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1.
Ag/Al2O3 is a promising catalyst for the selective catalytic reduction (SCR) by hydrocarbons (HC) of NO x in both laboratory and diesel engine bench tests. New developments of the HC-SCR of NO x over a Ag/Al2O3 catalyst are reviewed, including the efficiencies and sulfur tolerances of different Ag/Al2O3-reductant systems for the SCR of NO x ; the low-temperature activity improvement of H2-assisted HC-SCR of NO x over Ag/Al2O3; and the application of a Ag/Al2O3-ethanol SCR system with a heavy-duty diesel engine. The discussions are focused on the reaction mechanisms of different Ag/Al2O3-reductant systems and H2-assisted HC-SCR of NO x over Ag/Al2O3. A SO2-resistant surface structure in situ synthesized on Ag/Al2O3 by using ethanol as a reductant is proposed based on the study of the sulfate formation. These results provide new insight into the design of a high-efficiency NO x reduction system. The diesel engine bench test results showed that a Ag/Al2O3-ethanol system is promising for catalytic cleaning of NO x in diesel exhaust.  相似文献   

2.
Fullerenyl radicals (FR) RC60 · and chemiluminescence (CL) are generated in the presence of O2 in C60—R3Al (R = Et, Bui) solutions in toluene (T = 298 K). The FR are formed due to the addition of the R· radical, which is an intermediate of R3Al autooxidation, to C60. Mass spectroscopy and HPLC were used to identify EtnC60Hm (n, m = 1–6), EtpC60 (p = 2–6), and dimer EtC60C60Et as stable products of FR transformations. As found by ESR, the EtC60 · radical (g = 2.0037) is also generated by photolysis of solutions obtained after interaction in the (C60— R3Al)—O2 system. In the presence of dioxygen, the FR is not oxidized but yields complexes with O2, which appear as broadening of the ESR signals. Chemiluminescence arising in the (C60—R3Al)—O2 system is much brighter (I max = 1.86·108 photon s−1 mL−1) than the known background CL (I max = 6.0·106 photon s−1 mL−1) for the autooxidation of R3Al and is localized in a longer-wavelength spectral region (λmax = 617 and 664 nm). This CL is generated as a result of energy transfer from the primary emitter 3CH3CHO* to the products of FR transformation: RnC60Hm, RpC60, and EtC60C60Et. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 205–213, February, 2007.  相似文献   

3.
Direct on-line studies of a C2HCl3/He/O2 microwave discharge plasma made possible the evolution and detection of many unfamiliar ionic species. Numerous ionic chlorocarbons, chlorohydrocarbons, oxygenated chlorohydrocarbons, oxygenated hydrocarbon radicals, and simple hydrocarbon species were identified mass spectrometrically as by-products: C m Cl n (m = 1–4, 6, 8; n = 1–8), C m H n Cl x (m = 1–4, 6, 7, 10; n, x = 1–6), C m H n Cl x O y (m = 1–5, 12; n = 1–7; x = 1, 2, 4, 6; y = 1–3), C n H2n−1O (n = 2, 3), C m H n (m = 2, 4, 6, 8; n = 2, 4), and so on. The studies clearly showed the presence of various unfamiliar positive ionic O-containing species such as C2ClO2, CCl3CO, C2H2Cl4O2, and C4H2Cl6O3. It is apparent that positive-ion reactions play a significant role in producing many ionic species in the chemistry of C2HCl3 plasmas.  相似文献   

4.
Steady State Isotopic Transient Kinetic Analysis (SSITKA) experiments using on-line Mass Spectrometry (MS) and in situ Diffuse Reflectance Infrared Fourier-Transform Spectroscopy (DRIFTS) have been performed to study essential mechanistic aspects of the Selective Catalytic Reduction of NO by H2 under strongly oxidizing conditions (H2-SCR) in the 120–300°C range over a novel 0.1 wt % Pt/MgO-CeO2 catalyst. The N-path of reaction from NO to the N2 gas product was probed by following the 14NO/H2O215NO/H2/O2 switch (SSITKA-MS and SSITKA-DRIFTS) at 1 bar total pressure. It was found that the N-pathway of reaction involves the formation of two active NO x species different in structure, one present on MgO and the other one on the CeO2 support surface. Inactive adsorbed NO x species were also found on both the MgO-CeO2 support and the Pt metal surfaces. The concentration (mol/g cat) of active NO x leading to N2 was found to change only slightly with reaction temperature in the 120–300°C range. This leads to the conclusion that other intrinsic kinetic reasons are responsible for the volcano-type conversion of NO versus the reaction temperature profile observed.  相似文献   

