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1.
Highly ordered mesoporous Co3O4, NiO, and their metals were synthesized by nanocasting method using there corresponding mesoporous SBA-15 silica as a template. The obtained porous metal oxides have high surface areas, large pore volume, and a narrow pore size distribution. The N2-adsorption data for mesoporous metal oxides have provided the BET area of 257.7 m2 g−1 and the total pore volume of 0.46 cm3 g−1. The mesoporous metals were employed as a catalyst in the synthesis of (S)-3-pyrrolidinol from chiral (S)-4-chloro-3-hydroxybutyronitrile, and a high yield to (S)-3-pyrrolidinol-salt was obtained on the mesoporous Co metal catalyst.  相似文献   

2.
Periodic mesoporous composite catalysts, [(n-C4H9)4N]4[γ-SiW10O34(H2O)2]/SBA-15 (TBA-1*/SBA-15, where TBA-1* = [(n-C4H9)4N]4[γ-SiW10O34(H2O)2]), with TBA-1* loadings of 4.3-14.8% were prepared by simultaneous hydrolysis and co-condensation of the tetraethoxysilane (TEOS) in the presence of divacant Keggin-type polyoxometalate and triblock copolymer surfactant (P123) followed by hydrothermal treatment process. Structure integrity of the Keggin unit in as-prepared composites was studied by Fourier transform infrared spectroscopy (FT-IR), Raman scattering spectra, and 29Si magic-angle spinning (MAS) NMR. Periodic mesoporous structure of the composites was evaluated by low-angle X-ray powder diffraction (LXRD) patterns, nitrogen porosimetry, and transmission electron microscope (TEM) measurements. As-prepared TBA-1*/SBA-15 was used as an heterogeneous oxidation catalyst for the styrene epoxidation reaction to synthesize styrene oxide in the presence of dilute H2O2 (30%), and influences of solvent, molar ratio of styrene to H2O2, TBA-1* loading on the styrene conversion, styrene oxide yield and selectivity were considered.  相似文献   

3.
The promotion of sulfur oxides on the selective catalytic reduction (SCR) of NO by hydrocarbons in the presence of a low concentration of sulfur oxides over Ag/Al2O3 has been investigated by a flow reaction test and in situ infrared spectroscopy. When the C3H6 (or C10H22) + NO + O2 feed-flow reaction was tested, maximum NO reduction was below 30% over fresh Ag/Al2O3. After the addition of SO2 to the feed flow, conversion increased slightly. Conversion increased further after SO2 was cut-off from the feed flow. This demonstrated that the increase in NO reduction activity of the catalyst was related to SOx adsorbed on the catalyst. SOx adsorbed on the catalytic surface (1375 cm−1) was detected by IR spectroscopy and was stable within the temperature range. NCO species, as an intermediate in NO reduction, on SOx-adsorbed Ag/Al2O3 in a C3H6 + NO + O2 feed flow was observed in in situ IR spectra during the elevation of the reaction temperature from 473 to 673 K, while it was only observed at 673 K on fresh Ag/Al2O3 under the same experimental conditions. We suggest that SOx in low concentrations depressed the combustion of reductants by contaminating hydrocarbon combustion active sites on the catalyst, resulting in an increase in NO reduction efficiency of the reductants.  相似文献   

