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1.
The deactivation by sulfur and regeneration of a model Pt/Ba/Al 2O 3 NO x trap catalyst is studied by hydrogen temperature programmed reduction (TPR), X-ray diffraction (XRD), and NO x storage capacity measurements. The TPR profile of the sulfated catalyst in lean conditions at 400 °C reveals three main peaks corresponding to aluminum sulfates (550 °C), “surface” barium sulfates (650 °C) and “bulk” barium sulfates (750 °C). Platinum plays a role in the reduction of the two former types of sulfates while the reduction of “bulk” barium sulfates is not influenced by the metallic phase. The thermal treatment of the sulfated catalyst in oxidizing conditions until 800 °C leads to a stabilization of sulfates which become less reducible. Stable barium sulfides are formed during the regeneration under hydrogen at 800 °C. However, the presence of carbon dioxide and water in the rich mixture allows eliminating more or less sulfides and sulfates, depending on the temperature and time. The regeneration in the former mixture at 650 °C leads to the total recovery of the NO x storage capacity even if “bulk” barium sulfates are still present on the catalyst. 相似文献
2.
The kinetics of the selective catalytic reduction (SCR) of NO by NH 3 in the presence of O 2 has been studied on a 5.5% Cu-faujasite (Cu-FAU) catalyst. Cu-FAU was composed of cationic and oxocationic Cu species. The SCR was studied in a gas phase-flowing reactor operating at atmospheric pressure. The reaction conditions explored were: 458< TR<513 K, 250 3 (ppm) < 4000, 12 (%) < 4. The kinetic orders were 0.8–1 with respect to NO, 0.5–1 with respect to O2, and essentially 0 with respect to NH3. Based on these kinetic partial orders of reactions and elementary chemistry, a wide variety of mechanisms were explored, and different rate laws were derived. The best fit between the measured and calculated rates for the SCR of NO by NH3 was obtained with a rate law derived from a redox Mars and van Krevelen mechanism. The catalytic cycle is described by a sequence of three reactions: (i) CuI is oxidized by O2 to “CuII-oxo”, (ii) “CuII-oxo” reacts with NO to yield “CuII-NxOy”, and (iii) finally “CuII-NxOy” is reduced by NH3 to give N2, H2O, and the regeneration of CuI (closing of the catalytic cycle). The rate constants of the three steps have been determined at 458, 483, and 513 K. It is shown that CuI or “CuII-oxo” species constitute the rate-determining active center. 相似文献
3.
Mixed oxides of the general formula La 0.5Sr xCe yFeO z were prepared by using the nitrate method and characterized by XRD and Mössbauer techniques. The crystal phases detected were perovskites LaFeO 3 and SrFeO 3−x and oxides -Fe 2O 3 and CeO 2 depending on x and y values. The low surface area ceramic materials have been tested for the NO+CO and NO+CH 4+O 2 (“lean-NO x”) reactions in the temperature range 250–550°C. A noticeable enhancement in NO conversion was achieved by the substitution of La 3+ cation at A-site with divalent Sr +2 and tetravalent Ce +4 cations. Comparison of the activity of the present and other perovskite-type materials has pointed out that the ability of the La 0.5Sr xCe yFeO z materials to reduce NO by CO or by CH 4 under “lean-NO x” conditions is very satisfying. In particular, for the NO+CO reaction estimation of turnover frequencies (TOFs, s −1) at 300°C (based on NO chemisorption) revealed values comparable to Rh/-Al 2O 3 catalyst. This is an important result considering the current tendency for replacing the very active but expensive Rh and Pt metals. It was found that there is a direct correlation between the percentage of crystal phases containing iron in La 0.5Sr xCe yFeO z solids and their catalytic activity. O 2 TPD (temperature-programmed desorption) and NO TPD studies confirmed that the catalytic activity for both tested reactions is related to the defect positions in the lattice of the catalysts (e.g., oxygen vacancies, cationic defects). Additionally, a remarkable oscillatory behavior during O 2 TPD studies was observed for the La 0.5Sr 0.2Ce 0.3FeO z and La 0.5Sr 0.5FeO z solids. 相似文献
4.
