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1.
Open circuit dependence of potential on oxygen partial pressure as well as potentiostatic behavior in O2- and He-saturated solution were determined. Stable hydrogen-oxygen species were formed, but potential-determining reversbility was found only in the potential range from 0·64–0·70 V (nhe). This equilibrium could be reasonably explained by an O2/H2O2 exchange. Oxygen, H2O2, or other hydrogen-oxygen species may affect open circuit potentials and potentiostatic behavior, but analysis of data assuming reversibility or quasi-equilibrium kinetic theory may be justified only between 0·64 and 0·70 V.  相似文献   

2.
CeO2 and CeReOx_y catalysts are prepared by the calcination at different temperatures (y = 500–1000 °C) and having a different composition (Re = La3+ or Pr3+/4+, 0–90 wt.%). The catalysts are characterised by XRD, H2-TPR, Raman, and BET surface area. The soot oxidation is studied with O2 and NO + O2 in the tight and loose contact conditions, respectively. CeO2 sinters between 800–900 °C due to a grain growth, leading to an increased crystallite size and a decreased BET surface area. La3+ or Pr3+/4+ hinders the grain growth of CeO2 and, thereby, improving the surface catalytic properties. Using O2 as an oxidant, an improved soot oxidation is observed over CeLaOx_y and CePrOx_y in the whole dopant weight loading and calcination temperature range studied, compared with CeO2. Using NO + O2, the soot conversion decreased over CeLaOx_y catalysts calcined below 800 °C compared with the soot oxidation over CeO2_y. CePrOx_y, on the other hand, showed a superior soot oxidation activity in the whole composition and calcination temperature range using NO + O2. The improvement in the soot oxidation activity over the various catalysts with O2 can be explained based on an improvement in the external surface area. The superior soot oxidation activity of CePrOx_y with NO + O2 is explained by the changes in the redox properties of the catalyst as well as surface area. CePrOx_y, having 50 wt.% of dopant, is found to be the best catalyst due to synergism between cerium and praseodymium compared to pure components. NO into NO2 oxidation activity, that determines soot oxidation activity, is improved over all CePrOx catalysts.  相似文献   

3.
La2O3 films were deposited using O3 and the structural and electrical properties were investigated and compared with those of La2O3 films deposited using O2. The deposition temperature of the La2O3 films using O3 was slightly reduced compared to that of the La2O3 films generated using O2. After a post-annealing process at 600 and 900 °C, the crystallinity of the La2O3 films using O3 were smaller than that using O2. The leakage current density increased after annealing at 600 °C due to densification and then decreased after annealing at 900 °C due to interfacial layer growth. The effective dielectric constant of the La2O3 films deposited using O3 decreased at 900 °C due to interfacial layer growth. The La2O3 films deposited using O3 showed better structural and electrical properties in this study.  相似文献   

4.
Pt supported on CeO2 and 10 wt.% La3+-doped CeO2 catalysts have been prepared, characterised and tested for soot oxidation by O2 in TGA. The reaction mechanism has been studied in a TAP reactor with labelled O2. Isotopic oxygen exchange between molecular O2 and ‘O’ on the support/catalyst was observed and soot oxidation is being carried out by lattice oxygen. TAP studies further show that Pt improves O2 adsorption and, therefore, 5 wt.% Pt-containing catalysts are more active for soot oxidation than the counterpart supports. In addition, CeO2 doping by La3+ leads to an improved support, since La3+ stabilises the structure of CeO2 when calcined at high temperature (1000 °C) and minimises sintering. In addition, La3+ improves the Ce4+/Ce3+ reduction as deduced from H2-TPR experiments and favours oxygen mobility into the lattice. A synergetic effect of Pt and La3+ is observed, Pt-containing La3+-doped CeO2 being the most active catalyst for soot oxidation by O2 among the samples studied.  相似文献   

