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1.
《Microporous Materials》1994,2(2):127-136
The adsorption isotherms and 129Xe nuclear magnetic resonance (NMR) chemical shifts of xenon and the adsorption isotherms of carbon monoxide of Cu(II)- and Cu(I)-exchanged zeolites NaY were measured. The former zeolites of 53, 75, and 95% exchange degrees were investigated after various pretreatment steps comprising dehydration, oxidation and reduction with CO at 420°C as well as long-term CO reduction at 470°C. The Cu(I)Y zeolite of 70% exchange degree was prepared via a solid-state exchange procedure with CuCl and subjected to dehydration at 420°C. In all cases, except the dehydrated zeolites, almost linear xenon adsorption isotherms and linear 129Xe NMR chemical shift versus xenon concentration curves running parallel to each other are obtained. In contrast, the chemical shift curves for the dehydrated zeolites are non-linear at low xenon concentrations turning towards negative chemical shift values at very low pressures. The whole body of the experimental xenon data can be explained quantitatively with a unifying approach on the basis of a site adsorption model where the sites are (i) two types of cuprous ions of much different adsorption strength and 129Xe chemical shift, (ii) Na+ cations, (iii) Lewis acid sites generated through autoreduction and reduction of Cu2+ by CO, and (iv) framework sites free of cations. These five types of sites are each characterized by Langmuir adsorption isotherm constants and local 129Xe NMR chemical shifts. The adsorption site concentrations in the various zeolites are evaluated. The supercage Cu(I) concentration values are in nice agreement with the results deduced from the CO adsorption isotherm measurements.  相似文献   

2.
Various commercial zeolites, including FER, MOR, ZSM-5, BEA, and FAU frameworks, were treated with NH4F aqueous solutions to study the effects of fluoride etching on different zeolite frameworks. NH4F-treated small-medium pore FER, MOR, and ZSM-5 samples showed much higher mesoporosities than the untreated ones without alteration of the structural compositions and acidic properties. On the other hand, the 12-membered ring zeolites BEA and FAU showed severe dissolution of the framework aluminosilicate structure after NH4F etching due to the high accessibility of fluoride species into the framework structures. The effect of NH4F concentration on the fluoride treatment of H-ZSM-5 zeolite was specifically studied. From the results, we observed that structural etching with 20 wt % NH4F was optimal for fabricating open-pore H-ZSM-5 zeolite and resulted in a high mesoporosity with comparable relative crystallinity and acidity with respect to the untreated H-ZSM-5. The catalytic activities of the open-pore H-ZSM-5 were evaluated with acid-catalyzed methanol and bioethanol conversions. Remarkably, the hierarchical open-pore H-ZSM-5 zeolite fabricated via fluoride etching exhibited an enhanced catalytic performance in bioethanol conversion with >85 % conversion over 34 h TOS and a higher catalytic stability in methanol conversion than the parent H-ZSM-5 (~50 % of bioethanol conversion at 34 h TOS).  相似文献   

3.
Despite the extensive use of 129Xe NMR for characterization of high surface-to-volume porous solids, particularly zeolites, this method has not been widely used to explore the properties of microporous carbon materials. In this study, commercial amorphous carbons of different origin (produced from different precursors) and a series of activated carbons obtained by successive cyclic air oxidation/pyrolysis treatments of a single precursor were examined. Models of 129Xe chemical shift as a function of local Xe density, mean pore size, and temperature are discussed. The virial coefficient arising from binary xenon collisions, σXe-Xe, varied linearly with the mean pore size given by N2 adsorption analysis; σXe-Xe appeared to be a better probe of the mean pore size than the chemical shift extrapolated to zero pressure, σS.  相似文献   

4.
XAFS (both XANES and FT-EXAFS) measurements revealed that the Pb2+ /ZSM-5 catalyst prepared from precursor H-ZSM-5 by a conventional ion-exchange method includes a highly dispersed 3-fold coordinated Pb2+ ion species within the zeolite framework. UV-irradiation of Pb2+ /ZSM-5 led to effective decomposition of NO and N2O producing N2. The photocatalytic decomposition of NO is found to be slightly preferable than that of N2O. The isolated Pb2+ ions play a significant role in the decomposition of pollutant NO x . Ab initio and DFT quantum chemical studies at the HF/Lanl2dz and B3PW91/Lanl2dz levels further shed light on local structures of the Pb2+ active site of lead-containing zeolites, as well as on their interactions with pollutant NO and N2O molecules. In agreement with experiments, 3-fold coordination was found to be the most favorable state for the Pb2+ site within the zeolite framework.  相似文献   