To clarify the effect of substitutional electron doping on the thermoelectric figure of merit ( ZT = S2σTκ−1) of Ruddlesden–Popper phase SrO(SrTiO 3) n (or Sr n+1Ti nO 3n+1), measurements were conducted for several thermoelectric parameters, e.g. electrical conductivity ( σ), Seebeck coefficient ( S) and thermal conductivity ( κ), of (Sr 1−xREx) n+1Ti nO 3n+1 ( n = 1 or 2, RE (rare earth): La or Nd, x = 0.05 and 0.1) dense ceramics prepared by a conventional solid-state reaction and hot-pressing technique. Crystal structures of the resultant ceramics were represented as (Sr 1−xREx) n+1 Ti nO 3n+1 evaluated by powder X-ray diffraction followed by the Rietveld analysis. All the ceramics exhibited electrical conductivity and the σ values simply depended on the dopant concentration, indicating that both La 3+ and Nd 3+ ions act as electron donors. The | S| values increased with temperature due to decrease in the chemical potential. Significant reduction of the κ values was observed as compared to cubic-perovskite SrTiO 3. The ZT value increased with temperature and reached 0.15 at 1000 K for (Sr 0.95La 0.05) 3Ti 2O 7. 相似文献
5.
The chemisorption of a single water molecule on the Cu, Ag, Au and Zn, Cd, Hg low index faces and of the (H 2O) n associates ( n = 2−5) on Ag(111) and on a close-packed mercury surface has been investigated by CNDO method together with geometrical optimization of the atom positions. For substrate, a cluster consisting of a few atoms, as a model, has been used. A new “microscopic” sequence of the metal hydrophilicity is proposed. Calculations are critically discussed in the light of experimental and other quantum chemical data. Water structuring near a mercury surface has been also studied by using Metropolis Monte Carlo procedure. 相似文献
6.
LaMn 1−xMg xO 3 perovskite catalysts ( x=0–0.5) were synthesised by the so-called “citrates method”, characterised (chemical analysis, TEM, BET, XRD, temperature-programmed desorption of oxygen) and tested for their activity towards the catalytic combustion of methane. The role of MgO as a textural promoter, which hinders the sintering of the catalyst crystals by geometrical interposition, has also been assessed. Finally, a kinetics study was performed on the most promising catalysts prepared (LaMnO 3 and LaMn 0.8Mg 0.2O 3). The major results obtained are: (i) Mg substitution in the basic LaMnO 3 perovskite has a positive effect on the catalytic activity only at low x values ( x≤0.2); (ii) as opposed to the results of previous studies on the LaCr 1−xMg xO 3 system, the role of MgO as a textural promoter is not always significant and depends strongly on the calcination temperature of the samples (800–1200°C) and on the value of x; (iii) an Eley–Rideal mechanism could satisfactorily fit the experimental kinetics results for both catalysts, even though, as opposed to LaMnO 3, the catalytic combustion over LaMn 0.8Mg 0.2O 3 seems to involve two different types of adsorbed oxygen species, depending on the operating temperature. 相似文献
7.
The effects of ZrO 2 content on the CO oxidation activity in a series of CuO x/Ce xZr 1−xO 2 ( x = 0, 0.15, 0.5, 0.7 and 1) catalysts were investigated, both in the absence and in the presence of H 2, i.e. preferential CO oxidation—PROX. The investigation was performed under light-off conditions to focus the effects of transients and shut-down/start-up cycles on the performance; such phenomena are expected to affect the activity of PROX catalysts in small/delocalised fuel reformers. Evidence has been obtained for a transition from an “oxidized” towards a “reduced” state of the catalyst under the simulated PROX reaction conditions as a function of the reaction temperature, leading to different active species under the reaction conditions. Both CO oxidation activity and PROX selectivity appear to be affected by this process. IR characterisation of the surface copper species suggests an important role of reduced cerium sites in close contact with copper clusters on the CO oxidation activity at low temperatures. 相似文献
8.
Conductance measurements are reported for several salts in binary aqueous mixtures containing up to 60 mole % sulfolane, 20 mole % acetonitrile and 20 mole % dimethylsulfoxide. The variations of R = (λ ±0η 0) s/(λ ±0η 0) w with solvent composition have been compared with those observed in other water-rich mixtures. Alkali cations show R values greater than one with maxima in all the solvent mixtures. This behaviour has been discussed in terms of “sorting”, “averaging” and “steric” effects. Contrary to what happens to alkali cations, halide ions show R values greater or lesser than one according to whether the organic solvent respectively increases or decreases water structure. On these bases we suggest that conductometric behaviour of the halide ions may be indicative of the effect of the cosolvent on the water structure in water-rich mixtures and that DMSO is a water structure breaker. 相似文献
9.
