nanoscale interface layer (matrix‐filler) is investigated by SAXS. The dielectric constant of the composites filled with 10 wt % GP‐Al2O3 is 100.5 at 1 Hz, which is 5.6 times higher than that of pure PVDF‐HFP. The maximum energy storage density of the composite is 4.06 J cm?3 at an electrical field of 900 kV mm?1 with GP‐Al2O3 content of 1 wt %. Experimental results show that GP‐Al2O3 could induce uniform fillers’ distribution and increase the concentration of electroactive β‐phase as well as enhance interfacial polarization in the matrix, which resulted in enhancements of dielectric constant and energy storage density of the PVDF‐HFP composites. This work demonstrates that surface charged inorganic‐oxide nanoparticles exhibit promising potential in fabricating ferroelectric polymer composites with relatively high dielectric constant and energy storage. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 574–583  相似文献   

16.
The Li4.4Al0.4Si0.6O4‐xY2O3 (x = 0 to 0.5) ion conductors were prepared by the Sol‐Gel method and examined in detail. The powder and sintered samples were characterized by DTA‐TG, XRD, SEM, and AC impedance techniques. The experimental results show that the conductivity and sinterability increased with the amount of excess Y2O3 in the silicate. The particle size of the powder samples is about 0.12 μm. The maximum conductivity at 16 °C is 2.925 × 10?5s·cm?1 for Li4.4Al0.4Si0.6O4‐0.3 Y2O3.  相似文献   

17.
Electrocatalytic conversion of carbon dioxide (CO2) has recently received considerable attention as one of the most feasible CO2 utilization techniques. In particular, copper and copper‐derived catalysts have exhibited the ability to produce a number of organic molecules from CO2. Herein, we report a chloride (Cl)‐induced bi‐phasic cuprous oxide (Cu2O) and metallic copper (Cu) electrode (Cu2OCl) as an efficient catalyst for the formation of high‐carbon organic molecules by CO2 conversion, and identify the origin of electroselectivity toward the formation of high‐carbon organic compounds. The Cu2OCl electrocatalyst results in the preferential formation of multi‐carbon fuels, including n‐propanol and n‐butane C3–C4 compounds. We propose that the remarkable electrocatalytic conversion behavior is due to the favorable affinity between the reaction intermediates and the catalytic surface.  相似文献   

18.
Oxidative dehydrogenation of ethane (ODE) is limited by the facile deep oxidation and potential safety hazards. Now, electrochemical ODE reaction is incorporated into the anode of a solid oxide electrolysis cell, utilizing the oxygen species generated at anode to catalytically convert ethane. By infiltrating γ‐Al2O3 onto the surface of La0.6Sr0.4Co0.2Fe0.8O3‐δ‐Sm0.2Ce0.8O2‐δ (LSCF‐SDC) anode, the ethylene selectivity reaches as high as 92.5 %, while the highest ethane conversion is up to 29.1 % at 600 °C with optimized current and ethane flow rate. Density functional theory calculations and in situ X‐ray photoelectron spectroscopy characterizations reveal that the Al2O3/LSCF interfaces effectively reduce the amount of adsorbed oxygen species, leading to improved ethylene selectivity and stability, and that the formation of Al‐O‐Fe alters the electronic structure of interfacial Fe center with increased density of state around Fermi level and downshift of the empty band, which enhances ethane adsorption and conversion.  相似文献   

19.
Epoxy/Al2O3 nanocomposites were prepared using an epoxy resin, diglycidyl ether of bisphenol A, and cured with a polyoxypropylene diamine (Jeffamine D‐400). Transmission electron microscopy and wide angle X‐ray diffraction were employed to reveal the morphology of epoxy/Al2O3 nanocomposites. Dynamic mechanical analysis results showed that the storage modulus and the glass transition temperature (Tg) of epoxy were improved. Tensile strength and Young's modulus also increased with increasing Al2O3 loading. Fracture toughness, as indicated by the stress intensity factor, KQ, was determined using single edge notch bending method, and 40% increase in KQ was observed with only 2 vol % Al2O3. Scanning electron microscopy study of fracture surface showed a rather smooth and flat morphology for neat epoxy. However, massive plastic deformation was observed for epoxy/Al2O3 nanocomposites, leading to the significant increase in fracture toughness. The influence of spherical Al2O3 nanoparticles on thermophysical properties of epoxy was discussed and compared with that of sheet‐like nanoclays. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1466–1473, 2006  相似文献   

20.
A magnetically separable catalyst Al2O3‐MgO/Fe3O4 was prepared by Al2O3‐MgO supported on magnetic oxide Fe3O4 and charactered by FT‐IR, XRD and SEM. The mixed oxides afforded high catalytic activity and selectivity for synthesis of 1‐phenoxy‐2‐propanol from phenol and propylene oxide with 80.3% conversion and 88.1% selectivity to 1‐phenoxy‐2‐propanol. Especially, facile separation of the catalyst by a magnet was obtained and the catalytic performance of the recovered catalyst was unaffected even at the forth run.  相似文献   

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