5.
The effect of a commercial Pt/Al2O3 catalyst on the oxidation by NO2 and O2 of a model soot (carbon black) in conditions close to automotive exhaust gas aftertreatment is investigated. Isothermal oxidations of a physical mixture of carbon black and catalyst in a fixed bed reactor were performed in the temperature range 300–450 °C. The experimental results indicate that no significant effect of the Pt catalyst on the direct oxidation of carbon by O2 and NO2 is observed. However, in presence of NO2–O2 mixture, it is found that besides the well established catalytic reoxidation of NO into NO2, Pt also exerts a catalytic effect on the cooperative carbon–NO2–O2 oxidation reaction. An overall mechanism involving the formation of atomic oxygen over Pt sites followed by its transfer to the carbon surface is established. Thus, the presence of Pt catalyst increases the surface concentration of –C(O) complexes which then react with NO2 leading to an enhanced carbon consumption. The resulting kinetic equation allows to model more precisely the catalytic regeneration of soot traps for automotive applications.  相似文献   

6.
Dispersing La2O3 on δ- or γ-Al2O3 significantly enhances the rate of NO reduction by CH4 in 1% O2, compared to unsupported La2O3. Typically, no bend-over in activity occurs between 500° and 700°C, and the rate at 700°C is 60% higher than that with a Co/ZSM-5 catalyst. The final activity was dependent upon the La2O3 precursor used, the pretreatment, and the La2O3 loading. The most active family of catalysts consisted of La2O3 on γ-Al2O3 prepared with lanthanum acetate and calcined at 750°C for 10 h. A maximum in rate (mol/s/g) and specific activity (mol/s/m2) occurred between the addition of one and two theoretical monolayers of La2O3 on the γ-Al2O3 surface. The best catalyst, 40% La2O3/γ-Al2O3, had a turnover frequency at 700°C of 0.05 s−1, based on NO chemisorption at 25°C, which was 15 times higher than that for Co/ZSM-5. These La2O3/Al2O3 catalysts exhibited stable activity under high conversion conditions as well as high CH4 selectivity (CH4 + NO vs. CH4 + O2). The addition of Sr to a 20% La2O3/γ-Al2O3 sample increased activity, and a maximum rate enhancement of 45% was obtained at a SrO loading of 5%. In contrast, addition of SO=4 to the latter Sr-promoted La2O3/Al2O3 catalyst decreased activity although sulfate increased the activity of Sr-promoted La2O3. Dispersing La2O3 on SiO2 produced catalysts with extremely low specific activities, and rates were even lower than with pure La2O3. This is presumably due to water sensitivity and silicate formation. The La2O3/Al2O3 catalysts are anticipated to show sufficient hydrothermal stability to allow their use in certain high-temperature applications.  相似文献   

7.
The kinetics of CO and H2 oxidation over a CuO-CeO2 catalyst were simultaneously investigated under reaction conditions of preferential CO oxidation (PROX) in hydrogen-rich mixtures with CO2 and H2O. An integral packed-bed tubular reactor was used to produce kinetic data for power-law kinetics for both CO and H2 oxidations. The experimental results showed that the CO oxidation rate was essentially independent of H2 and O2 concentrations, while the H2 oxidation rate was practically independent of CO and O2 concentrations. In the CO oxidation, the reaction orders were 0.91, −0.37 and −0.62 with respect to the partial pressure of CO, CO2 and H2O, respectively. In the H2 oxidation, the orders were 1.0, −0.48 and −0.69 with respect to the partial pressure of H2, CO2 and H2O, respectively. The activation energies of the CO oxidation and the H2 oxidation were 94.4 and 142 kJ/mol, respectively. The rate expressions of both oxidations were able to predict the performance of the PROX reactor with accuracy. The independence between the CO and the H2 oxidation suggested different sites for CO and H2 adsorption on the CuO-CeO2 catalyst. Based on the results, we proposed a new reaction model for the preferential CO oxidation. The model assumes that CO adsorbs selectively on the Cu+ sites; H2 dissociates and adsorbs on the Cu0 sites; the adsorbed species migrates to the interface between the copper components and the ceria support, and reacts there with the oxygen supplied by the ceria support; and the oxygen deficiency on the support is replenished by the oxygen in the reaction mixture.  相似文献   