5.
以氨水为矿化剂,通过添加NH4+离子水热合成了具有较低骨架硅铝比的ZSM-5分子筛。通过X射线衍射(XRD)、扫描电镜(SEM)、固体核磁共振(MAS-NMR)等表征手段,研究了硅源、铝源、矿化剂、阳离子等对ZSM-5分子筛的结晶度、形貌尺寸和骨架硅铝比等的影响,研究了ZSM-5分子筛的骨架硅铝比对正庚烷催化裂化反应的影响。研究表明,投料硅铝比越低,铝原子越难进入到分子筛骨架中;当氨水为矿化剂、正硅酸四乙酯为硅源时可以合成骨架硅铝比较低的氢型ZSM-5分子筛,添加NH4+离子可以增强骨架铝的嵌入,进一步降低分子筛的骨架硅铝比(24.2)。正庚烷裂化反应结果表明,降低分子筛的骨架硅铝比可以提高正庚烷裂化反应的活性,但会降低低碳烯烃的选择性。  相似文献   

6.
This paper reports a study of the decomposition of water by gamma radiolysis in the presence of zeolites ZSM-5, SAPO-5, and MOR. The irradiation is performed using 60Co as a source with 1.12×1015 Bq activity at a 8.3 kGy/h dose rate. The stable products of radiolysis as well as the other chemical species are measured by mass spectrometry. The calculated radiation yield (GH 2) generally decreases in the order: H-ZSM-5>Na-ZSM-5>H-SAPO-5>MOR under the given experimental conditions; the yield is higher in the presence of these catalysts than in their absence.  相似文献   

7.
It has been established that catalytic activity in the CO oxidation of bimetal-containing zeolite Co,Pd-systems based on ZSM-5 and obtained via ion exchange and impregnation at different orders of the introduction of metal cations is higher than that of monometal-containing systems Co-ZSM-5 and Pd—ZSM-5. Through TPD of NH3, it was determined that coordination-unsaturated bicationic associates are formed in Co,Pd/ZSM-5 zeolites obtained by ion exchange. It was found that the activity of bimetal-containing systems depends on the relation of the active components.  相似文献   

8.
The isotropic 129Xe NMR chemical shift of atomic Xe dissolved in liquid benzene was simulated by combining classical molecular dynamics and quantum chemical calculations of 129Xe nuclear magnetic shielding. Snapshots from the molecular dynamics trajectory of xenon atom in a periodic box of benzene molecules were used for the quantum chemical calculations of isotropic 129Xe chemical shift using nonrelativistic density functional theory as well as relativistic Breit?CPauli perturbation corrections. Thus, the correlation and relativistic effects as well as the temperature and dynamics effects could be included in the calculations. Theoretical results are in a very good agreement with the experimental data. The most of the experimentally observed isotropic 129Xe shift was recovered in the nonrelativistic dynamical region, while the relativistic effects explain of about 8% of the total 129Xe chemical shift.  相似文献   

9.
The isotropic 129Xe nuclear magnetic resonance (NMR) chemical shift (CS) in Xe@C60 dissolved in liquid benzene was calculated by piecewise approximation to faithfully simulate the experimental conditions and to evaluate the role of different physical factors influencing the 129Xe NMR CS. The 129Xe shielding constant was obtained by averaging the 129Xe nuclear magnetic shieldings calculated for snapshots obtained from the molecular dynamics trajectory of the Xe@C60 system embedded in a periodic box of benzene molecules. Relativistic corrections were added at the Breit–Pauli perturbation theory (BPPT) level, included the solvent, and were dynamically averaged. It is demonstrated that the contribution of internal dynamics of the Xe@C60 system represents about 8% of the total nonrelativistic NMR CS, whereas the effects of dynamical solvent add another 8%. The dynamically averaged relativistic effects contribute by 9% to the total calculated 129Xe NMR CS. The final theoretical value of 172.7 ppm corresponds well to the experimental 129Xe CS of 179.2 ppm and lies within the estimated errors of the model. The presented computational protocol serves as a prototype for calculations of 129Xe NMR parameters in different Xe atom guest–host systems. © 2013 Wiley Periodicals, Inc.  相似文献   