Supported LaCoO 3 perovskites with 10 and 20 wt.% loading were obtained by wet impregnation of different Ce 1−xZr xO 2 ( x = 0–0.3) supports with a solution prepared from La and Co nitrates, and citric acid. Supports were also prepared using the “citrate method”. All materials were calcined at 700 °C for 6 h and investigated by N 2 adsorption at −196 °C, XRD and XPS. XRD patterns and XPS measurements evidenced the formation of a pure perovskite phase, preferentially accumulated at the outer surface. These materials were comparatively tested in benzene and toluene total oxidation in the temperature range 100–500 °C. All catalysts showed a lower T50 than the corresponding Ce 1−xZr xO 2 supports. Twenty weight percent LaCoO 3 catalysts presented lower T50 than bulk LaCoO 3. In terms of reaction rates per mass unit of perovskite calculated at 300 °C, two facts should be noted (i) the activity order is more than 10 times higher for toluene and (ii) the reverse variation with the loading as a function of the reactant, a better activity being observed for low loadings in the case of benzene. For the same loading, the support composition influences drastically the oxidative abilities of LaCoO 3 by the surface area and the oxygen mobility. 相似文献
10.
The water-gas shift (WGS) activity of platinum catalysts dispersed on a variety of single metal oxides as well as on composite MO x/Al 2O 3 and MO x/TiO 2 supports (M = Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, La, Ce, Nd, Sm, Eu, Gd, Ho, Er, Tm) has been investigated in the temperature range of 150–500 °C, using a feed composition consisting of 3% CO an 10% H 2O. For Pt catalysts supported on single metal oxides, it has been found that both the apparent activation energy of the reaction and the intrinsic rate depend strongly on the nature of the support. In particular, specific activity of Pt at 250 °C is 1–2 orders of magnitude higher when supported on “reducible” compared to “irreducible” metal oxides. For composite Pt/MO x/Al 2O 3 and Pt/MO x/TiO 2 catalysts, it is shown that the presence of MO x results in a shift of the CO conversion curve toward lower reaction temperatures, compared to that obtained for Pt/Al 2O 3 or Pt/TiO 2, respectively. The specific reaction rate is in most cases higher for composite catalysts and varies in a manner which depends on the nature, loading, and primary crystallite size of dispersed MO x. Results are explained by considering that reducibility of small oxide particles increases with decreasing crystallite size, thereby resulting in enhanced WGS activity. Therefore, evidence is provided that the metal oxide support is directly involved in the WGS reaction mechanism and determines to a significant extent the catalytic performance of supported noble metal catalysts. Results of catalytic performance tests obtained under realistic feed composition, consisting of 3% CO, 10% H 2O, 20% H 2 and 6% CO 2, showed that certain composite Pt/MO x/Al 2O 3 and Pt/MO x/TiO 2 catalysts are promising candidates for the development of active WGS catalysts suitable for fuel cell applications. 相似文献
11.
The reduction of NO under cyclic “lean”/“rich” conditions was examined over two model 1 wt.% Pt/20 wt.% BaO/Al 2O 3 and 1 wt.% Pd/20 wt.% BaO/Al 2O 3 NO x storage reduction (NSR) catalysts. At temperatures between 250 and 350 °C, the Pd/BaO/Al 2O 3 catalyst exhibits higher overall NO x reduction activity. Limited amounts of N 2O were formed over both catalysts. Identical cyclic studies conducted with non-BaO-containing 1 wt.% Pt/Al 2O 3 and Pd/Al 2O 3 catalysts demonstrate that under these conditions Pd exhibits a higher activity for the oxidation of both propylene and NO. Furthermore, in situ FTIR studies conducted under identical conditions suggest the formation of higher amounts of surface nitrite species on Pd/BaO/Al 2O 3. The IR results indicate that this species is substantially more active towards reaction with propylene. Moreover, its formation and reduction appear to represent the main pathway for the storage and reduction of NO under the conditions examined. Consequently, the higher activity of Pd can be attributed to its higher oxidation activity, leading both to a higher storage capacity ( i.e., higher concentration of surface nitrites under “lean” conditions) and a higher reduction activity ( i.e., higher concentration of partially oxidized active propylene species under “rich” conditions). The performance of Pt and Pd is nearly identical at temperatures above 375 °C. 相似文献
12.
The NO x storage and reduction functions of a Pt–Ba/Al 2O 3 “NO x storage–reduction” catalyst has been investigated in the present work by applying the transient response and the temperature programmed reaction methods, by using propylene as the reducing agent. It is found that: (i) the storage of NO x occurs first at BaO and then at BaCO 3, which are the most abundant sites following regeneration of catalyst with propylene; (ii) the overall storage process at BaCO 3 is slower than at BaO; (iii) CO 2 inhibits the NO x storage at low temperatures; (iv) the amount of NO x stored up to catalyst saturation at 350 °C corresponds to 17.6% of Ba; (v) the reduction of stored NO x groups is fast and is limited by the concentration of propylene in the investigated T range (250–400 °C); (vi) selectivity to N 2 is almost complete at 400 °C but is significantly lower at 300 °C due to the formation of NO which can be tentatively ascribed to the presence of unselective Pt–O species. 相似文献
13.