4.
In H2 and H2/CO oxidation, the H + O2 + M termination step is one of the most important reactions at elevated pressures. With the recent, increased interest in synthetic fuels, an accurate assessment of its rate coefficient becomes increasingly important, especially for real fuel/air mixtures. Ignition delay times in shock-tube experiments at the conditions selected in this study are only sensitive to the rates of the title reaction and the branching reaction H + O2 = OH + O, the rate of which is known to a high level of accuracy. The rate coefficient of the title reaction for M = N2, Ar, and H2O was determined by adjusting its value in a detailed chemical kinetics model to match ignition delay times for H2/CO/O2/N2, H2/CO/O2/Ar, and H2/CO/O2/N2/H2O mixtures with fuel/air equivalence ratios of ? = 0.5, 0.9, and 1.0. The rate of H + O2 + N2 = HO2 + N2 was measured to be 2.7 (−0.7/+0.8) × 1015 cm6/mol2 s for T = 916-1265 K and P = 1-17 atm. The present determination agrees well with the recent study of Bates et al. [R.W. Bates, D.M. Golden, R.K. Hanson, C.T. Bowman, Phys. Chem. Chem. Phys. 3 (2001) 2337-2342], whose rate expressions are suggested herein for modeling the falloff regime. The rate of H + O2 + Ar = HO2 + Ar was measured to be 1.9 × 1015 cm6/mol2 s for T = 932-965 K and P = 1.4 atm. The rate of H + O2 + H2O = HO2 + H2O was measured to be 3.3 × 1016 cm6/mol2 s for T = 1071-1161 K and P = 1.3 atm. These are the first experimental measurements of the rates of the title reactions in practical combustion fuel/air mixtures.  相似文献   

5.
A series of highly ordered mesoporous materials (CF-SBA-15) with heat-resistant magnetism have been successfully prepared from impregnation of cobalt salt, iron salt, and citric acid with as-synthesized SBA-15. XRD and N2 isotherms indicate that these materials have highly ordered hexagonal mesoporous symmetry and open pore systems. The measurement of magnetic property shows that these materials are ferromagnetic even if calcined at 550 °C for 10 h in air, indicating their good heat-resistant magnetism. These results would be very important for recycle and regeneration of adsorbents and catalysts in practical applications. Moreover, this method may be useful for other mesoporous materials with thermally stable magnetism from a combination of other mesoporous materials such as MCM-41 with magnetic nanoparticles of MnFe2O4 and NiFe2O4.  相似文献   

6.
Blue phosphors Ca1 − xAl2O4: xEu2+ were prepared by high temperature solid-state method. Their structure, morphology and luminescent properties were investigated by X-ray diffraction (XRD), scanning electron microscope (SEM) and fluorescence spectroscopy. The effect of different amounts of fluxing agent H3BO3 on structure, morphology and luminescent properties of blue phosphors Ca1 − xAl2O4: xEu2+ luminous intensity caused by different amount of H3BO3 was also investigated. The amount of H3BO3 doped Ca1 − xAl2O4: xEu2+ in optimal luminous intensity had been determined. The results showed that both the excitation and emission spectra of samples were all broad bands, and that the peak of emission spectra was near 442 nm, which was corresponding to the 4f65d → 4f7 transition of Eu2+ illuminating blue light. Ca1 − xAl2O4: xEu2+ (x = 3.5 mol%) could be gained with good morphology and the best luminous intensity when H3BO3 mass ratio was 0.5 wt%.  相似文献   

7.
The effects of temperature and pressure on the formation and decomposition of C6H5C2H2O2 in the C6H5C2H2 + O2 reaction have been investigated at temperatures from 298 to 378 K by directly monitoring the C6H5C2H2O2 radical in the visible region by cavity ringdown spectrometry (CRDS). The rate constant for the C6H5C2H2 + O2 association and that for fragmentation of C6H5C2H2O2 were found to be k1 (C6H5C2H2 + O2 → C6H5C2H2O2) = (3.20 ± 1.19) × 1011 exp(+760/T) cm3 mol−1 s−1 and k2 (C6H5C2H2 O2 → C6H5CHO + HCO) = (1.68 ± 0.13) × 104 s−1, respectively. Additional kinetic measurements by pulsed laser photolysis/mass spectrometry show that C6H5CHO was produced in the C6H5C2H2 + O2 reaction as predicted and the formation of C6H5CHO from the decomposition of C6H5C2H2O2 is temperature-independent, consistent with the CRDS experimental data.  相似文献   

