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1.
Ta 3N 5 was synthesized by nitridation of Ta 2O 5 under NH 3 flow at 700 °C. The catalyst was pure Ta 3N 5 according to X-ray diffraction (XRD), and was about 5 nm in size with a BET specific surface area 52.8 m 2/g. When Ta 3N 5 was added to Fe 3+/H 2O 2 solution (known as Fenton-like system), most Fe 3+ were adsorbed on the Ta 3N 5 surface and could not react with H 2O 2 in the dark, which is different from the general Fenton reaction. Under visible light irradiation, adsorbed Fe 3+ ions were reduced to Fe 2+ rapidly and Fe 2+ were reoxidized by H 2O 2 on the Ta 3N 5 surface, thus a fast Fe 3+/Fe 2+ cycling was established. Kinetics and ESR measurements supported this mechanism. The Ta 3N 5/Fe 3+/H 2O 2 system could efficiently decompose H 2O 2 to generate hydroxyl radicals driven by visible light, which could accelerate significantly the degradation of organic molecules such as N, N-dimethylaniline (DMA), and 2,4-dichlorophenol (DCP). A mechanism was proposed for iron cycling on the basis of experimental results. 相似文献
2.
SnO 2-based varistors doped with 0.5% cobalt, 0.5% zinc and various tantalum amounts were prepared by the solid-state route. Experimental evidence shows that small quantities of Ta 2O 5 improve the nonlinear properties of the samples significantly. It was found that samples doped with 0.05 mol% Ta 2O 5 exhibit the highest density (98.5%), the lowest electric breakdown field ( Eb=1050 V/cm) and the highest coefficient of nonlinearity (=11.5). The effect of Ta 2O 5 dopant could be explained by the substitution of Ta 5+ by Sn 4+. 相似文献
3.
Two series of catalysts, V 2O 5/TiO 2 and modified V 2O 5/TiO 2, were prepared with a conventional impregnation method. They were tested in the selective oxidation of toluene to benzoic acid under microwave irradiation. The reaction conditions were optimized over V 2O 5/TiO 2. It was found that in the microwave catalytic process the optimum reactor bed temperature of the titled reaction decreases to 500 K (600 K in the conventional process). The modification of V 2O 5/TiO 2 with MoO 3, WO 3, Nb 2O 5 or Ta 2O 5, which has no negative influence on the reaction in the conventional catalytic process, can greatly promote the catalytic activities in the microwave process, leading to a high yield of benzoic acid (41%). The effects of microwave electromagnetic field on the catalysts are discussed. 相似文献
4.
The physical, electronic and reactivity properties of bulk and supported Group V metal oxides (V, Nb, Ta and Db) were compared at the molecular level. Dubnium is a very short-lived element, 60 s, whose properties have not been extensively studied, but can be predicted from knowledge of the other members of the Group V metal oxides. Bulk V 2O 5 possesses platelet morphology with the active surface sites only located at the edges: primarily surface redox sites and some surface acidic sites. Bulk Nb 2O 5 and Ta 2O 5, as well as to be expected for bulk Db 2O 5, possess isotropic morphologies and the active surface sites relatively homogeneously dispersed over their surfaces: only surface acidic sites. However, the bifunctional bulk V 2O 5 was found to exhibit a much higher specific acidic catalytic activity than the acidic bulk Nb 2O 5 and Ta 2O 5, the latter being almost identical in their specific acidic catalytic activity. The bulk properties of the Group V metal oxides were essentially transferred to the analogous supported Group V metal oxides, where the active Group V metal oxides were present as a two-dimensional monolayer on various oxide supports (e.g., Al 2O 3, TiO 2, ZrO 2 as well as Nb 2O 5 and Ta 2O 5). For supported vanadia catalysts, the active surface sites were essentially redox sites, with the exception of supported V 2O 5/Al 2O 3 that also contained strong acidic sites. For supported niobia and tantala catalysts, as well as to be expected for supported dubnia catalysts, the active surface sites were exclusively acidic sites. However, the TOF redox for the supported vanadia catalysts and the TOF acidic for the supported niobia and tantala catalysts varied over several orders of magnitude as a function of the specific oxide support with the electronegativity of the oxide support cation. However, the TOF redox varied inversely to that of the TOF acidic variation because of the opposite requirements of these active surface sites. Surface redox sites are enhanced by reduction and surface acidic sites are enhanced by stabilization (lack of reduction). The current fundamental understanding of the Group V metal oxides allows for the molecular engineering of their metal oxide applied catalytic materials. 相似文献
5.
