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Solid state NMR method for the determination of 3D zeolite framework/sorbate structures: H-1/Si-29 CP MAS NMR study of the high-loaded form of p-xylene in ZSM-5 and determination of the unknown structure of the low-loaded form

TitleSolid state NMR method for the determination of 3D zeolite framework/sorbate structures: H-1/Si-29 CP MAS NMR study of the high-loaded form of p-xylene in ZSM-5 and determination of the unknown structure of the low-loaded form
Publication TypeJournal Article
Year of Publication2005
AuthorsFyfe, CA, Diaz, AC, Grondey, H, Lewis, AR, Forster, H
JournalJournal of the American Chemical Society
Volume127
Pagination7543-7558
Date PublishedMay
Type of ArticleArticle
ISBN Number0002-7863
Keywords3-DIMENSIONAL BONDING CONNECTIVITIES, CROSS-POLARIZATION, CRYSTAL STRUCTURE-ANALYSIS, LATTICE, MAGIC-ANGLE, NATURAL-ABUNDANCE, NUCLEAR-MAGNETIC-RESONANCE, PROTON-ENHANCED NMR, SINGLE-CRYSTAL, SPINNING NMR, structures
Abstract

A general protocol is described for structure determinations of organic sorbate-zeolite complexes based on the selective, through-space, distance-dependent transfer of magnetization from protons in selectively deuterated organics to framework silicon nuclei. The method was developed using the known structure of the high-loaded ZSM-5/p-xylene complex containing p-xylene-d(6) or p-xylene-d(4). It was then applied to determine the unknown structure of the low-loaded ZSM-5/p-xylene complex using NMR alone. For the high-loaded complex improved data were obtained below 273 K, where slow motions and exchange processes of the p-xylene are eliminated. The general approach was validated by. the exact agreement of the experimental H-1-Si-29 CPMAS spectra obtained at a specific contact time and the complete 24-line spectra simulated using 1/T-CP vs M-2 correlations from only the six clearly resolved resonances. For the low-loaded complex the Si-29 resonances were assigned at 267 K, and variable contact time CP experiments were carried out between 243 and 173 K using the same specifically deuterated p-xylenes. All possible locations and orientations of the p-xylene guests were sampled, and those solutions that gave acceptable linear 1/T-CP vs M-2 correlations were selected. The optimum p-xylene location in this temperature range was determined to be in the channel intersection with the long molecular axis parallel to [0,1,0] (ring center fractional coordinates {-0.009, 0.250, 0.541}) with the ring plane oriented at an angle of 30 +/- 3 degrees about the crystallographic b axis. A subsequent single-crystal X-ray study confirmed this predicted structure.

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