8.
The gas-phase hydrogenolysis of methylcyclopentane (MCP) was investigated over the bimetallic Ir-Au/γ-Al2O3 catalysts. The bimetallic systems containing the atomic Au/Ir ratios in the range of 0.125-8 and a fixed total metal content of 8 wt.%, were prepared by the sequential impregnation (SI) and co-impregnation (CI) methods. The corresponding monometallic Ir/γ-Al2O3 and Au/γ-Al2O3 catalysts were also prepared. The materials were characterized by ICP, XRD, N2 adsorption, TEM, and H2 chemisorption. Highly dispersed Ir nanoparticles were obtained in all cases, while the size of Au nanoparticles increased (up to 50 nm) upon the increasing Au content in the catalyst. The monometallic gold catalyst did not adsorb H2. The incorporation of Au increased the amount of irreversible adsorbed H2 in the Ir-Au/γ-Al2O3 catalysts with respect to the monometallic ones. The products obtained in the MCP hydrogenolysis were 2-methylpentane (2-MP), 3-methylpentane (3-MP) and n-hexane (n-H). The initial rate (molecules of MCP reacted s−1 gIr−1) increased with the Au content. The deactivation was lower for bimetallic catalysts, particularly for the CI ones. The addition of Au played a significant effect on chemisorption and catalytic properties of Ir.  相似文献   

9.
Bifunctional magnetic-optical Fe3O4/ZnO nanocomposites with different molar ratio were successfully synthesized by a facile two-step strategy. Compared with the other methods, it was found to be mild, inexpensive, green, convenient and efficient. Fe3O4 nanocrystal was used as seed for the deposit and growth of ZnO nanoparticle. A series of the characterizations manifested that the combination of Fe3O4 with ZnO nanoparticles was successful. Photocatalytic activity studies confirmed that as-prepared nanocomposites had excellent photodegradating behavior to Methyl Orange (MO) compared to the pure ZnO nanoparticles. The results showed that the degradation percentage of MO was about 93.6% for 1 h when the amount of catalyst was 0.51 g L−1 and initial concentration of MO was 6 × 10−5 mol L−1 in the pH 7 solution. Moreover, the kinetics of photocatalytic degradation reaction could be expressed by the first-order reaction kinetic model. Furthermore, the Fe3O4/ZnO nanocomposites could be also served as convenient recyclable photocatalysts because of their magnetic properties.  相似文献   

10.
A series of Ce1−xCuxO2 nanocomposite catalysts with various copper contents were synthesized by a simple hydrothermal method at low temperature without any surfactants, using mixed solutions of Cu(II) and Ce(III) nitrates as metal sources. These bimetal oxide nanocomposites were characterized by means of XRD, TEM, HRTEM, EDS, N2 adsorption, H2-TPR and XPS. The influence of Cu loading (5-25 mol%) and calcination temperature on the surface area, particle size and catalytic behavior of the nanocomposites have been discussed. The catalytic activity of Ce1−xCuxO2 nanocomposites was investigated using the test of CO oxidation reaction. The optimized performance was achieved for the Ce0.80Cu0.20O2 nanocomposite catalyst, which exhibited superior reaction rate of 11.2 × 10−4 mmol g−1 s−1 and high turnover frequency of 7.53 × 10−2 s−1 (1% CO balanced with air at a rate of 40 mL min−1, at 90 °C). No obvious deactivation was observed after six times of catalytic reactions for Ce0.80Cu0.20O2 nanocomposite catalyst.  相似文献   

11.
TiO2 thick films deposited on macroporous reticulated Al2O3 foams with pore size of 10 ppi and 15 ppi were prepared using dip coating from slurries of Aeroxide® P25 nanopowder and precipitated titania. All prepared films have sufficiently good adhesion to the surface of the substrate also in case of strongly cracked films. No measurable release of deposited TiO2 after repeated photocatalytic cycles was observed. The photocatalytic activity was characterized as the rate of mineralization of aqueous phenol solution under irradiation of UVA light by TOC technique. The best activity was obtained with Aeroxide® P25 coated Al2O3 foam with the pore size of 10 ppi, annealed at 600 °C. The optimal annealing temperature for preparation of films from precipitated titania could be determined at 700 °C. Films prepared by sol-gel deposition technique were considerably thinner compared to coatings made of suspensions and their photocatalytic activity was significantly smaller.  相似文献   

