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1.
The effect of the support oxide, Pt precursor and reactant gas composition on the catalysis of soot oxidation was investigated using carbon black as a model soot and simulated exhaust gases. The Pt precursors used were Pt(NH 3) 4(OH) 2, H 2PtCl 6·6H 2O, Pt(NH 3) 4(NO 3) 2, and Pt(NH 3) 4Cl 2. The support metal oxides used were SiO 2, Al 2O 3, and ZrO 2. Pt/SiO 2 prepared from Pt(NH 3) 4(OH) 2 showed the highest carbon oxidation activity. It had much higher activity in the condition of N 2+O 2+H 2O+NO+SO 2 than without NO and SO 2. 相似文献
2.
A series of Pd/Al 2O 3 catalysts with a wide range of mean Pd particle sizes (ca. 2–30 nm in diameter) was prepared by using various precursors (H 2PdCl 4, Pd(NO 3) 2 and Pd(AcAc) 2) and pre-treatments. The mean particle size of reduced samples was determined by H 2 chemisorption. The catalytic activity in methane oxidation under lean burn conditions was measured. The oxidation of reduced samples was studied at 300 °C. The extent of oxidation was found to decrease with increasing mean particle size. While small particles (<5 nm) oxidised very rapidly, the oxidation of large particles (ca. >15 nm) proceeded via a two-step process, being first fast and then slow. The decomposition of oxide species was studied by temperature-programmed experiments under vacuum. Two distinct oxidised species with different stability were evidenced depending on the particle size. Oxidised species in larger particles were found of lower stability than in smaller ones. A correlation between the existence of distinct types of oxide species and catalytic properties in methane oxidation was discussed. 相似文献
3.
以海绵铂为原料合成出[Pt(NH 3) 6]Cl 4络合物,采用热重分析(TG)、扫描电镜-能谱(SEM-EDS)、紫外-可见分光光度计(UV-Vis)、质谱(MS)、X射线光电子能谱(XPS)等手段确定了[Pt(NH 3) 6]Cl 4的结构组成;以H 2PtCl 6、Pt(NH 3) 4Cl 2和[Pt(NH 3) 6]Cl 4为前驱体,采用等体积浸渍法制得Pt/Beta催化剂,采用X射线衍射(XRD)、X射线荧光光谱(XRF)、氨程序升温脱附(NH 3-TPD)、氢氧滴定(H 2-O 2)、透射电镜(TEM)、氢气程序升温脱附(H 2-TPD)等表征了Pt/Beta催化剂的物化性质,并考察了Pt/Beta催化剂的多环芳烃选择性开环性能。结果表明,[Pt(NH 3) 6]Cl 4络合物具有更高的“抗自还原”能力,可从前驱体结构上降低铂氨前驱体受热分解时的自还原现象。前驱体结构对铂纳米颗粒的几何尺寸及分布有较大影响,一方面络合物的价态显著影响前驱体与分子筛间的静电作用,进而影响铂纳米颗粒的落位与尺寸;另一方面络合物的空间结构影响前驱体在分子筛微孔中的分布,影响铂纳米颗粒的Ostwald熟化速率。前驱体结构可调变Pt/Beta催化剂的双功能匹配关系,显著影响Pt/Beta催化剂转化甲基萘的活性、稳定性,采用[Pt(NH 3) 6]Cl 4前驱体制备的Pt/Beta催化剂具有更优的活性及长周期稳定性。 相似文献
4.
Catalytic wet air oxidation of p-hydroxyphenylacetic acid and p-hydroxybenzoic acid, two important pollutants present in the olive oil mill wastewaters, was studied in a batch reactor using platinum and ruthenium catalysts supported on titanium and zirconium oxides at 140 °C and 50 bar of total air pressure. Reaction pathways for the oxidation of these two substrates were proposed, with formation of different aromatic compounds and short-chain organic acids through hydroxylation and decarboxylation reactions. It was observed that the conversion and the mineralization of these two substrates were markedly affected by the nature of the ruthenium precursor (RuCl3 or Ru(NO)(NO3)3), with the non-chlorine containing salt giving the best performances. Calcination of the catalyst precursor before reduction was detrimental. The nature of the metallic precursor (H2PtCl6 or Pt(NH3)4(NO3)2) had little influence on the catalytic properties of platinum catalysts, whereas the textural properties of the support were an important factor. 相似文献
5.