10.
One- and two-dimensional 129Xe NMR spectroscopy has been employed to study the porosity of cocrystallized MCM-49/ZSM-35 zeolites under the continuous flow of hyperpolarized xenon gas. It is found by variable-temperature experiments that Xe atoms can be adsorbed in different domains of MCM-49/ZSM-35 cocrystallized zeolites and the mechanically mixed counterparts. The exchange of Xe atoms in different types of pores is very fast at ambient temperatures. Even at very low temperature two-dimensional exchange spectra (EXSY) show that Xe atoms still undergo much faster exchange between MCM-49 and ZSM-35 analogues in the cocrystallized zeolites than in the mechanical mixture. This demonstrates that the MCM-49 and ZSM-35 analogues in cocrystallized zeolites may be stacked much closer than in the physical mixture, and some parts of intergrowth may be formed due to the partially similar basic structure of MCM-49 and ZSM-35.  相似文献   

11.
The chemical environments of europium-exchanged NaX (Si/Al =1.16) and NaY (Si/Al = 2.29) zeolites have been investigated by means of 129Xe NMR and isotherm measurements of adsorbed xenon. EuNaX and EuNaY samples with varied concentrations of Eu cations were subjected to diverse chemical and thermal treatments, namely dehydration, reduction, oxidation, and re-reduction. Thermal analyses of hydrated EuNaX and EuNaY samples indicate that both the structural stability and the saturation concentration of water increase with increasing Eu content. For dehydrated EuNaY zeolites, the Eu3+ cations tend to replace Na+ ions at S2 sites and tend to be located in framework supercages; similar behavior is found for Eu2+ ions after reduction. After subsequent oxidation, Eu3+ ions migrate from supercages into small sodalite and/or D6R cages; similar results were deduced for samples after re-reduction. In contrast to the behavior observed in EuNaY, Eu3+ ions tend to exchange for Na+ ions in the sodalite and/or D6R cages in dehydrated EuNaX zeolites, regardless of the thermal treatment; this behavior is ascribed to the existence of unlocalized S3 Na+ in EuNaX samples.  相似文献   

12.
本文主要采用~(129)Xe-NMR,并结合~(29)Si-与~(27)Al-NMR技术,探讨了在ZSM-5沸石上引入的锌及NaY沸石上引入的稀土阳离子的存在状况,高温焙烧过程对HZSM-5骨架结构的影响。  相似文献   

13.
Studies on Oxide Catalysts. XLIII. Thermoanalytic and Catalytic Investigations of Platinum-Containing Zeolites H-ZSM-5 By impregnation with H2PtCl6 from ethanolic solution, after reduction a higher metal dispersion in zeolites Pt/H-ZSM-5 is achieved than by impregnation from aqueous solution. Over such samples, bifunctional catalyzed reactions are more favoured than over zeolites Pt/H-ZSM-5 obtained by impregnation with H2PtCl6 from aqueous solution.  相似文献   

14.
The catalytic activity of ZSM-5 zeolites containing Mg cations in various concentrations has been studied in the alkylation of toluene by ethylene. The concentration of acid centers of different nature in these zeolites was characterized by IR spectroscopy of OH-groups and adsorbed CO. The state of Mg cations in the samples was studied by15N NMR of the adsorbed N2O. The increase of Mg content was shown to decrease both the concentration of non-protic acid sites of medium strength and the activity of samples, which is related to the increase of association degree of Mg cations in the zeolite.  相似文献   

15.
《Chemical physics letters》1987,137(4):341-344
It is shown that the chemical shifts characteristic of molecules trapped in zeolites (129Xe, and 13C for (CH3)4N+ ions) correlate directly with the surface curvature effects influencing the physisorption (dispersion) energy. Pore size is the determining parameter and other factors have negligible effect.  相似文献   

16.
MCM-41分子筛的合成及129Xe核磁共振的研究   总被引:5,自引:0,他引:5  
Purely siliceous MCM-41 with a narrow pore-size distribution, different pore size, high surface area was synthesized . As prepared, calcined and catalytically tested MCM-41 materials have been comprehensively characterized by N2 adsorption/desorption at 77K and 129Xe NMR. By adding mesitylene during the synthesis, the pore size of MCM-41 was enlarged to 5.2nm. The chemical shift in 129Xe NMR spectroscopy of adsorbed xenon indicates that the MCM-41 is one dimensional pore channels .  相似文献   