12.
Er/Tm/Yb codoped Y2O3 nanocrystals and Er/Tm/Yb/Li codoped Y2O3 nanocrystals have been synthesized by sol-gel method, bright white light emission has been observed at 976 nm excitation. The blue, green, and red emissions, respectively, arise from the transitions 1G4 → 3H6 of Tm3+, 2H11/2/4S3/2 → 4I15/2, and 4F9/2 → 4I15/2 of Er3+ ion. Moreover, after doping Li+ ions into Er/Tm/Yb codoped Y2O3 nanocrystals, the white light emission increase greatly. CIE coordinate of Er/Tm/Yb/Li codoped Y2O3 nanocrystals is X = 0.32 and Y = 0.36 at 10 W/cm2 excitation, which is very close to the standard equal energy white light illuminate (X = 0.33, Y = 0.33).  相似文献   

13.
A highly dispersed and ultrafine carbon supported Pd nanoparticles (Pd/C) catalyst is synthesized by a facile homogeneous precipitation-reduction reaction method. Under the appropriate pH conditions, [PdCl4]2− species in PdCl2 solution are slowly transformed into the insoluble palladium oxide hydrate (PdO·H2O) precipitation by heat treatment due to a slow hydrolysis reaction, which results in the generation of carbon supported PdO·H2O nanoparticles (PdO·H2O/C) sample with the high dispersion and small particle size. Consequently, a highly dispersed and ultrafine Pd/C catalyst can be synthesized by PdO·H2O → Pd0 in situ reduction reaction path in the presence of NaBH4. As a result, the resulting Pd/C catalyst possesses a significantly electrocatalytic performance for formic acid electrooxidation, which is attributed to the uniformly sized and highly dispersed nanostructure.  相似文献   

14.
Nanosized ZSM-5 type ferrisilicates were successfully prepared using hydrothermal process. Several parameters including gel initiative compositions (Na+ or K+ alkali system), SiO2/Fe2O3 molar ratios and hydrothermal temperature were systematically investigated. The samples were characterized by XRD, TEM, SEM-EDS, BET surface area and ICP techniques. It was found that surface areas and the total pore volume increase with increasing in the SiO2/Fe2O3 molar ratio at Na-FZ ferrisilicates. The catalytic performance of the synthesized catalysts was evaluated in ethylbenzene dehydrogenation to styrene in the presence of N2O or steam at temperatures ranging from 400 °C to 660 °C under atmospheric pressure. The effects of gel initiative compositions, SiO2/Fe2O3 molar ratio as well as the hydrothermal synthesis temperature on the catalytic performance of these catalysts have been addressed. It was shown that styrene yield significantly influenced by altering in the SiO2/Fe2O3 ratio but was not greatly influenced by changes in hydrothermal synthesis temperatures. The comparison between performance of potassium and sodium containing catalysts was shown that the one with potassium has higher yield and selectivity toward styrene production at an optimum temperature of 610 °C.  相似文献   

15.
D.R. Mullins 《Surface science》2006,600(13):2718-2725
A dysprosium oxide thin film was deposited on Ru(0 0 0 1) by vapor depositing Dy in 2 × 10−7 torr O2 while the Ru was at 700 K. The film was ca. 5 nm thick and produced a p(1.4 × 1.4) LEED pattern relative to the Ru(0 0 0 1) substrate. The adsorption and reaction of CO and C2H4 adsorbed on Rh supported on the Dy2O3 film were studied by TPD and SXPS. The CO initially reacted with loosely bound oxygen in the substrate to produce CO2. After the loosely bound oxygen was removed, the CO adsorbed non-dissociatively in a manner similar to what is seen on Rh(1 1 1). C2H4 adsorbed on the Rh particles and underwent progressive dehydrogenation to produce H2 during TPD. The C from the C2H4 reacted with the O in Dy2O3 to produce CO. CO dissociation on the Rh particles could be promoted by treating the Dy2O3 with C2H4 before CO exposure.  相似文献   