Catalytic properties of supported gallium oxides have been examined for the selective reduction of NO by CH 4 in excess oxygen. The activity was greatly affected by the support; Ga 2O 3/Al 2O 3 (Al 2O 3 supported Ga 2O 3) and Ga 2O 3–Al 2O 3 mixed oxide exhibited high activity and selectivity as comparable to Ga-ZSM-5, while unsupported Ga 2O 3 and the other supported Ga 2O 3 were ineffective. For Ga 2O 3/Al 2O 3, the activity changed with Ga 2O 3 content, and was highest at about 30 wt% Ga 2O 3, which corresponds to a theoretical monolayer coverage. Gallium oxide highly dispersed on Al 2O 3 is considered to be responsible for the high activity and selectivity. The reaction characteristics of Ga 2O 3/Al 2O 3 were studied and compared with Ga-ZSM-5 and Co-ZSM-5. Ga 2O 3/Al 2O 3 exhibited the highest activity and selectivity at high temperature. In addition, Ga 2O 3/Al 2O 3 showed higher tolerance against water than Ga-ZSM-5. C 3H 8 and C 3H 6 were also evaluated as reducing agents, and Ga 2O 3/Al 2O 3 showed higher activity than Ga-ZSM-5 above 723 K achieving almost complete reduction of NO to N 2. 相似文献
6.
The role of vanadium oxide and palladium on the benzene oxidation reaction over Pd/V 2O 5/Al 2O 3 catalysts was investigated. The Pd/V 2O 5/Al 2O 3 catalysts were more active than V 2O 5/Al 2O 3 and Pd/Al 2O 3 catalysts. The increase of vanadium oxide content decreased the Pd dispersion and increased the benzene conversion. A strong Pd particle size effect on benzene oxidation reaction was observed. Although the catalysts containing high amount of V 4+ species were more active, the Pd particle size effect was responsible for the higher activity. 相似文献
7.
Nb 2O 5 loaded on the supports and mixed with oxides was studied to investigate the activity and acidity for Friedel-Crafts benzylation of anisole. From the study on the loaded catalysts, a preliminary conclusion for the selection of metal oxide was obtained; namely, such an acidic oxide as silica was suitable for the support of Nb 2O 5. Then, MoO 3 and WO 3 were mixed with Nb 2O 5, and prominent high catalytic activity and acidities were observed. Both oxides of Nb 2O 5-MoO 3 and Nb 2O 5-WO 3 showed almost similar behavior with respect to characterization and catalytic activity. Surface area increased, X-ray diffraction (XRD) and Raman bands were lost, acid sites, both Brønsted and Lewis characters generated, and surface acid site density was as high as 2–4 nm −2. The acid sites were generated on the amorphous metal oxides consisting of Nb and Mo or W oxides, different in nature from those of Nb 2O 5 calcined and un-calcined, and active for Friedel-Crafts benzylation. 相似文献
8.
Ammonium oxalate complex of niobium was investigated as an aqueous precursor for the preparation of x% Nb 2O 5/Al 2O 3 ( x=5, 10, 20 and 30 wt.%) samples. Catalysts with the same Nb 2O 5 contents were also prepared from the traditional niobium oxalate/oxalic acid aqueous solution. The catalysts were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), temperature-programmed reduction (TPR), infrared spectroscopy of chemisorbed pyridine and X-ray photoelectron spectroscopy (XPS). A comparison with the preparation method using the niobium oxalate salt was performed. The results showed that the niobium precursor influence the species growing leading to phases with different reducibility. The XPS revealed the presence of multilayers of niobium oxide on the Nb 2O 5/Al 2O 3 samples prepared by using niobium ammonium oxalate complex, while the ones obtained from niobium oxalate led to Nb 2O 5 particles islands. The addition of niobium oxide decreased the fraction of Lewis acid sites and increased the fraction of Brønsted acid sites, independent of the precursor salt. However, the creation of BAS was more pronounced on the Nb 2O 5/Al 2O 3 samples prepared from niobium oxalate. 相似文献
9.
Pd/Nb 2O 5/Al 2O 3 catalysts were investigated on propane oxidation. Diffuse reflectance spectroscopy (DRS) and X-ray photoelectron spectroscopy (XPS) analysis suggested that monolayer coverage was attained between 10 and 20 wt.% of Nb 2O 5. Temperature programmed reduction (TPR) evidenced the partial reduction of niobium oxide. The maximum propane conversion observed on the Pd/10% Nb 2O 5/Al 2O 3 corresponded to the maximum Nb/Al surface ratio. The presence of NbO x polymeric structures near to the monolayer could favor the ideal Pd 0/Pd 2+ surface ratio to the propane oxidation which could explain the promoting effect of niobium oxide. 相似文献
10.