17.
Temperature and pressure dependences of the 129Xe NMR chemical shift and the signal intensity have been investigated using ZSM-5 as an adsorbent under routine conditions without using any high-pressure or especially high-temperature facilities. The use of a rigorously shielded system and a calibration sample for the signal intensity was found to be valuable to obtain reliable data about the chemical shift and the signal intensity. The 129Xe NMR data obtained between 0.05 and 1.5 atm and from 24 to 80 degrees C were analyzed based on the Dubinin-Radushkevich equation as well as the Langmuir type equation. In both analyses, chemical shift data succeeded only partially in providing the profile of adsorption, such as energetic aspects, surface area, saturated amount of Xe adsorption and specific parameters of 129Xe chemical shift. It was shown that the reliable total analysis was achieved when the chemical shift data were used together with the intensity data. Such an analysis of the chemical shift data, aided by the intensity data, will be useful in performing nano-material analysis on 129Xe NMR without invoking the traditional methodology of gravimetric or volumetric adsorption experiments.  相似文献   

18.
Model aqueous dispersions of polystyrene, poly(methyl methacrylate), poly(n-butyl acrylate) and a statistical copolymer poly(n-butyl acrylate-co-methyl methacrylate) were studied using xenon NMR spectroscopy. The 129Xe NMR spectra of these various latexes reveal qualitative and quantitative differences in the number of peaks and in their line widths and chemical shifts. Above the glass transition temperature, exchange between xenon sorbed in the particle core and free xenon outside the particles is fast on the 129Xe spectral time-scale and a single 129Xe signal is observed. At temperatures below the glass transition temperature, the exchange between sorbed and free xenon is slow on the 129Xe spectral time-scale and two 129Xe NMR signals can be observed. If the signal of sorbed 129Xe is observed, its chemical shift, line width and integral relative to the integral of free 129Xe can be used for the characterization of the particle core. The line width of free 129Xe provides the residence time of xenon outside the particles and can be used to determine the rate constant characterizing the kinetics of penetration of xenon in the particles. This rate constant emerges as promising parameter for the characterization of the polymer particle surface.  相似文献   

19.
采用固态离子交换法制备了一系列Fe/Al摩尔比为0.33的Fe/分子筛(ZSM-35,ZSM-5,beta和mordenite (丝光沸石))样品,并利用紫外-可见漫反射光谱、原位红外光谱和可见拉曼光谱以及瞬态应答实验考察了分子筛种类对N2O分解反应性能的影响.研究表明,经高温处理(HT)后分子筛的催化活性顺序为 Fe/ZSM-35 > Fe/beta > Fe/ZSM-5 > Fe/mordenite,与骨架外铝稳定的双核铁物种含量一致.这说明双核铁物种是高温处理后Fe/分子筛样品中N2O分解的活性位,而它的形成与分子筛种类密切相关.Fe/ZSM-35分子筛十元环孔道中相邻两个α位和八元环孔道中相邻两个β位都能稳定两个Fe(II)离子而形成能高效分解N2O的双核铁活性中心.Fe/beta和Fe/ZSM-5分子筛中只有落在相邻两个β位上的两个Fe(II)离子才能形成参与N2O分解的高活性的双铁活性中心.Fe/mordenite-HT分子筛上的铁物种绝大部分以孤立Fe离子的形式存在,因此其催化N2O分解反应活性很低.  相似文献   

20.
An approach for hyperpolarized 129Xe molecular sensors is explored using paramagnetic relaxation agents that can be deactivated upon chemical or enzymatic reaction with an analyte. Cryptophane encapsulated 129Xe within the vicinity of the paramagnetic center experiences fast relaxation that, through chemical exchange of xenon atoms between cage and solvent pool, causes accelerated hyperpolarized 129Xe signal decay in the dissolved phase. In this proof‐of‐concept work, the relaxivity of Gadolinium III‐DOTA on 129Xe in the solvent was increased eightfold through tethering of the paramagnetic molecule to a cryptophane cage. This potent relaxation agent can be ′turned off′ specifically for 129Xe through chemical reactions that spatially separate the GdIII centre from the attached cryptophane cage. Unlike 129Xe chemical shift based sensors, the new concept does not require high spectral resolution and may lead to a new generation of responsive contrast agents for molecular MRI.  相似文献   

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