8.
In this study, in order to develop low-temperature sintering ceramics for a multilayer piezoelectric transformer application, we explored CuO and Bi2O3 as sintering aids at low temperature (900 °C) sintering condition for Sb, Li and Mn-substituted 0.8Pb(Zr0.48Ti0.52)O3–0.16Pb(Zn1/3Nb2/3)O3–0.04Pb(Ni1/3Nb2/3)O3 ceramics. These substituted ceramics have excellent piezoelectric and dielectric properties such as d33  347 pC/N, kp  0.57 and Qm  1469 when sintered at 1200 °C. The addition of CuO decreased the sintering temperature through the formation of a liquid phase. However, the piezoelectric properties of the CuO-added ceramics sintered below 900 °C were lower than the desired values. The additional Bi2O3 resulted in a significant improvement in the piezoelectric properties. The composition Sb, Li and Mn-substituted 0.8Pb(Zr0.48Ti0.52)O3–0.16Pb(Zn1/3Nb2/3)O3–0.04Pb(Ni1/3Nb2/3)O3 + 0.5 wt% CuO + 0.5 wt% Bi2O3 showed the value of kp = 0.56, Qm = 1042 (planar mode), d33 = 350 pC/N, when it was sintered at 900 °C for 2 h. These values indicated that the newly developed composition might be suitable for multilayer piezoelectric transformer application.  相似文献   

9.
Fine powders of submicron-sized crystallites of BaTiO3 were prepared at 85–130°C by the hydrothermal method, starting from TiO2.ξH2O gel and Ba(OH)2 solution. The products obtained below 110°C incorporated considerable amounts of H2O and OH in the lattice. As-prepared BaTiO3 is cubic and converts to the tetragonal phase after heat treatment at 1200°C, accompanied by the loss of residual OH ions. Hydrothermal reaction of SnO2.ξH2O gel with Ba(OH)2 at 150–260°C gives rise to the hydrated phase, BaSn(OH)6.3H2O, due to the amphoteric nature of SnO2.ξH2O which stabilises Sn(OH)62− anions in basic media. On heating in air or releasing the pressure in situ at 260°C, BaSn(OH)6.3H2O converts to BaSnO3 through an intermediate, BaSnO(OH)4. Solid solutions of Ba(Ti,Sn)O3 are directly formed from (TiO2 + SnO2)..ξH2O gel up to 35 mol% SnO2. At higher Sn contents, the hydrothermal products are mixtures of BaSn(OH)6.3H2O and BaTiO3, which on annealing at 1000°C result in monophasic Ba(Ti,Sn)O3. The sintering characteristics and the dielectric properties of the ceramics prepared out of these fine powders are presented. The dielectric properties of fine-grained Ba(Ti,Sn)O3 ceramics are explained on the basis of the prevailing diffuse phase transition behaviour.  相似文献   

10.
The electrical and electromechanical properties of Pb(Mg1/3Nb2/3)O3–Pb(Ni1/3Nb2/3)O3–Pb(Zr,Ti)O3 (PMN–PNN–PZT, PMN/PNN/PZT = 20/10/70) on Pt/Ti/SiO2/Si substrates by chemical solution deposition was investigated. The PMN–PNN–PZT films annealed at 650 °C exhibited slim polarization hysteresis curves and a high dielectric constant of 2100 at room temperature. A broad dielectric maximum at approximately 140–170 °C was observed. The field-induced displacement was measured by scanning probe microscopy, the bipolar displacement was not hysteretic, and the effective piezoelectric coefficient (d33) was 66 × 10−12 m/V. The effective d33 decreased with temperature, but the value at 100 °C remained 45 × 10−12 m/V.  相似文献   

11.
This paper reports results of studies on structure and activity in soot combustion of nanocrystalline CeO2 and CeLnOx mixed oxides (Ln = Pr, Tb, Lu, Ce/Ln atomic ratios 5/1). Nano-sized (4–5 nm) oxides with narrow size distribution were prepared by a microemulsion method W/O. Microstructure, morphology and reductivity of the oxides annealed up to 950 °C in O2 and H2 were analyzed by HRTEM, XRD, FT-IR, Raman spectroscopy and H2-TPR. Obtained mixed oxides had fluorite structure of CeO2 and all exhibited improved resistance against crystal growth in O2, but only CeLuOx behaved better than CeO2 in hydrogen.