The preparation of CeO 2–ZrO 2 mixed oxides preparation was studied by evaluating the influence of several conditions. Coprecipitation was taken as the standard method and the effects brought about by the cerium salt precursor ((NH 4) 2Ce(NO 3) 6 or Ce(NO 3) 3), the introduction of drying and aging steps as well as pH controlling upon precipitation were analyzed. The samples were characterized by X-ray diffraction, Raman spectroscopy, temperature-programmed reduction, infrared spectroscopy, oxygen storage capacity and surface area. The use of Ce(NO 3) 3 leads to the formation of c-CeO 2 and t-ZrO 2 mixed oxide whereas a solid solution is achieved by using (NH 4) 2Ce(NO 3) 6. It was observed that the cerium precursor is the most significant parameter of preparation procedure since it defines the crystalline phases and consequently the reducibility behavior of the CeO 2–ZrO 2 system. 相似文献
6.
The effect of pretreatment on the dispersion of supported noble metal Catalyst prepared from amine precursors in basic solution have been studied. The following metal precursors were used: Pt(NH 3) 4(NO 3) 2, Pd(NH 3) 4(NO 3) 2, Ru(NH 3) 6Cl 3 and [Rh(NH 3) 5Cl]Cl 2 Pretreatment in oxygen, prior to reduction in H 2 at 400C, resulted in poor dispersions for Ru and Rh, moderate dispersions for Pd and high dispersions for Pt. Pretreatment in H 2 resulted in poor dispersions for Pd and Pt and high dispersions for Ru and Rh. Decomposition of the adsorbed Pt and Pd precursors in argon resulted in very high dispersions. 相似文献
7.
In this paper, the effect of CO 2 and H 2O on NO x storage and reduction over a Pt–Ba/γ-Al 2O 3 (1 wt.% Pt and 30 wt.% Ba) catalyst is shown. The experimental results reveal that in the presence of CO 2 and H 2O, NO x is stored on BaCO 3 sites only. Moreover, H 2O inhibits the NO oxidation capability of the catalyst and no NO 2 formation is observed. Only 16% of the total barium is utilized in NO storage. The rich phase shows 95% selectivity towards N 2 as well as complete regeneration of stored NO. In the presence of CO 2, NO is oxidized into NO 2 and more NO x is stored as in the presence of H 2O, resulting in 30% barium utilization. Bulk barium sites are inactive in NO x trapping in the presence of CO 2·NH 3 formation is seen in the rich phase and the selectivity towards N 2 is 83%. Ba(NO 3) 2 is always completely regenerated during the subsequent rich phase. In the absence of CO 2 and H 2O, both surface and bulk barium sites are active in NO x storage. As lean/rich cycling proceeds, the selectivity towards N 2 in the rich phase decreases from 82% to 47% and the N balance for successive lean/rich cycles shows incomplete regeneration of the catalyst. This incomplete regeneration along with a 40% decrease in the Pt dispersion and BET surface area, explains the observed decrease in NO x storage. 相似文献
8.
The release and reduction of NO x in a NO x storage-reduction (NSR) catalyst were studied with a transient reaction analysis in the millisecond range, which was made possible by the combination of pulsed injection of gases and time resolved time-of-flight mass spectrometry. After an O 2 pulse and a subsequent NO pulse were injected into a pellet of the Pt/Ba/Al 2O 3 catalyst, the time profiles of several gas products, NO, N 2, NH 3 and H 2O, were obtained as a result of the release and reduction of NO x caused by H 2 injection. Comparing the time profiles in another analysis, which were obtained using a model catalyst consisting of a flat 5 nmPt/Ba(NO 3) 2/cordierite plate, the release and reduction of NO x on Pt/Ba/Al 2O 3 catalyst that stored NO x took the following two steps; in the first step NO molecules were released from Ba and in the second step the released NO was reduced into N 2 by H 2 pulse injection. When this H 2 pulse was injected in a large amount, NO was reduced to NH 3 instead of N 2. A only small amount of H2O was detected because of the strong affinity for alumina support. We can analyze the NOx regeneration process to separate two steps of the NOx release and reduction by a detailed analysis of the time profiles using a two-step reaction model. From the result of the analysis, it is found that the rate constant for NOx release increased as temperature increase. 相似文献
9.