16.
A novel technique has been developed to synthesize Sn-Fe-Mo-Al2O3, while nanoscale dispersion of a highly active tin phase was finely distributed in a stable inert multi-phase. The precursor was prepared by co-precipitation method with SnCl4, FeCl3, AlCl3 and (NH4)6Mo7O24 as the raw materials. Sn-Fe-Mo-Al2O3 mixture was produced by reducing the precursor with H2. The product was characterized by X-ray diffraction (XRD), ICP and scanning electron microscopy (SEM). The performance of the electrode was investigated. The Sn-Fe-Mo-Al2O3 electrode was found to have an initial charge capacity of over 461 mAh/g, and a reversible volumetric capacity of 2090 mAh/cm3, which is two times larger than that of graphite electrode (800 mAh/cm3). The coulomb efficiency in the first cycle was over 55%, but its cyclability was not improved significantly. In order to enhance the cycle performance, we investigated the anode after heat treated at 270 °C for 12 h. Under the same condition, the first charge-discharge characteristics were almost equivalent to the as-coated anode, and the retention capacity ratio after 20 cycles was improved from 41.1% to 86.5%. The heat-treated Sn-Fe-Mo-Al2O3 electrode exhibited better cycle life. The electrochemical reaction of the Sn-Fe-Mo-Al2O3 electrode with Li may obey the alloying-dealloying mechanism of LixSn(x?4.4) formation in the other tin-based electrodes.  相似文献   

17.
Electron paramagnetic resonance (EPR) and infrared (IR) spectroscopy were used to study the formation of ruthenium and adsorbed species appearing on the catalyst during O2, NO, and CO adsorption at room temperature on 1 wt% Ru/MgF2 catalysts prepared from Ru3(CO)12 . Both EPR and IR results provided clear evidence for the interaction between surface ruthenium and probe molecules. No EPR signals due to ruthenium (Ru) species were recorded at 300 and 77 K after H2-reduction of the catalyst at 673 K. However, at 4.2 K a very weak EPR spectrum due to low-spin (4d5) Ru3+ complexes was detected. A weak anisotropic O2- radicals signal with g∣∣=2.017 and g=2.003 superimposed on a broad (ΔBpp=120 mT), slightly asymmetric line at g=2.45(1) was identified after O2 admission to the reduced sample. Adsorption of NO gives only a broad, Gaussian-shaped EPR line at g=2.43(1) indicating that the admission of NO, similarly to O2 adsorption, brings about an oxidation of Ru species in the course of the NO decomposition reaction. Introduction of NO over the CO preadsorbed catalyst leads to EPR spectrum with parameters g=1.996, g∣∣=1.895, and AN=2.9 mT assigned to surface NO species associated with Ru ions. The IR spectra recorded after adsorption of NO or CO probe molecules showed the bands in the range of frequency characteristic of ruthenium nitrosyl, nitro, and nitrate/nitrite species and the bands characteristic of ruthenium mono-and multicarbonyls, respectively. Addition of CO after NO admission to the catalyst leads to appearance in the IR spectrum, beside the ones characteristic of NO adsorption, the bands which can be attributed to Ru-CO2 and Ru-NCO species, indicating that the reaction between NO and CO occurs. These species were also detected after CO adsorption followed by NO adsorption, additionally to the band at 1850 cm−1 being due to cis-type species.  相似文献   