The catalytic activity of CeO2, CeLnOx and physical mixtures of CeO2 + Ln2O3 in a model soot oxidation by air was studied in “tight contact” mode by using thermogravimetry. Half oxidation temperature T1/2 for soot oxidation catalysed by nano-sized CeO2 and CeLnOx was similar and ca. 100 °C lower than non-catalysed oxidation. However, the mixed oxides were much more active during successive catalytic cycles, due to better resistance to sintering. Physical mixtures of nanooxides (CeO2 + Ln2O3) showed exceptionally high initial activity in soot oxidation (decrease in T1/2 by ca. 200 °C) but degraded strongly in successive oxidation cycles. The high initial activity was due to the synergetic effect of nitrate groups present in highly disordered surface of nanocrystalline Ln2O3 and enhanced reductivity of nanocrystalline CeO2.  相似文献   


12.
Catalytic partial oxidation of methane to synthesis gas over ZrO2 and yttrium-stabilized zirconia (YSZ) is studied using O2 and N2O as oxidants. ZrO2 is much more active than YSZ in oxidation of methane with N2O. In contrast, YSZ is significantly more active than ZrO2 when O2 is used as an oxidant. The presence of O2 does not influence the rate of N2O decomposition over ZrO2 and YSZ, while the presence of H2O in the system decreases N2O conversion significantly. O2 and N2O are activated at different active sites. Y-induced oxygen vacancies are active for O2 activation, whereas oxygen co-ordinatively unsaturated Zr cations (Zr-CUS) located at corners, edges, steps and kinks are responsible for N2O activation. These sites are also capable of dissociating H2O, resulting in competition between H2O and N2O. As compared with N2O, molecular O2 is easier to be activated over YSZ and ZrO2.  相似文献   

13.
Properties of the oxidized activated carbon KAU treated at different temperatures in inert atmosphere were studied by means of DTA, Boehm titration, XPS and AFM methods and their catalytic activity in H2S oxidation by air was determined. XPS analysis has shown the existence of three types of oxygen species on carbon catalysts surface. The content of oxygen containing groups determined by Boehm titration is correlated with their amount obtained by XPS. Catalytic activity of the KAU catalysts in selective oxidation of hydrogen sulfide is connected with chemisorbed charged oxygen species (O3.1 oxygen type with BE 536.8–537.7 eV) present on the carbons surface.

Formation of dense sulfur layer (islands of sulfur) on the carbons surface and removal of active oxygen species are the reason of the catalysts deactivation in H2S selective oxidation. The treatment of deactivated catalyst in inert atmosphere at 300 °C gives full regeneration of the catalyst activity at low temperature reaction but only its partial reducing at high reaction temperature. The last case is connected with transformation of chemisorbed charged oxygen species into CO groups.

The KAU samples treated in flow of inert gas at 900–1000 °C were very active in H2S oxidation to elemental sulfur transforming up to 51–57 mmol H2S/g catalyst at 180 °C with formation of 1.7–1.9 g Sx/g catalyst.  相似文献   


14.
A new mixed-valent iron MOF, formulated as Fe3O(F4BDC)3(H2O)3·(DMF)3.5 (1), has been synthesized by using a perfluorinated linear dicarboxylate to link trigonal prismatic Fe33-O)(O2C–)6 clusters. The structure refinement based on single crystal X-ray diffraction data collected from 1 reveals the material exhibits the acs topology with large channels along the crystallographic c-axis. Due to the presence of fluorine atoms the organic link, 2,3,5,6-tetrafluorobenzene-1,4-dicarboxylate (F4BDC), has a 63° torsion angle between the carboxylate and aromatic planes, resulting in larger channels compared to those in the isoreticular material MOF-235. While few iron-based MOFs have demonstrated porosity, nitrogen and hydrogen sorption experiments carried out at 77 K proved the porosity of outgassed 1, which has a Langmuir surface are of 635 m2/g and a gravimetric capacity of 0.9 wt% of hydrogen at 1 bar.  相似文献   