The inhibition effect of H 2O on V 2O 5/AC catalyst for NO reduction with NH 3 is studied at temperatures up to 250 °C through TPD, elemental analyses, temperature-programmed surface reaction (TPSR) and FT-IR analyses. The results show that H 2O does not reduce NO and NH 3 adsorption on V 2O 5/AC catalyst surface, but promotes NH 3 adsorption due to increases in Brønsted acid sites. Many kinds of NH 3 forms present on the catalyst surface, but only NH 4+ on Brønsted acid sites and a small portion of NH 3 on Lewis acid sites are reactive with NO at 250 °C or below, and most of the NH 3 on Lewis acid sites does not react with NO, regardless the presence of H 2O in the feed gas. H 2O inhibits the SCR reaction between the NH 3 on the Lewis acid sites and NO, and the inhibition effect increases with increasing H 2O content. The inhibition effect is reversible and H 2O does not poison the V 2O 5/AC catalyst. 相似文献
10.
The reactivation of thermally sintered Pt/Al 2O 3 catalysts used in the simultaneous oxidation of CO and propene has been achieved by an oxychlorination treatment. The catalyst can be considered to model the active component of the catalytic converter fitted to diesel driven cars. Platinum crystallites redispersion was verified by XRD, H 2 chemisorption, TEM and FTIR. The extent of regeneration reflects the platinum particle redispersion achieved by such a treatment. Oxychlorination also introduced electronic effects in the Pt particle caused by the presence of chlorine at the Pt-Al 2O 3 interface but no detrimental result of this was observed in the oxidation reactions. The results indicate that the deactivation of the diesel oxidation catalysts (DOCs) can be reverted by this simple treatment resulting in a remarkable recovery of the catalytic activity. 相似文献
11.
We have investigated the catalytic behavior of Pt encapsulated TiO 2 nanotubes for the water gas shift reaction as well as the hydrogenation of CO. Pt–TiO 2 nanotube catalysts were prepared by employing fine fiber shaped crystals of [Pt(NH 3) 4](HCO 3) 2 complex as a structure determining template material. The turnover frequencies (TOF) of these nanotube catalysts were more than one order of magnitude larger than conventional impregnation Pt/TiO 2 catalysts, and the selectivity for methanol in CO–H 2 reaction was extraordinary high compared to the impregnation catalysts. The XPS and XRD analyses of the nanotubes revealed characteristic electronic state of reduced TiO 2 (Ti 3+ in rutile structure) with zerovalent Pt even after the calcination at 773 K. In WGS reaction, electron rich Ti 3+ on the nanotube wall may play an important role to activate water molecules for the oxidation of CO. In CO–H 2 reaction, similar promotion effect of Ti 3+ species may be operating for selective methanol formation by supplying active OH(a). 相似文献
12.
Conductivity of molten Mg(NO 3) 2. 6H 2O + NH 4NO 3 system containing up to 80 mole percent of the latter was measured in the temperature range 320–400 K. Temperature dependence of conductivity exhibited Arrhenian behaviour. Conductivity—composition isotherms were non-linear indicating weak ordering tendencies. Equivalent conductivity data did not obey Markov equation; deviations have been interpreted in terms of the Tobolsky parameter (θ). Constancy of θ indicate that the water of hydration in the system remains with Mg 2+ ions and is unaffected by the addition of NH +4 ions. 相似文献
13.
CeO 2–ZrO 2–La 2O 3 (CZL) mixed oxides were prepared by citric acid sol–gel method. The as-received gel was calcined at 500, 700, 900 and 1050 °C to obtain the so-called C5, C7, C9 and CK, respectively. The C5, C7 and C9 powders were impregnated with H 2PtCl 6 and then calcined at 500 °C to prepare P5C5, P5C7 and P5C9, respectively. The impregnated CK powders were calcined at 500, 700 and 900 °C to prepare P5CK, P7CK and P9CK, respectively. The XRD and XPS analyses show that the surface distribution of Pt is evidently influenced by the structural and textural properties of the support. The CO adsorption followed by FTIR reveals that the dispersion and the chemisorption sites of Pt are reduced as the calcination temperature of CZL support increases. The chemisorption ability of the CK samples is even completely deactivated. The encapsulation mechanism, which has been applied to explain the so-called strong metal–support interaction (SMSI) after reductive treatment, is introduced here to demonstrate the abnormal observations though the samples were prepared in oxidative atmosphere. The HRTEM results also confirm this explanation. The effects of oxygen vacancies, the chemisorption sites on the Pt surface and Pt/Ce interfacial sites on the three-way catalytic activities are discussed. 相似文献
14.
