On 29Si NMR relaxation as a structural criterion for studying paramagnetic supermicroporous silica-based materials: silica-based materials incorporating Mn2+ ions into the silica matrix of SiO2-Al2O3-MnO

• Published in: Solid state nuclear magnetic resonance 2009-11, Vol.36 (3), p.129-136
• Main Authors: Bakhmutov, Vladimir I, Shpeizer, Boris G, Prosvirin, Andrey V, Dunbar, Kim R, Clearfield, Abraham
• Format: Article
• Language: English
• Subjects: Aluminum Oxide - chemistry; Isotopes; Magnetic Resonance Spectroscopy - methods; Manganese Compounds - chemistry; Oxides - chemistry; Porosity; Silicon; Silicon Dioxide - chemistry
• ISSN: 0926-2040; 1527-3326
• DOI: 10.1016/j.ssnmr.2009.08.002

Supermicroporous paramagnetic materials SiO(2)-Al(2)O(3)-MnO and SiO(2)-MnO with different manganese concentrations have been probed by solid-state (29)Si NMR and magnetic susceptibility measurements. The (29)Si T(1) and T(2) experiments, performed in static and spinning samples, have resulted in determination of electron relaxation times, providing, in turn, quantitative interpretations of (29)Si T(1) times in terms of distances Mn-Si. The NMR relaxation data have revealed (29)Si T(1) time distributions, which are close to Gaussian and observed as different T(1) values obtained in MAS NMR experiments for isotropic (29)Si resonances and their sidebands. Such (29)Si T(1) distributions, being a common phenomenon in paramagnetic silica-based materials, can be however masked by the bulk magnetic susceptibility (BMS) effects increasing with concentrations of paramagnetic centers. The presence of T(1) distributions, in itself, is not a criterion for incorporation of paramagnetic ions into the silica matrix or its surface. However, a quantitative analysis of the experimentally-observed short (29)Si T(1) components, based on the well-determined electron relaxation times, can provide such a criterion.