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Atomic Description of the Interface between Silica and Alumina in Aluminosilicates through Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy and First-Principles Calculations.

ABSTRACT: Despite the widespread use of amorphous aluminosilicates (ASA) in various industrial catalysts, the nature of the interface between silica and alumina and the atomic structure of the catalytically active sites are still subject to debate. Here, by the use of dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP SENS) and density functional theory (DFT) calculations, we show that on silica and alumina surfaces, molecular aluminum and silicon precursors are, respectively, preferentially grafted on sites that enable the formation of Al(IV) and Si(IV) interfacial sites. We also link the genesis of Brønsted acidity to the surface coverage of aluminum and silicon on silica and alumina, respectively.

SUBMITTER: Valla M

PROVIDER: S-EPMC4671101 | biostudies-literature | 2015 Aug

REPOSITORIES: biostudies-literature

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Atomic Description of the Interface between Silica and Alumina in Aluminosilicates through Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy and First-Principles Calculations.

Valla Maxence M Rossini Aaron J AJ Caillot Maxime M Chizallet Céline C Raybaud Pascal P Digne Mathieu M Chaumonnot Alexandra A Lesage Anne A Emsley Lyndon L van Bokhoven Jeroen A JA Copéret Christophe C

Journal of the American Chemical Society 20150817 33

Despite the widespread use of amorphous aluminosilicates (ASA) in various industrial catalysts, the nature of the interface between silica and alumina and the atomic structure of the catalytically active sites are still subject to debate. Here, by the use of dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP SENS) and density functional theory (DFT) calculations, we show that on silica and alumina surfaces, molecular aluminum and silicon precursors are, respectively, preferentia ...[more]

PMID: 26244620

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Project description:Isotopic enrichment of 29Si and DNP-enhanced NMR spectroscopy are combined to determine the detailed surface structure of a silicated alumina catalyst. The significant sensitivity enhancement provided by DNP is vital to the acquisition of multinuclear and multidimensional experiments that provide information on the atomic-level structure of the species present at the surface. Isotopic enrichment not only facilitates spectral acquisition, particularly given the low (1.5 wt %) Si loading, but also enables spectra with higher resolution than those acquired using DNP to be obtained. The unexpected similarity of conventional, CP, and DNP NMR spectra is attributed to the presence of adventitious surface water that forms a sufficiently dense 1H network at the silica surface so as to mediate efficient polarization transfer to all Si species regardless of their chemical nature. Spectra reveal the presence of Si-O-Si linkages at the surface (identified as Q4(3Al)-Q4(3Al)) and confirm that the anchoring of the surface overlayer with the alumina occurs through AlIV and AlV species only. This suggests the presence of Q3/Q4 Si at the surface affects the neighboring Al species, modifying the surface structure and making it less likely AlVI environments are in close spatial proximity. In contrast, Q1/Q2 species, bonded to the surface by fewer covalent bonds, have less of an effect on the surface, and more AlVI species are consequently found nearby. The combination of isotropic enrichment and DNP provides a definitive and fully quantitative description of the Si-modified alumina surface, and we demonstrate that almost one-third of the silicon at the surface is connected to another Si species, even at the low level of coverage used, lowering the propensity for the formation of Brønsted acid sites. This suggests that a variation in the synthetic procedure might be required to obtain a more even coverage for optimum performance. The work here will allow for more rigorous future investigations of structure-function relationships in these complex materials.

Dataset Information

Atomic Description of the Interface between Silica and Alumina in Aluminosilicates through Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy and First-Principles Calculations.

Publications

Atomic Description of the Interface between Silica and Alumina in Aluminosilicates through Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy and First-Principles Calculations.

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