Supported molybdenum and tungsten carbides were synthesized by temperature-programmed reactions. These materials were characterized by XRD, EDS analysis, HRTEM and CO chemisorption. Hydrogenation of tetralin was carried out at a total pressure of 4 MPa (3.06 MPa of H 2), at 573 K, without or with sulfur (200 ppm of sulfur as DMDS). The resulting activities were compared with those of MoS 2/Al 2O 3 and Pt (1% (w/w) metal loading) supported on Al 2O 3 or SiO 2. In the absence of sulfur, WC/Al 2O 3 showed an initial activity similar to that of Pt/SiO 2, higher than that of MoS 2/Al 2O 3 but lower than that of Pt/Al 2O 3. In the presence of H 2S, WC/Al 2O 3 showed a steady-state activity similar to that of Pt/Al 2O 3 (which suffered a marked deactivation). Post-reaction characterization did not show any sulfur poisoning of the supported carbides. Therefore the supported carbides are sulfur-tolerant and promising catalysts for the hydrogenation of aromatics in diesel fuels in the presence of small amounts of S-containing compounds. 相似文献
15.
A method to quantify DRIFT spectral features associated with the in situ adsorption of gases on a NO x adsorber catalyst, Pt/K/Al 2O 3, is described. To implement this method, the multicomponent catalyst is analysed with DRIFT and chemisorption to determine that under operating conditions the surface comprised a Pt phase, a pure γ-Al 2O 3 phase with associated hydroxyl groups at the surface, and an alkalized-Al 2O 3 phase where the surface –OH groups are replaced by –OK groups. Both DRIFTS and chemisorption experiments show that 93–97% of the potassium exists in this form. The phases have a fractional surface area of 1.1% for the 1.7 nm-sized Pt, 34% for pure Al 2O 3 and 65% for the alkalized-Al 2O 3. NO 2 and CO 2 chemisorption at 250 °C is implemented to determine the saturation uptake value, which is observed with DRIFTS at 250 °C. Pt/Al 2O 3 adsorbs 0.087 μmol CO 2/m 2and 2.0 μmol NO 2/m 2, and Pt/K/Al 2O 3 adsorbs 2.0 μmol CO 2/m 2and 6.4 μmol NO 2/m 2. This method can be implemented to quantitatively monitor the formation of carboxylates and nitrates on Pt/K/Al 2O 3 during both lean and rich periods of the NO x adsorber catalyst cycle. 相似文献
16.
The influence of NO on the adsorption and desorption of NO 2 on BaO/TiO 2 has been studied under lean conditions. The adsorption of NO 2 involves the disproportionation of NO 2 into an adsorbed nitrate species and NO released to the gas phase with a 3:1 ratio, Three different nitrate species form on the catalyst: surface nitrates on the TiO 2 support, surface nitrates on BaO, and bulk barium nitrate. The stability of the three species in different gas feeds was investigated by temperature-programmed desorption (TPD). The reverse reaction of the NO2 disproportionation has also been observed. If NO is added to the feed, nitrates previously formed on the sorbent will decompose into NO2. Therefore, the above chemical equation should be considered as an equilibrium reaction. Applying this finding to the NOx storage and reduction catalyst means that NO probably reacts with the previously formed nitrates yielding NO2 as an intermediate product. This NO2 is subsequently reduced by the reducing agents (hydrocarbons and CO) present during the regeneration period. 相似文献
17.