5.
Inorganic-organic hybrid membranes containing silica as the structure matrix, poly(N-vinylpyrrolidone) (PVP) as the organic mediating agent and silver ions as olefinic carriers were prepared using sol–gel method and dip-coating process. The structure and permeances of the membranes for N2, He, C2H4, C2H6 at different temperatures indicated that defect-free membranes were obtained and the transportation of the C2H4 through the membranes followed the dissolution and diffusion mechanism. Ideal separation factors of C2H4/C2H6 through the membranes were evaluated at the temperature of 298, 373 and 423 K respectively using mixture gas of 50% C2H4-50% C2H6. The results showed that the ideal separation factors of C2H4/C2H6 through the membranes were obviously greater than the ratio of PC2H4/PC2H6 obtained from the single gas measurement due to the hindering effect by the adsorbed C2H4. The ideal separation factors of C2H4/C2H6 increased with temperature and reached 10 at 423 K, which suggested that C2H4 and C2H6 could be separated at lower humidity compared to the reported organic polymer/silver salt membranes in which humidified gases and higher silver loading were usually used. The transport of C2H4 in the inorganic-organic hybrid membrane was proposed to follow the hopping mechanism, that is, olefins moved across the fixed silver sites.  相似文献   

6.
The efflorescence and deliquescence processes of Mg(NO3)2 aerosol particles deposited on ZnSe substrate have been investigated through in situ Fourier transform infrared-attenuated total reflection (FTIR-ATR) technique at the molecular level. At relative humidity (RH) of ∼3%, Mg(NO3)2 particles existed as amorphous states. The amorphous Mg(NO3)2 particles were transformed into crystalline Mg(NO3)2 · nH2O (n ≤ 5) with slight increasing of RH. Thermodynamically stable Mg(NO3)2·6H2O crystals were gradually formed on the particle surface and started to be dissolved at the saturation point (∼53% RH). At the same time, a continuous phase transition from Mg(NO3)2 · nH2O (n≤5) to Mg(NO3)2·6H2O occurred on the particle surface. This led the solid particles to completely deliquesce at 76% RH, which was much higher than the saturation point of 53% RH. In the efflorescence process, Mg(NO3)2 droplets entered into the supersaturated region due to the gradual evaporation of water. Finally, amorphous particles were formed when RH decreased below 5%. In the FTIR-ATR spectra of the supersaturated Mg(NO3)2 droplets, the absorbance of the symmetric stretching vibration of NO 3 (v 1- NO 3 ) clearly became stronger. It resulted from the continuous formation of solvent share ion pairs (SIPs), and even the contact ion pairs (CIPs) between Mg2+ and NO 3 . Supported by the Trans-Century Program Foundation for the Talents by the Ministry of Education of China, the National Natural Science Foundation of China (Grant Nos. 20073004, 20473012, and 20673010), the 111 Project (B07012), and the State Key Laboratory of Physical Chemistry for Solid Surface of Xiamen University  相似文献   

7.
In the framework of synchronous gas-phase electron diffraction and mass spectrometry experiment, the saturated vapor of N,N′-ethylenebis(salicylaldiminate) copper(II) CuO2N2C16H14 is studied at a temperature T 574(5) K. It is found that evaporation is congruent and the saturated vapor consists of monomeric molecules. Electron diffraction data are proved to correspond to the geometric model for the CuO2N2C16H14 molecule of C 2 symmetry with an almost planar structure of the CuN2O2 coordination fragment and internuclear distances \(r_{h_1 } \)(Cu-O) = 1.917(13) Å and \(r_{h_1 } \)(Cu-N) = 1.931(15) Å. The stuctural parameters obtained are compared to those quantum chemically calculated and molecular parameters in crystals.  相似文献   

