Tetrapropylammonium Occlusion in Nanoaggregates of Precursor of Silicalite-1 Zeolite Studied by 1H and 13C NMR
The dynamic behavior of tetrapropylammonium (TPA) cations in the clear precursor sols for silicalite synthesis has been investigated by 1H diffusion ordered spectroscopy (DOSY), T1, T2, and T1ρ 1H relaxation, as well as 1H→13C cross polarization (CP) nuclear magnetic resonance. The DOSY NMR experime...
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MDPI AG
2016-06-01
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| Series: | Inorganics |
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| Online Access: | http://www.mdpi.com/2304-6740/4/2/18 |
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| author | Mohamed Haouas David P. Petry Michael W. Anderson Francis Taulelle |
| author_facet | Mohamed Haouas David P. Petry Michael W. Anderson Francis Taulelle |
| author_sort | Mohamed Haouas |
| collection | DOAJ |
| description | The dynamic behavior of tetrapropylammonium (TPA) cations in the clear precursor sols for silicalite synthesis has been investigated by 1H diffusion ordered spectroscopy (DOSY), T1, T2, and T1ρ 1H relaxation, as well as 1H→13C cross polarization (CP) nuclear magnetic resonance. The DOSY NMR experiments showed the presence of strong solute–solvent interactions in concentrated sols, which are decreasing upon dilution. Similarities in dependence of diffusion coefficients with fractional power of the viscosity constant observed for nanoparticles, TPA cations and water led to the conclusion that they aggregate as anisotropic silicate-TPA particles. Relaxation studies as well as 1H→13C CP experiments provide information on dynamic properties of ethanol, water and TPA cations, which are function of silicate aggregates. The general tendency showed that the presence of silicate as oligomers and particles decreases the relaxation times, in particular T2 and T1ρH, as a consequence of involvement of these latter in ion-pairing interactions with water-solvated TPA molecules slowing down their mobility. Furthermore, from the 1H→13C CP dynamics curve profiles a change in the CP transfer regime was observed from fast (TCH << T1ρH) for solutions without silicates to moderate (TCH~T1ρH) when silicates are interacting with the TPA cations that may reflect the occlusion of TPA into flexible silicate hydrate aggregates. |
| first_indexed | 2024-04-12T04:51:10Z |
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| issn | 2304-6740 |
| language | English |
| last_indexed | 2024-04-12T04:51:10Z |
| publishDate | 2016-06-01 |
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| spelling | doaj.art-51528f361c3a4a7d9f338dc99d4d67dd2022-12-22T03:47:18ZengMDPI AGInorganics2304-67402016-06-01421810.3390/inorganics4020018inorganics4020018Tetrapropylammonium Occlusion in Nanoaggregates of Precursor of Silicalite-1 Zeolite Studied by 1H and 13C NMRMohamed Haouas0David P. Petry1Michael W. Anderson2Francis Taulelle3Institut Lavoisier de Versailles, Tectospin, UMR CNRS 8180, Université de Versailles Saint-Quentin-en-Yvelines, 78035 Versailles cedex, FranceInstitut Lavoisier de Versailles, Tectospin, UMR CNRS 8180, Université de Versailles Saint-Quentin-en-Yvelines, 78035 Versailles cedex, FranceCentre for Nanoporous Materials, School of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UKInstitut Lavoisier de Versailles, Tectospin, UMR CNRS 8180, Université de Versailles Saint-Quentin-en-Yvelines, 78035 Versailles cedex, FranceThe dynamic behavior of tetrapropylammonium (TPA) cations in the clear precursor sols for silicalite synthesis has been investigated by 1H diffusion ordered spectroscopy (DOSY), T1, T2, and T1ρ 1H relaxation, as well as 1H→13C cross polarization (CP) nuclear magnetic resonance. The DOSY NMR experiments showed the presence of strong solute–solvent interactions in concentrated sols, which are decreasing upon dilution. Similarities in dependence of diffusion coefficients with fractional power of the viscosity constant observed for nanoparticles, TPA cations and water led to the conclusion that they aggregate as anisotropic silicate-TPA particles. Relaxation studies as well as 1H→13C CP experiments provide information on dynamic properties of ethanol, water and TPA cations, which are function of silicate aggregates. The general tendency showed that the presence of silicate as oligomers and particles decreases the relaxation times, in particular T2 and T1ρH, as a consequence of involvement of these latter in ion-pairing interactions with water-solvated TPA molecules slowing down their mobility. Furthermore, from the 1H→13C CP dynamics curve profiles a change in the CP transfer regime was observed from fast (TCH << T1ρH) for solutions without silicates to moderate (TCH~T1ρH) when silicates are interacting with the TPA cations that may reflect the occlusion of TPA into flexible silicate hydrate aggregates.http://www.mdpi.com/2304-6740/4/2/18silicaliteNMR spectroscopydynamicsDOSY |
| spellingShingle | Mohamed Haouas David P. Petry Michael W. Anderson Francis Taulelle Tetrapropylammonium Occlusion in Nanoaggregates of Precursor of Silicalite-1 Zeolite Studied by 1H and 13C NMR Inorganics silicalite NMR spectroscopy dynamics DOSY |
| title | Tetrapropylammonium Occlusion in Nanoaggregates of Precursor of Silicalite-1 Zeolite Studied by 1H and 13C NMR |
| title_full | Tetrapropylammonium Occlusion in Nanoaggregates of Precursor of Silicalite-1 Zeolite Studied by 1H and 13C NMR |
| title_fullStr | Tetrapropylammonium Occlusion in Nanoaggregates of Precursor of Silicalite-1 Zeolite Studied by 1H and 13C NMR |
| title_full_unstemmed | Tetrapropylammonium Occlusion in Nanoaggregates of Precursor of Silicalite-1 Zeolite Studied by 1H and 13C NMR |
| title_short | Tetrapropylammonium Occlusion in Nanoaggregates of Precursor of Silicalite-1 Zeolite Studied by 1H and 13C NMR |
| title_sort | tetrapropylammonium occlusion in nanoaggregates of precursor of silicalite 1 zeolite studied by 1h and 13c nmr |
| topic | silicalite NMR spectroscopy dynamics DOSY |
| url | http://www.mdpi.com/2304-6740/4/2/18 |
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