1H/27Al TRAPDOR NMR studies on aluminum species in dealuminated zeolites.
(1998)
Journal - Solid state nuclear magnetic resonance (NETHERLANDS )
Abstract :
Aluminum species in several dealuminated zeolites (ultrastable HY, HZSM-5 and mordenite) were investigated in detail by means of the newly introduced 1H/27Al TRAPDOR method in combination with 27Al MAS NMR, and the quadrupole coupling constants (Q[CC]s) for aluminum atoms associated with these species were obtained. A signal at ca. 6.8 ppm, due to water molecules adsorbed on Lewis acid sites, was observed in the 1H MAS spectra for all the three zeolites. The TRAPDOR NMR provides direct evidence that there is a strong interaction between the adsorbed water molecules and the aluminum atoms of the Lewis-acid sites. The Q(CC) values for this aluminum species of 8.3, 6.7 and 11.3 MHz were determined from the TRAPDOR profiles for the ultrastable HY, HZSM-5 and mordenite zeolites, respectively. The Q(CC)s calculated from the TRAPDOR curves are usually larger than 10 MHz for both Bronsted-acid sites (SiOHAI) and non-framework aluminum species in the three zeolites. Three narrow peaks at 54, 30 and 0 ppm are separately superimposed on a broad hump in the 27Al MAS spectra of the three dehydrated zeolites, while the latter is associated with the 'NMR invisible' Al. The NMR experimental results suggest that the three kinds of aluminum species (non-framework aluminum species, Bronsted- and Lewis-acid sites) are all responsible for the resonance of the broad hump in dehydrated zeolites, which makes it difficult to explain the 27Al MAS spectra. Fortunately, the TRAPDOR NMR provides a direct method for individually studying different aluminum species with large Q(CC)s via their dipolar coupling to nearby proton nuclei.
| ISSN : | 0926-2040 |
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| Mesh Heading : | Aluminum Magnetic Resonance Spectroscopy Protons Zeolites |
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| Mesh Heading Relevant : | chemistry methods chemistry |
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Solid-state NMR investigation of acid sites in dealuminated HZSM-5 zeolite.
(1997)
Journal - Magnetic resonance imaging (UNITED STATES )
Abstract :
The acid sites and the hydration behaviors of dealuminated HZSM-5 zeolites (calcined at 550, 600, 650, and 700 degrees C) were characterized by high-resolution 1H MAS, 1H{27A1} spin-echo double resonance in combination with 27A1 MAS NMR. Apart from the usually observed peaks for dealuminated zeolite HZSM-5, a narrow plus a broad peak simultaneously appears at ca. 6.9 ppm in the 1H spectra and they exhibit different decay behavior in the 1H [27A1] double-resonance experiments. The existence of the former signal indicates that Lewis acid sites may'be formed in the zeolites after calcination. By means of the spin echo double resonance technique, we observed for the first time a previously unexpected narrow signal at 5.2 ppm, which resonates on the downfield side of Bronsted acid signal (4.3 ppm) and cannot be resolved in the 1H MAS spectra. This new signal is probably due to another kind of Bronsted acid site, locating in the small cages bounded by four- and five-membered rings. Three narrow peaks at 50 ppm, 30 ppm, and 0 ppm are superimposed on a very broad signal in the 27A1 MAS NMR spectra of dried HZSM-5. The intensity of the line at 50 ppm is significantly reduced compared with that of the rehydrated sample. 27A1 MAS NMR suggests that most part of the four-coordinated framework A1 turns into a intermediate case between four- and three-coordinated A1 after the dehydration and this process is reversible upon dehydration/rehydration. While some framework A1 atoms are transformed into three-coordinated A1 species and Lewis acid sites are, thus, generated in the dealuminated zeolites. For the signal at 30 ppm, the hydration leads to a dispersion in the chemical shift or the quadrupole interaction, which broadens its linewidth in hydrated samples.
| ISSN : | 0730-725X |
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| Mesh Heading Relevant : | Magnetic Resonance Spectroscopy Zeolites |
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1H MAS and 1H[23Na] double resonance NMR studies on the modification of surface hydroxyl groups of gamma-alumina by sodium.