Surface-phase ZrO 2 on SiO 2 (SZrOs) and surface-phase La 2O 3 on Al 2O 3 (SLaOs) were prepared with various loadings of ZrO 2 and La 2O 3, characterized and used as supports for preparing Pt/SZrOs and Pt/SLaOs catalysts. CH 4/CO 2 reforming over the Pt/SZrOs and Pt/SLaOs catalysts was examined and compared with Pt/Al 2O 3 and Pt/SiO 2 catalysts. CO 2 or CH 4 pulse reaction/adsorption analysis was employed to elucidate the effects of these surface-phase oxides. The zirconia can be homogeneously dispersed on SiO2 to form a stable surface-phase oxide. The lanthana cannot be spread well on Al2O3, but it forms a stable amorphous oxide with Al2O3. The Pt/SZrOs and Pt/SLaOs catalysts showed higher steady activity than did Pt/SiO2 and Pt/Al2O3 by a factor of three to four. The Pt/SZrOs and Pt/SLaOs catalysts were also much more stable than the Pt/SiO2 and Pt/Al2O3 catalysts for long stream time and for reforming temperatures above 700 °C. These findings were attributed to the activation of CO2 adsorbed on the basic sites of SZrOs and SLaOs. 相似文献
11.
The effect of Nb 2O 5 as an additive to MgO catalyst for vapor phase hydrogen transfer reaction between methacrolein and ethanol to form methallyl alcohol and acetaldehyde has been studied. Nb 2O 5 itself was not effective for this reaction, but when Nb 2O 5 was added to MgO, the catalytic performance was enhanced. This result suggests that the preferable active sites on catalyst are increased by combination of Nb 2O 5 and MgO and so the catalytic performance is improved. On the other hand, when BaO or alkali metal oxide was added to Nb 2O 5, the catalytic performance became higher than that of Nb 2O 5 alone. This result suggests that the preferable active site is formed newly by combination of Nb 2O 5 and BaO or alkali metal oxide. 相似文献
12.
Reticular oxygen of Al 2O 3 or CeO x supported on Al 2O 3 was used for the epoxidation of propene without any double bond cleavage. In batch reaction, Al 2O 3 alone was able to convert propene into propene oxide (PO) with 100% selectivity and 2% conversion of propene with a close to 3:1 ratio with respect to the number of Al(III) reduced to elemental Al. When Ce 2O 3/Al 2O 3 or CeO 2/Al 2O 3 was used, Al remained in its +3 oxidation state, while the Ce oxide was the oxidant as demonstrated by XPS analyses. CeO x/Al 2O 3 was more active (propene conversion yield of 4–5%) but the selectivity was lower (70%) as PO was isomerized into acetone and propionaldehyde. Interestingly the use of reticular oxygen very much improves the selectivity with respect to the use of pure O2. In fact, while propene was more efficiently oxidized (10%) with O2 in presence of Al2O3 or CeOx/Al2O3, the selectivity was as low as 40% because C1 and C2 products were formed. However, the use of reticular oxygen represents a selective two-step technique for the use of molecular oxygen as oxidant of propene. The used oxides can be re-oxidized and the whole process can be further improved towards higher yields. PO is quantitatively converted into propene carbonate by reaction with CO2 in presence of Nb2O5. 相似文献
13.
TaON and Ta 3N 5, Ta 5+-based (oxy)nitrides, were studied as visible light driven photocatalysts. Under visible light irradiation (λ≥420 nm), the (oxy)nitrides oxidize water to O 2 and reduce H + to H 2 in the presence of sacrificial reagents (Ag + and methanol). TaON oxidizes water into O 2 efficiently, with a maximum quantum yield of 10%. The photocatalytic reactions proceed via the bandgap transitions ( Eg, TaON: 2.5 eV, Ta 3N 5: 2.1 eV) without any noticeable degradation of the catalysts. The small energy gaps of TaON and Ta 3N 5 are ascribed to the valence band structures consisting of N 2p orbitals. 相似文献
14.