Activities of a series of metals (Pt, Pd, Rh, Cu, Mn) supported on TiO 2 were investigated for the catalytic oxidation of formaldehyde. Among them, Pt/TiO 2 was found to be the most promising catalyst. Nitrogen adsorption, hydrogen chemisorption, X-ray diffraction (XRD), transmission electron microscopy (TEM) and temperature programmed reduction (TPR) by H 2 were used to characterize the platinum catalysts. Using Ce 0.8Zr 0.2O 2, Ce 0.2Zr 0.8O 2, SiO 2 as supports instead of TiO 2, the activity sequence of 0.6 wt.% platinum with respect to the supports is TiO 2 > SiO 2 > Ce 0.8Zr 0.2O 2 > Ce 0.2Zr 0.8O 2, and this appears to be correlated with the dispersion of platinum on supports rather than the specific surface areas of the catalysts. Platinum loading on TiO 2 has a great effect on the catalytic activity, and 0.6 wt.% Pt/TiO 2 catalyst was observed to be the most active, which could be attributed to the well-dispersed platinum surface phase. The reduction temperature greatly affects the particle size and, consequently, the catalytic activity. The smaller particle size of platinum, due to its high dispersion on support, has a positive effect on catalytic performance. Increasing formaldehyde concentration and space velocity exhibits an inhibiting effect on the catalytic activity. 相似文献
18.
Phase changes in high temperature treated (>900 °C) 8 or 20 wt% BaO supported on γ-Al 2O 3 model lean NO x trap (LNT) catalysts, induced by NO 2 and/or H 2O adsorption, were investigated with powder X-ray diffraction (XRD), solid state 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, and NO 2 temperature programmed desorption (TPD) experiments. After calcination in dry air at 1000 °C, the XRD and solid state 27Al MAS NMR results confirm that stable surface BaO and bulk BaAl 2O 4 phases are formed for 8 and 20 wt% BaO/Al 2O 3, respectively. Following NO 2 adsorption over these thermally treated samples, some evidence for nanosized Ba(NO 3) 2 particles are observed in the XRD results, although this may represent a minority phase. However, when water was added to the thermally aged samples after NO 2 exposure, the formation of bulk crystalline Ba(NO 3) 2 particles was observed in both samples. Solid state 27Al MAS NMR is shown to be a good technique for identifying the various Al species present in the materials during the processes studied here. NO 2 TPD results demonstrate a significant loss of uptake for the 20 wt% model catalysts upon thermal treatment. However, the described phase transformations upon subsequent water treatment gave rise to the partial recovery of NO x uptake, demonstrating that such a water treatment of thermally aged catalysts can provide a potential method to regenerate LNT materials. 相似文献
19.
The effects of pretreatment of catalyst on its surface properties and the HDS activity of a 0.49% Ru/Al 2O 3 catalyst were studied in a single-pass, differential microreactor. The surface properties of the catalyst were measured by NH 3-TPD and XPS analysis. The Ru/Al 2O 3 catalyst was pretreated in three ways: reduced in H 2 (Ru-R catalyst), oxidized in air and subsequently reduced in H 2 (Ru-OR catalyst), or sulfided in H 2S/H 2 (Ru-S catalyst). Three types of peaks (low, middle, and high temperatures) were observed in the NH 3-TPD study. The predominant high-temperature peak was observed for both the Ru-OR and Ru-S catalyst, pretreated at 300°C. Mass spectrometry showed that the high-temperature peak in NH 3-TPD consisted of N 2 and H 2 formed from the decomposition of NH 3 on the ruthenium sites. NO adsorption of unsaturated Ru species was related to the low-temperature peak in the NH 3-TPD. The XPS analysis showed that the peaks at 279.9 eV, 280.6 eV, and 282.5 eV were ascribed to metallic ruthenium, RuO 2, and RuO 3, respectively. The low-, middle-, and high-temperature peaks were assigned to RuO 2, acid sites on alumina, and metallic Ru, respectively. Metallic ruthenium was effective in the HDS of thiophene and the decomposition of NH 3. 相似文献
20.
A novel regenerable Fe/activated coke (AC) desulfurizer prepared by impregnation of Fe(NO 3) 3 on an activated coke was investigated. Experiment results showed that at 200 °C the SO 2 adsorption capacity of the Fe/AC was higher than that of AC or Fe 2O 3. Temperature-programmed desorption (TPD) revealed that H 2SO 4 and Fe 2(SO 4) 3 were generated on the desulfurizer upon adsorption of SO 2. Effect of desulfurization temperature was also investigated which revealed that with increasing temperature from 150 to 250 °C, the SO 2 removal ability gradually increases. The used Fe/AC can be regenerated by NH 3 at 350 °C to directly form solid ammonium-sulfate salts. 相似文献
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