15.
Ceria (CeO2) and rare-earth modified ceria (CeReOx with Re = La, Pr, Sm, Y) catalysts are prepared by nitrate precursor calcination and are characterised by BET surface area, XRD, H2-TPR, and Raman spectroscopy. Potential of the catalysts in the soot oxidation is evaluated in TGA with a feed gas containing O2. Seven hundred degree Celsius calcination leads to a decrease in the surface area of the rare-earth modified CeO2 compared with CeO2. However, an increase in the meso/macro pore volume, an important parameter for the soot oxidation with O2, is observed. Rare-earth ion doping led to the stabilisation of the CeO2 surface area when calcined at 1000 °C. XRD, H2-TPR, and Raman characterisation show a solid solution formation in most of the mixed oxide catalysts. Surface segregation of dopant and even separate phases, in CeSmOx and CeYOx catalysts, are, however, observed. CePrOx and CeLaOx catalysts show superior soot oxidation activity (100% soot oxidation below 550 °C) compared with CeSmOx, CeYOx, and CeO2. The improved soot oxidation activity of rare-earth doped CeO2 catalysts with O2 can be correlated with the increased meso/micro pore volume and stabilisation of external surface area. The segregation of the phases and the enrichment of the catalyst surface with unreducible dopant decrease the intrinsic soot oxidation activity of the potential CeO2 catalytic sites. Doping CeO2 with a reducible ion such as Pr4+/3+ shows an increase in the soot oxidation. However, the ease of catalyst reduction and the bulk oxygen-storage capacity is not a critical parameter in the determination of the soot oxidation activity. During the soot oxidation with O2, the function of the catalyst is to increase the ‘active oxygen’ transfer to the soot surface, but it does not change the rate-determining step, as evident from the unchanged apparent activation energy (around 150 kJ mol−1), for the catalysed and un-catalysed soot oxidation. Spill over of oxygen on the soot surface and its subsequent adsorption at the active carbon sites is an important intermediate step in the soot oxidation mechanism.  相似文献   

16.
A series of CeO2 promoted cobalt spinel catalysts were prepared by the co-precipitation method and tested for the decomposition of nitrous oxide (N2O). Addition of CeO2 to Co3O4 led to an improvement in the catalytic activity for N2O decomposition. The catalyst was most active when the molar ratio of Ce/Co was around 0.05. Complete N2O conversion could be attained over the CoCe0.05 catalyst below 400 °C even in the presence of O2, H2O or NO. Methods of XRD, FE-SEM, BET, XPS, H2-TPR and O2-TPD were used to characterize these catalysts. The analytical results indicated that the addition of CeO2 could increase the surface area of Co3O4, and then improve the reduction of Co3+ to Co2+ by facilitating the desorption of adsorbed oxygen species, which is the rate-determining step of the N2O decomposition over cobalt spinel catalyst. We conclude that these effects, caused by the addition of CeO2, are responsible for the enhancement of catalytic activity of Co3O4.  相似文献   

17.
Kinetics of N2O decomposition over catalyst prepared by calcination of Co–Mn hydrotalcite was examined in integral fixed-bed reactor () at various N2O and O2 initial partial pressure at temperature range of 330–450 °C. Kinetic data were evaluated by linear and non-linear regression method, 15 kinetic expressions were tested. Based on the obtained results a redox model of N2O decomposition was proposed. At low pressures of O2, adsorbed oxygen is formed by the N2O decomposition; the N2O chemisorption is considered as the rate-determining step. On the contrary, at high O2 pressure it could be assumed that adsorbed oxygen species appear as a result of O2 adsorption and the Eley–Rideal mechanism is the rate determining. N2O decomposition is well described by the 1st rate law at N2O and O2 concentrations typical for waste gases.  相似文献   