Investigation of the mechanism of the selective reduction of NO x by propane over the individual samples of commercial catalysts NTK, STK, and Ni–Cr-oxide catalyst and over their binary mechanical mixtures has shown that the synergistic effect observed in the latter case is caused by the oxidative activation of propane on the STK and Ni–Cr-oxide surface which results in the formation of more effective reducing agents, propylene and hydrogen correspondingly. In the case of the Ni–Cr-oxide and NTK catalytic system, hydrogen forms over the former catalyst in propane oxidation, migrates through the gas phase to the latter catalyst, where NO x is activated with the formation of nitrate structures which interact with the said hydrogen giving the products of the overall reaction, N 2 and H 2O. When the pair of NTK and STK is concerned, the interaction of C 3H 8 and O 2 over the latter catalyst gives stable products of partial propane oxidation and/or oxidative dehydrogenation which are transported due to interphase diffusion to NTK surface. The nature of observed synergistic enhancement of catalysis in the case of binary mixtures is proposed under the terms of “remote control” mechanism described in literature and can serve a useful purpose in the design of catalysts for this reaction. 相似文献
14.
Lamella spacings, specific volumes and melting points have been determined for a series of well characterized poly(ethylene oxide)/poly(propylene oxide) type PEP block copolymers with E-block length 48 chain units and P-block lengths 0 to 7 chain units. These properties are interpreted in terms of a stacked lamella model with alternating amorphous and crystalline layers. Both extended-chain and once-folded-chain crystalline lamellae are found, the former with thickness about 32 E chain units and the latter with thickness about 21 E chain units. Compared with the specific volume of supercooled melt of the same composition the specific volume of the polymer in the amorphous lamellae is lower in the extended-chain polycrystals and higher in the once-folded-chain polycrystals. The melting points of the copolymers are low compared to that of perfectly crystalline poly(ethylene oxide), i.e. 37 to 55°C compared with T0m = 76°C. This is due to the large positive free energy of formation from the melt of the crystalline/amorphous end interface (σ o) and the amorphous layer (σ a). For extended-chain polycrystals we find σ o 3 kJ/mol and σ a 3.5 kJ/mol; for once-folded-chain polycrystals we find σ o 6 kJ/mol and σ a 2 kJ/mol. We also find σ o,x = 2.5 kJ/mol for a completely extended-chain end interface and σ o,f = 10 kJ/mol for a completely folded-chain end interface. 相似文献
15.
Surface energies of amorphous cellulose “beads” were measured by IGC at different temperatures (50 to 100°C) using n-alkane probes (pentane to undecane). The equation of Schultz and Lavielle was applied which relates the specific retention volume of the gas probe to the dispersive component of the surface energy of the solid and liquid, γ ds and γ dl, respectively, and a parameter (“a”) which represents the surface area of the gas probe in contact with the solids. At 50°C, γ ds was determined to be 71.5 mJ/m 2, and its temperature dependence was 0.36 mJ m -2 K -1. Compared with measurements obtained by contact angle, IGC results were found to yield higher values, and especially a higher temperature dependence, d(γ ds)/dT. Various potential explanations for these elevated values were examined. The surface energy, as determined by the Schultz and Lavielle equation, was found to depend mostly on the parameter “a”. Two experimental conditions are known to affect the values of “a”: the solid surface and the temperature. While the surface effect of the parameter “a” was ignored in this study, the dependence of the surface energy upon temperature and probe phase was demonstrated to be significant. Several optional treatments of the parameter “a” were modeled. It was observed that both experimental imprecision, but mostly the fundamental difference between the liquid-solid vs the gas-solid system (and the associated theoretical weakness of the model used), could explain the differences between γ ds and d(γ ds)/dT measured by contact angle and IGC. It was concluded that the exaggerated temperature dependence of the IGC results is a consequence of limitations inherent in the definition of parameter “a”. 相似文献
16.