8.
It has been demonstrated by quantitative spectrokinetic measurements that, on the surface of zirconia stabilized as a tetragonal phase, the rate-limiting step of the selective catalytic reduction of nitrogen oxides (SCR of NO x ) with propylene is the interaction of surface nitrates with C3H6 yielding organic nitro compounds. It is hypothesized that propylene reacts not with the nitrates themselves but with the activated complex NO2 ads whose structure is intermediate between the structures of the monodentate NO3 ? and NO2 species. Deep C3H6 oxidation exerts an adverse effect on the rate of the SCR of NO x with propylene, and the interaction between O2 and NO, which yields NO2 and NO3 ? stimulates further nitrogen reduction to N2. The effect of the reaction between oxygen and O2N?C n H m on the NO x reduction rate is variable and is determined by the C3H6/NO x ratio. A generalized scheme of the SCR of NO x with propylene on the surface of ZrO2 partially stabilized as a tetragonal phase has been developed by comparing experimental data of this study and data available from the literature.  相似文献   

9.
The Wiener index of a graph G is defined as , where V(G) is the set of all vertices of G and for denotes the length of a minimal path between x and y. A C 4 C 8 net is a trivalent decoration made by alternating squares C 4 and octagons C 8. It can cover either a cylinder or a torus. In this paper, an algorithm for computing the distance matrix of a C 4 C 8(R) nanotorus T = T[p,q] is given. Using this matrix, the Wiener index of T is computed.  相似文献   

10.
Gas-phase electron diffractometry was used to study the molecular structure of N,N′-ethylenebis(salicylaldiminato)nickel(II), NiO2N2C16H14, [hereinafter Ni(salen)] at 583(5) K. The molecule has C 2 symmetry with a practically planar structure of the NiN2O2 coordination unit and with internuclear distances r α (Ni-O) = 1.882(21) Å and r α (Ni-N) = 1.889(22) Å. The results of B3LYP/CEP-31G molecular structure calculations are in good agreement with experimental data, whereas the RHF/CEP-31G method significantly overestimates the Ni-N internuclear distance and gives worse results for other structural parameters. According to 3LYP/CEP-31G calculations, the 1 A low-spin state is 28 kJ/mole lower in energy than the 3 B high-spin state.  相似文献   

11.
Large-scale Li1+x V3O8 nanobelts were successfully fabricated using filter paper as deposition substrate through a simple surface sol–gel method. The nanobelts were as long as tens of micrometers with widths of 0.4–1.0 μm and thickness of 50–100 nm. The nanobelts were characterized by X-ray diffration (XRD), Fourier infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM). The formation mechanism of the nanobelts was investigated, showing that the morphology of the nanobelts is mainly determined by the calcination temperature. Electrochemical properties of the Li1+x V3O8 nanobelts were characterized by charge–discharge experiments, and the results demonstrate that the Li1+x V3O8 nanobelts exhibit a high discharge capacity (278 mAh g−1) and excellent cycling stability.  相似文献   

12.
The effects of H2 and H2 + O2 gas mixtures of varying composition on the state of the surface of the Pt/MoO3 model catalyst prepared by vacuum deposition of platinum on oxidized molybdenum foil were investigated by X-ray photoelectron spectroscopy (XPS) at room temperature and a pressure of 5–150 Torr. For samples with a large Pt/Mo ratio, the XP spectrum of large platinum particles showed that the effect of hydrogen-containing mixtures on the catalyst was accompanied by the reduction of molybdenum oxide. This effect results from the activation of molecular hydrogen due to the dissociation on platinum particles and subsequent spill-over of hydrogen atoms on the support. The effect was not observed at low platinum contents in the model catalyst (i.e., for small Pt particles). It is assumed for the catalyst that the loss of its hydrogen-activating ability is a consequence of the formation of platinum hydride. Possible participation of platinum hydride as intermediate in hydrogen oxidation to H2O2 is discussed.  相似文献   