18.
The effect of additives on Pt-ZSM-5 catalysts was studied for the selective NO reduction by H2 in the presence of excess O2 (NO–H2–O2 reaction) at 100 °C. The reaction of NO in a stream of 0.08% NO, 0.28% H2, 10% O2, and He balance yielded N2 with less than 10% selectivity, which could not be increased by changing Pt loading or H2 concentration in the gas feed. Co-impregnation of NaHCO3 and Pt onto ZSM-5 decreased the BET surface area and the Pt dispersion. Nevertheless, the Na-loaded catalyst (Na-Pt-ZSM-5) exhibited the higher NOx conversion (>90%) and the N2 selectivity (ca. 50%). Such a high catalytic activity even at high Na loadings (≥10 wt.%) is completely contrast to other Na-added Pt catalyst systems reported so far. Further improvement of N2 selectivity was attained by the post-impregnation of NaHCO3 onto Pt-ZSM-5. In situ DRIFT measurements suggested that the addition of Na promotes the adsorption of NO as NO2-type species, which would play a role of an intermediate to yield N2. The introduction of Lewis base to the acidic supports including ZSM-5 would be applied to the catalyst design for selective NO–H2–O2 reaction at low temperatures.  相似文献   

19.
A multi-component NOx-trap catalyst consisting of Pt and K supported on γ-Al2O3 was studied at 250 °C to determine the roles of the individual catalyst components, to identify the adsorbing species during the lean capture cycle, and to assess the effects of H2O and CO2 on NOx storage. The Al2O3 support was shown to have NOx trapping capability with and without Pt present (at 250 °C Pt/Al2O3 adsorbs 2.3 μmols NOx/m2). NOx is primarily trapped on Al2O3 in the form of nitrates with monodentate, chelating and bridged forms apparent in Diffuse Reflectance mid-Infrared Fourier Transform Spectroscopy (DRIFTS) analysis. The addition of K to the catalyst increases the adsorption capacity to 6.2 μmols NOx/m2, and the primary storage form on K is a free nitrate ion. Quantitative DRIFTS analysis shows that 12% of the nitrates on a Pt/K/Al2O3 catalyst are coordinated on the Al2O3 support at saturation.

When 5% CO2 was included in a feed stream with 300 ppm NO and 12% O2, the amount of K-based nitrate storage decreased by 45% after 1 h on stream due to the competition of adsorbed free nitrates with carboxylates for adsorption sites. When 5% H2O was included in a feed stream with 300 ppm NO and 12% O2, the amount of K-based nitrate storage decreased by only 16% after 1 h, but the Al2O3-based nitrates decreased by 92%. Interestingly, with both 5% CO2 and 5% H2O in the feed, the total storage only decreased by 11%, as the hydroxyl groups generated on Al2O3 destabilized the K–CO2 bond; specifically, H2O mitigates the NOx storage capacity losses associated with carboxylate competition.  相似文献   


20.
The influence of sintering and poling conditions on dielectric properties and microstructures of the system 0·125Pb(Mg1/3Nb2/3)O3−0·875Pb (Zr0·5Ti0·5)O3 was investigated. Specimens were prepared by the conventional mixed-oxide technique. On account of eliminating the pyrochlore phase and lowering the sintering temperature, the calcined 0·125PZT−0·875PMN ceramic was doped with 4PbO.B2O3 glass powder. The 4PbO.B2O3 glass frit not only has a low flow temperature, but also a high polarizability. Additions of 4PbO.B2O3 to the perovskite 0·125PMN–0·875PZT solid solution will form a liquid phase, which served as a densification aid for the ceramics. With additions of 0·2 wt% glass frit, densities in excess of 98% of theoretical were obtained after sintering at 115°C. By variation of the fabrication processes, the influence of sintering and poling conditions on the properties of the ceramics was studied.  相似文献   

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