18.
Y-doped La0.7Sr0.3CrO3−δ is a promising anode catalyst for solid oxygen fuel cell (SOFC). The performances of chemical and physical are measured by SEM, XRD and FT-IR. The conductivities of catalyst are measured by DC four-probe method in 20% H2S-N2, 3% H2-N2 and air from 573 K to 1173 K, respectively. The results show that Y-doped La0.7Sr0.3CrO3−δ powders have perfect perovskite phase structure with no extra peaks and exhibit good chemical compatibility with Ce0.8Sm0.2O1.9 (as electrolyte) in air. Through XRD and FT-IR analysis no sulfur-containing species is detected after exposure to the 20% H2S at 1173 K for 5 h. Meanwhile, Y-doped La0.7Sr0.3CrO3−δ shows that the highest conductivity is 0.21 S/cm at 1173 K in H2S. The open circuit voltages are 0.85 V at 1173 K in H2S and 1.04 V at 823 K in H2. The maximal power densities are 12.4 mW/cm2 in H2S and 1.59 W/cm2 in H2 for cells comprising Y-doped La0.7Sr0.3CrO3−δ-Sm0.2Ce0.8O1.9/Sm0.2Ce0.8O1.9/Ag.  相似文献   

19.
The response of ordered ultrathin Al2O3 films on NiAl(1 1 0) and Ni3Al(1 1 0) substrates to sequential exposures at varying pressures of H2O between 10−7 Torr and 10−3 Torr, ambient temperature, was characterized by LEED, AES and density functional theory (DFT) calculations. In all cases, an increase in average oxide thickness, as determined by AES, was observed, consistent with a field-induced oxide growth mechanism. Ordered oxide films of initial average thicknesses of 7 Å and 12 Å grown on NiAl(1 1 0) achieved a limiting thickness of 17(1) Å, while films of initial thickness of 7 Å and 11 Å grown on Ni3Al(1 1 0) achieved a limiting thickness of 12(1) Å. The LEED patterns for the thinner (7 Å) films were not observed after exposure to 10−5 Torr (NiAl(1 1 0)), or 10−4 Torr (Ni3Al(1 1 0)). In contrast, LEED patterns for the films of greater initial thickness persisted after exposures to 10−3 Torr UHV. DFT calculations indicate an Al vacancy formation energy that is significantly greater (by ∼0.5 eV) on the surface that has the thicker oxide film, directly opposite to what may be naively expected. A simple coordination argument supports these numerical results. Therefore, the greater limiting oxide thickness observed on NiAl(1 1 0) demonstrates that the rate determining step in the oxide growth process is not Al removal from the metal substrate and transport across the oxide/metal interface. Instead, the results indicate that the determining factor in the oxide growth mechanism is the kinetic barrier to Al diffusion from the substrate bulk to the oxide/metal interface. The persistence of the LEED patterns observed for the films of greater initial oxide thickness indicates that the surface disorder generally observed for alumina films grown on aluminide substrates and exposed to intermediate pressures of H2O is due to the growth of a disordered alumina layer over an ordered substrate, rather than to direct H2O interaction with terrace sites.  相似文献   

20.
Yuhai Hu 《Surface science》2007,601(21):5002-5009
The influence of pre-dosed O2 on the catalytic reduction of NO with 13C2H5OH on the surface of stepped Pt(3 3 2) was investigated using Fourier transform infra red reflection-absorption spectroscopy (FTIR-RAS) and thermal desorption spectroscopy (TDS). We show that the oxidation of 13C2H5OH with O2 is a very effective reaction, occurring at 150 K and giving rise to acetate. The presence of NO does not lead to any evident oxidation of 13C2H5OH irrespective of the annealing temperature. For the case of O2 + 13C2H5OH + NO co-adlayers, oxidation of 13C2H5OH also takes place at 150 K. However, no new surface species that are supposed to be an intermediate for the production of N2 are detected.The influence of O2 on the production and desorption of N2 is intimately related to both O2 and 13C2H5OH coverage. The presence of pre-dosed O2 does not greatly promote N2 desorption. In fact, N2 desorption is suppressed quantitatively with increasing O2 coverage, after which unreacted, or left-over O atoms appear and remain on steps. It is concluded that the presence of pre-dosed O2 does not play a role of activating reactants in the catalytic reduction of NO with 13C2H5OH on the surface of Pt(3 3 2).  相似文献   

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