13.
Osmotic coefficients and water activities for the Li2B4O7+LiCl+H2O system have been measured at T=273.15 K by the isopiestic method, using an improved apparatus. Two types of osmotic coefficients, φ S and φ E, were determined. φ S is based on the stoichiometric molalities of the solute Li2B4O7(aq), and φ E is based on equilibrium molalities from consideration of the equilibrium speciation into H3BO3,B(OH)4 and B3O3(OH)4. The stoichiometric equilibrium constants K m for the aqueous speciation reactions were estimated. Two types of representations of the osmotic coefficients for the Li2B4O7+LiCl+H2O system are presented with ion-interaction models based on Pitzer’s equations with minor modifications: model (I) represents the φ S data with six parameters based on considering the ion-interactions between three ionic species of Li+, Cl, and B4O72−, and model (II) for represents the φ E data based on considering the equilibrium speciation. The parameters of models (I) and (II) are presented. The standard deviations for the two models are 0.0152 and 0.0298, respectively. Model (I) was more satisfactory than model (II) for representing the isopiestic data.  相似文献   

14.
Solid solution phases of a formula Fe8V10W16–xMoxO85 where 0≤x≤4, have been obtained, possessing a structure of the compound Fe8V10W16O85. It was found on the base of XRD and DTA investigations that these solution phases melted incongruently, with increasing the value of x, in the temperature range from 1108 (x=0) to 1083 K (x=4) depositing Fe2WO6 and WO3. The increase of the Mo6+ ions content in the crystal lattice of Fe8V10W16O85 causes the lattice parameters a=b contraction with cbeing almost constant. IR spectra of the Fe8V10W16–xMoxO85 solid solution phases have been recorded.  相似文献   

15.
Studies on photo-catalytic reduction of CO2 using TiO2 photo-catalyst (0.1%, w/v) as a suspension in water was carried out at 350 nm light. CO2 from both commercially available source, as well as generated in situ through 2-propanol oxidation, was used for this study. The photolytic products such as hydrogen (H2), carbon monoxide (CO) andmethane (CH4) generated were monitored in TiO2 suspended aqueous solution with and without a hole scavenger, viz., 2-propanol. Similar photolytic experiments were also carried out with varying ambient such as air, O2, N2 and N2O. The yields of CO and CH4 in all these systems under the present experimental conditions were found to be increasing with light exposure time. H2 yield in N2-purged systems containing 2-propanol was found to be more as compared to the without 2-propanol system. The rate of H2 production in N2-purged aqueous solutions containing 0.1% TiO2 suspension were evaluated to be 0.226 and 5.8 μl/h, without and with 0.5 M 2-propanol, respectively. This confirmed that 2-propanol was an efficient hole scavenger and it scavenged photo-generated holes (h+), allowing its counter ion, viz., e, to react with water molecule/H+ to yield more H2. The formation of both CO and CH4 in the photolysis of CO2-purged aqueous solutions containing suspended TiO2 in absence of 2-propanol reveal that the generation of CH4 is taking place mainly through CO intermediate. In presence of air/O2, the yield of H2 in the system without 2-propanol was observed to be negligible as compared to the system containing 2-propanol in which low yield of H2 was obtained with a formation rate of approx. 0.5 μl/h.  相似文献   

16.
By functional density quantum-chemical method (DFT/B3LYP using the 6-311++G(3df)) it has been shown that the molecular structures of N2O5 with Cs and C2 symmetries are energetically equivalent. It follows from calculations of the vibrational frequencies that both structures are characterized by potential energy minima and correspond to stationary states of the N2O5 molecule. It is proposed, on the basis of a comparison of the calculated and experimental vibrational spectra of N2O5, that dinitrogen pentaoxide exists in the gas phase as an equimolecular mixture of N2O5 molecules with Cs and C2 symmetry, while in the solid phase it is characterized by the C2 molecular structure. __________ Translated from Teoreticheskaya I éksperimental’naya Khimiya, Vol. 43, No. 1, pp. 58–63, January–February, 2007.  相似文献   