Lanthanum cobaltate LaCoO x supported onto MCM-41 mesoporous molecular sieve was prepared by in-situ oxidative decomposition of mixed LaCo citrate complexes inside the mesopores of this support. The prepared materials were characterized by EDX, EPR and UV-Vis DRS techniques as well as by N 2-BET measurements. The nanosized LaCoO x particles within the mesopores of MCM-41 matrix contains cobalt atoms in lower than Co(III) average oxidation state. Also, the supported cobaltate does not form short-range order species of LaCoO 3 but presents as the highly disordered, oxygen deficient Co oxide nanophase. Catalytic activity in MeOH oxidation was tested using both conventional fixed-bed flow system and “operando” mode of DRIFT technique. The very high activity of MCM-41-supported cobaltate is not only due to highly dispersed LaCoO 3 phase but also because of rather low oxidation state of Co. 相似文献
17.
Pd n+/Ce n+/Na +/γ-Al 2O 3-type materials used as FCC additives for CO/NO x control were characterized by extended X-ray absorption fine structure (EXAFS) spectroscopy and in situ FTIR. The EXAFS data indicate that in freshly prepared samples palladium is present in the form of highly dispersed PdO species. Reduction with H 2 at 500 °C leads to the formation of small Pd clusters incorporating on average approximately six to eight metal atoms at a Pd−Pd bond distance of 2.76 Å. All components of these materials can interact with NO and promote the formation of nitrate/nitrite species, essentially “trapping” NO x species on the catalyst surface. However, the Na + species dominate the surface chemistry and readily form sodium nitrates with a characteristic IR band at 1370–1385 cm −1. Finally, hydroxyls from the support are also actively participating in the formation of HNO x type compounds with characteristic stretching vibrations in the 3500–3572 cm −1 region. 相似文献
18.
The photocatalytic degradation of a number of organic compounds in solution, including alcohols and organic acids, has been investigated under unaerated conditions with the use of Pt/TiO 2 photocatalyst and solar or UV irradiation. It has been found that production of CO 2 is in all cases accompanied by evolution of hydrogen, the production rate of which is significantly enhanced, compared with that obtained in the absence of organic additives in solution. Results are explained by considering that organic compounds act as sacrificial electron donors, which become progressively oxidized toward CO 2 by consuming photogenerated holes and/or oxygen. This results in decreased rates of electron–hole recombination and oxygen–hydrogen back reaction and, concomitantly, in increased H 2-production rates. The rate of photoinduced hydrogen production depends strongly on the concentration of the sacrificial agent employed and to a lesser extent on solution pH and temperature. When complete mineralization of the sacrificial agent is achieved, photogenerated oxygen can no longer be removed from the photocatalyst surface and the H 2-production rate drops to steady-state values, comparable to those obtained in the absence of the organic compound in solution. The amounts of carbon dioxide and “additional” hydrogen produced depend on the nature of the organic additive and are directly proportional to its initial concentration in solution. Quantification of results shows that the overall process may be described as “photoinduced reforming of organic compounds at room temperature”. It is concluded that mineralization of organic pollutants such as alcohols and organic acids, which are common waste products of biomass processing industries, can be achieved with simultaneous production of H 2 fuel. The process may provide an efficient and cost effective method for cleaning up waste streams. 相似文献
19.
The melt viscosity of polycaprolactam can be enhanced by incorporation of chromium (III) ions into the resin. As a possible interpretation of this phenomenon, formation of a mixed complex is suggested by X-ray diffraction, infrared and uv. absorption spectroscopic studies. By comparison with a model compound, it was found that the carbonyl oxygen and the water occurring in the polymer appear to be the coordination centres of chromium (III) ions. The hypothetical composition of the mixed complex is [Cr(CO amide) n(H 2O) 6−n] 3+ where 2 n 6. 相似文献
20.
In order to improve a “Three Function Catalysts Model”, the present paper deals with alumina based catalysts containing cobalt and palladium for the NO reduction by methane. The deNOx temperature window was estimated by adsorption and subsequent desorption of NO in lean conditions. Two NOx desorption peaks were detected for both catalysts. For Pd(0.63)Co(0.58)/Al2O3, the two desorption peaks appeared at 205 and 423 °C, whereas for Pd(0.14)Co(0.57)/Al2O3, the maxima desorption temperature peaks were at 205 and 487 °C. In addition, NO oxidation was also studied to evaluate the catalyst first function. It was found that, the oxidation begins on Co–Pd/Al2O3 around 250 °C. On Pd(0.63)Co(0.58)/Al2O3, 8% of deNOx were found in the range of the second NOx desorption peak temperature (410 °C). During TPSR, CxHyOz species such as formaldehyde were detected. These oxygenate species are the reactive intermediate for deNOx by methane. 相似文献
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