The role of ceria, niobium and molybdenum oxides on the promotion of the NO reduction by CO was studied. A bifunctional mechanism was discussed as a function of both the nature of interaction between metal oxide and palladium and the redox properties of each metal oxide. The NO dissociation was better on the Pd/MoO3/Al2O3 catalyst than on the Pd/CeO2/Al2O3 and Pd/Nb2O5/Al2O3 catalysts. The explanation for the very high N2 production on Pd–Mo catalyst during the TPD analysis may be attributed to the NO+Meδ+ stoichiometric reaction. The promoting effect of a reducible oxide for the NO+CO reaction at low temperature can be ascribed mainly to its easiness for a redox interchange and its interaction with the noble metal particles. This would increase the surface redox ability and favor the dynamic equilibrium needed for high N2 selectivity. 相似文献
15.
The molecular structures and reactivity of the group V metal oxides (V 2O 5, Nb 2O 5 and Ta 2O 5) were compared. Their solid state structural chemistry, physical and electronic properties, number of active surface sites and their chemical reactivity properties were examined. For the bulk oxides, the solid state structural chemistry and the physical and electronic properties are well established. The number of active surface sites and the distribution of surface redox/acid sites were determined with methanol chemisorption and methanol oxidation, respectively. These studies revealed that the active surface sites present in pure V 2O 5 are primarily redox sites and the active surface sites in pure Nb 2O 5 are essentially acidic in nature. Furthermore, the surface redox sites present in pure V 2O 5 are orders of magnitude more active than the surface acid sites in pure Nb 2O 5. Consequently, the catalytic properties of bulk V 2O 5–Nb 2O 5 mixed oxides are dominated by the vanadia component. For the supported metal oxides, where the group V metal oxides are present as two-dimensional metal oxide overlayers, the structural and electronic properties are not well established in the literature. From a combination of molecular spectroscopic characterization methods (e.g., XANES, Raman, IR and UV–Vis DRS), it was possible to obtain this fundamental information. Methanol chemisorption studies demonstrated that a similar number of active surface sites are present in the supported vanadia and niobia catalyst systems. Similar to their bulk oxides, the surface vanadia species possess redox characteristics and the surface niobia species primarily possess acidic characteristics (Lewis acidity). The surface niobia species was a very sluggish redox site during oxidation reactions (e.g., methanol oxidation to formaldehyde and SO 2 oxidation to SO 3), but significantly promoted the surface vanadia redox sites for oxidation reactions that required dual surface redox and acid sites (e.g., butane oxidation to maleic anhydride and selective catalytic reduction of NO x by NH 3 to produce N 2). These new fundamental insights are allowing for the molecular engineering of group V metal oxide catalysts (especially vanadia and niobia). In contrast, the molecular structure and reactivity properties of Ta 2O 5 catalysts are not yet established and will require significant research efforts. 相似文献
16.
Co 3O 4/CeO 2 composite oxides with different cobalt loading (5, 15, 30, 50, 70 wt.% as Co 3O 4) were prepared by co-precipitation method and investigated for the oxidation of methane under stoichiometric conditions. Pure oxides, Co 3O 4 and CeO 2 were used as reference. Characterization studies by X-ray diffraction (XRD), BET, temperature programmed reduction/oxidation (TPR/TPO) and X-ray photoelectron spectroscopy (XPS) were carried out. An improvement of the catalytic activity and thermal stability of the composite oxides was observed with respect to pure Co3O4 in correspondence of Co3O4–CeO2 containing 30% by weight of Co3O4. The combined effect of cobalt oxide and ceria, at this composition, strongly influences the morphological and redox properties of the composite oxides, by dispersing the Co3O4 phase and promoting the efficiency of the Co3+–Co2+ redox couple. The presence in the sample Co3O4(30 wt.%)–CeO2 of a high relative amount of Ce3+/(Ce4+ + Ce3+) as detected by XPS confirms the enhanced oxygen mobility. The catalysts stability under reaction conditions was investigated by XRD and XPS analysis of the used samples, paying particular attention to the Co3O4 phase decomposition. Methane oxidation tests were performed over fresh (as prepared) and thermal aged samples (after ageing at 750 °C for 7 h, in furnace). The resistance to water vapour poisoning was evaluated for pure Co3O4 and Co3O4(30 wt.%)–CeO2, performing the tests in the presence of 5 vol.% H2O. A methane oxidation test upon hydrothermal ageing (flowing at 600 °C for 16 h a mixture 5 vol.% H2O + 5 vol.%O2 in He) of the Co3O4(30 wt.%)–CeO2 sample was also performed. All the results confirm the superiority of this composite oxide. 相似文献
17.