17.
Reactions of an amino derivative of the closo-decaborate anion [1-B10H9NH3] with aromatic aldehydes afforded Schiff bases [1-B10H9NH=CHAr] (Ar=Ph, C6H4-2-OMe, or C6H4-4-NHCOMe). The reduction of the latter with sodium borohydride gave the corresponding benzylamino derivatives [1-B10H9NH2CH2Ar].Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2004–2007, September, 2004.  相似文献   

18.
A photo-triggered discharge is used to study the influence of three hydrocarbons (HCs), propene (C3H6), n-decane (C10H22), and toluene (C6H5CH3) on NO conversion in N2/O2/NO/HC mixtures, with 18.5% O2 concentration, 700 ppm of NO, and an hydrocarbon concentration ranging between 190 ppm and 2,700 ppm. The electrical system generates a transient homogeneous plasma, working under 400 mbar total pressure, with a 50 ns short current pulse at a repetition frequency up to a few Hz. The NO concentration at the exit of the reactor is quantified using absolute FTIR spectroscopy measurements, as a function of the specific deposited energy in the discharge and the mixture composition. Owing to the plasma homogeneity, the experimental results can be compared to predictions of a self-consistent 0-D discharge and kinetic model based on available data in the literature about reactions and their rate constants. It is shown that the addition of either propene (as for DBD or corona discharges) or n-decane to N2/O2/NO leads to an improvement of the NO removal as compared to the mixture without hydrocarbon molecules. The adopted kinetic schemes explain this effect for the two mixture types. On the other hand, both the experiments and model predictions emphasize that the addition of toluene does not lead to the improvement of NO conversion. Moreover, compounds that are useful for NO x reduction catalysis, such as aldehydes, are less produced in the mixture with toluene.  相似文献   

19.
Fe3O4 nanorods and Fe2O3 nanowires have been synthesized through a simple thermal oxide reaction of Fe with C2H2O4 solution at 200–600°C for 1 h in the air. The morphology and structure of Fe3O4 nanorods and Fe2O3 nanowires were detected with powder X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The influence of temperature on the morphology development was experimentally investigated. The results show that the polycrystals Fe3O4 nanorods with cubic structure and the average diameter of 0.5–0.8 μm grow after reaction at 200–500°C for 1 h in the air. When the temperature was 600°C, the samples completely became Fe2O3 nanowires with hexagonal structure. It was found that C2H2O4 molecules had a significant effect on the formation of Fe3O4 nanorods. A possible mechanism was also proposed to account for the growth of these Fe3O4 nanorods. Supported by the Fund of Weinan Teacher’s University (Grant No. 08YKZ008), the National Natural Science Foundation of China (Grant No. 20573072) and the Doctoral Fund of Ministry of Education of China (Grant No. 20060718010)  相似文献   

20.
采用多种物理化学手段研究了在模拟的轻型柴油车尾气中不同Co担载量及Cu掺杂的Co/ZSM-5催化剂的Co组分分散状态、可还原性、NO吸附脱附性质对C3H8选择性催化还原NOx性能的影响。结果表明,浸渍法制备的Co/ZSM-5催化剂上既有外表面上的Co3+和Co2+物种,也有孔内的Co2+离子。富氧条件下Co/ZSM-5催化剂上C3H8选择性催化还原NOx的活性主要与ZSM-5载体孔外表面分散的CoOx物种中的钴离子可还原能力和NO吸附脱附性能密切相关。Co/ZSM-5催化剂上适宜的Co担载量约为4.0wt%,低担载量时随Co担载量增加,表面CoOx物种中钴离子可还原能力增强,C3H8选择性催化还原NOx的低温转化活性增加;高担载量时,随Co担载量增加,单位Co离子的NO吸附量的减少以及催化剂表面活性中心数的减少,导致了Co/ZSM-5催化剂NOx的转化率和催化剂比速率(k)的下降。孔外表面Co3O4晶体的存在使催化剂表面产生较强的NO吸附,并在高温时有利于C3H8的氧化燃烧,使C3H8选择性催化还原NOx的活性降低。  相似文献   

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