(1997)
Journal - Solid state nuclear magnetic resonance (NETHERLANDS )
Abstract :
The modification of surface hydroxyl groups with sodium in a series of Na2CO3-gamma-Al2O3 catalysts was investigated as a function of both the Na2CO3 loading and the calcination temperature by means of 1H magic angle spinning (MAS) and 1H(23Na) spin-echo double resonance NMR techniques. The 1H NMR experiments revealed that sodium ions are homogeneously distributed over the alumina surface and closely coordinated with the surface hydroxyl groups. In the catalysts calcined at 250 degrees C, the acidic hydroxyl groups (with a chemical shift of 2.0 ppm) are preferentially associated with sodium ions at low Na2CO3 coverages (5 and 10%), while both the acidic and the basic (0 ppm) hydroxyl groups are accessible for sodium ions at high coverages (15 and 20%). The coordination causes a low-field shift of about 2 ppm in the 1H MAS spectra, and a broad signal at 4.5 ppm appears. It is interesting that the 4.5 ppm signal is completely suppressed in the 1H(23Na) MAS experiments, providing direct evidence that a strong interaction exists between adsorbed sodium ions and the surface hydroxyl groups. Increasing the calcination temperature to 450 degrees C results in preferential removal of the acidic hydroxyl groups, and only the most basic hydroxyl groups remain when the calcination temperature is raised to 600 degrees C. This is attributed to the formation of the coordinated species. [formula: see text] which enhances the acidity of the surface hydroxyl groups and prompts their dehydroxylation, especially at high calcination temperature. Correlation of the 1H MAS NMR results and catalytic activity measurements indicates that the basic hydroxyl groups are essential for the carbonyl sulfide hydrolysis reaction.
| ISSN : | 0926-2040 |
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| Mesh Heading : | Aluminum Oxide Magnetic Resonance Spectroscopy Sodium |
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| Mesh Heading Relevant : | chemistry pharmacology |
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Solid-state NMR studies of 1H spin diffusion in adsorbed organic molecules.
(1995)
Journal - Solid state nuclear magnetic resonance (NETHERLANDS )
Abstract :
1H spin diffusion times of toluene (MB) and tetrahydrofuran (THF) adsorbed on a series of porous solids (charcoal, SiO2 and Al2O3) were measured by a selective inversion technique. The experimental results show that they cover a wide range (from less than one millisecond to several hundreds of milliseconds). For all samples, a tri-exponential behavior was observed in the magnetization recovery processes of the negative peaks. This is attributed to the existence of the two different kinds of spin diffusion processes in addition to the T1 relaxation. One is assigned to the intermolecular spin diffusion between the surface acidic protons of the adsorbent and the organic molecules adsorbed on the solid surface, the other to the intramolecular spin diffusion of adsorbed molecules. Due to hydrogen bonding between the surface hydroxyl groups and the adsorbate, the intermolecular spin diffusion of THF adsorbed on various solids is more effective compared to that of adsorbed MB. In addition, the intermolecular 1H spin diffusion between charcoal and adsorbed THF molecules was confirmed by indirect measurement suggested by Tekely et al.
| ISSN : | 0926-2040 |
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| Mesh Heading : | Charcoal Chemistry, Physical Diffusion Furans Hydrogen Magnetic Resonance Spectroscopy Toluene methods analysis chemistry analysis chemistry |
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| Mesh Heading Relevant : | chemistry methods |
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Adsorption of Na+ onto gamma-alumina studied by solid-state 23Na and 27Al nuclear magnetic resonance spectroscopy.
(1995)
Journal - Solid state nuclear magnetic resonance (NETHERLANDS )
Abstract :
The adsorption of Na+ on gamma-alumina surfaces at four coverages of Na2CO3[5, 10, 15 and 20% w/w)] was characterized by solid-state 23Na and 27Al nuclear magnetic resonance (NMR) spectroscopy. The experimental results suggest that two distinct adsorbed species are present on the alumina surface: surface species and surface salts. At the lower coverages of Na2CO3 (5 and 10%), the surface species is predominant, in which the Na+ cations are associated with the oxygen atoms of gamma-alumina. Increasing the loading level to 15% results in the appearance of a second adsorbed species that is attributed to the surface salt, Na2CO3, deposited on the solid surface. Further adsorption of Na2CO3 leads to an increase in the amount of surface salt while the amount of surface species remains unchanged. 1H-27Al Cross-polarization magic angle spinning (CP-MAS) experiments give the evidence that some Na+ cations in the form of surface species are coordinated with the Brönsted acid sites of gamma-alumina. This may be the main driving force that improves appreciably the catalytic efficiency of an Na2CO3-Al2O3 catalyst.
| ISSN : | 0926-2040 |
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| Mesh Heading : | Adsorption Aluminum Sodium Isotopes |
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| Mesh Heading Relevant : | Aluminum Oxide Magnetic Resonance Spectroscopy Sodium |
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