Combustion of CO, ethyl acetate and ethanol was studied over CuO x/Al 2O 3, CuO x–CeO 2/Al 2O 3, CuMn 2O 4/Al 2O 3 and Mn 2O 3/Al 2O 3 catalysts. It was found that modification of the alumina with ceria before subsequent copper oxide deposition increases the activity for combustion of CO substantially, but the effect of ceria was small on the combustion of ethyl acetate and ethanol. The activity increases with the CuO x loading until crystalline CuO particles are formed, which contribute little to the total active surface. The CuO x–CeO 2/Al 2O 3 catalyst is more active than the CuMn 2O 4/Al 2O 3 catalyst for the oxidation of CO but the CuMn 2O 4/Al 2O 3 catalyst is more active for the combustion of ethyl acetate and ethanol. Thermal ageing and water vapour in the feed caused a modest decrease in activity and did not affect the CuOx–CeO2/Al2O3 and CuMn2O4/Al2O3 catalysts differently. In addition, no difference in intermediates formed over the two catalysts was observed. Characterisation with XRD, FT-Raman and TPR indicates that the copper oxide is present as a copper aluminate surface phase on alumina at low loading. At high loading, bulk CuO crystallites are present as well. Modification of the alumina with ceria before the copper oxide deposition gives well dispersed copper oxide species and bulk CuO crystallites associated to the ceria, in addition to the two copper oxide species on the bare alumina. The distribution of copper species depends on the ceria and copper oxide loading. The alumina supported copper manganese oxide and manganese oxide catalysts consist mainly of crystalline CuMn2O4 and Mn2O3, respectively, on Al2O3. 相似文献
18.
Catalytic activities of various Pt/MO x/SiC systems for carbon oxidation under simulated diesel exhaust gas were investigated in temperature-programmed reactions. When Pt/MO x (MO x=TiO 2, ZrO 2, Al 2O 3) was loaded onto silicon carbide (SiC), the oxidation activities became higher than those of Pt/MO x alone or other Pt/MO x/SiC systems (MO x=Ta 2O 5, WO 3, Nb 2O 5, SnO 2, SiO 2, CeO 2, MoO 3, V 2O 5). Among them, Pt/TiO 2/SiC exhibited the highest activity. We discuss the activity of MO x=TiO 2, ZrO 2, and Al 2O 3 in connection with NO oxidation activity, adsorption of sulfate onto the support, Pt dispersion, and specific surface area of the catalyst. Furthermore, we investigated the catalytic performance of Pt/TiO 2/SiC in more detail under isothermal conditions and in a staged arrangement. 相似文献
19.
The physico-chemical characteristics and the reactivity of sub-monolayer V 2O 5-WO 3/TiO 2 deNO x catalysts is investigated in this work by EPR, FT-IR and reactivity tests under transient conditions. EPR indicates that tetravalent vanadium ions both in magnetically isolated form and in clustered, magnetically interacting form are present over the TiO 2 surface. The presence of tungsten oxide stabilizes the surface V IV and modifies the redox properties of V 2O 5/TiO 2 samples. Ammonia adsorbs on the catalysts surface in the form of molecularly coordinated species and of ammonium ions. Upon heating, activation of ammonia via an amide species is apparent. V 2O 5-WO 3/TiO 2 catalysts exhibits higher activity than the binary V 2O 5/TiO 2 and WO 3/TiO 2 reference sample. This is related to both higher redox properties and higher surface acidity of the ternary catalysts. Results suggest that the catalyst redox properties control the reactivity of the samples at low temperatures whereas the surface acidity plays an important role in the adsorption and activation of ammonia at high temperatures. 相似文献
20.
SiC/Si 3N4 composites with rare earth oxide additions have been prepared by glass encapsulated hot isostatic pressing at 1850 °C and 200 MPa pressure. Mechanical properties and microstructures of the sintered samples have been studied. It is shown that different molar ratios of La 2O 3 to Y 2O 3 and the total amount of La 2O 3 and Y 2O 3 additions can affect the mechanical properties significantly. With 3 wt% La 2O 3 + Y 2O 3 additions, lower La 2O 3/Y 2O 3 molar ratio exhibits higher bending strength and median fracture toughness, but relatively lower Vickers hardness. For addition of 6 wt% La 2O 3 + Y 2O 3, the higher bending strength, Vickers hardness and fracture toughness correspond to a certain La 2O 3/Y 2O 3 molar ratio of 1.5, 1.0 and 0.5, respectively. SEM observation shows that the SiC matrix composite with fine grain size and homogeneous microstructure can be obtained. 相似文献
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