NMR Relaxation Dispersion of Liquids Adsorbed on Modified Surfaces of SBA-15 Mesoporous Silica

• Published in: Journal of physical chemistry. C 2024-05, Vol.128 (21), p.8785-8796
• Main Authors: Gizatullin, Bulat, Mattea, Carlos, Stapf, Siegfried, Wissel, Till, Buntkowsky, Gerd
• Format: Article
• Language: English
• Subjects: C: Physical Properties of Materials and Interfaces
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/acs.jpcc.4c00645

The NMR relaxation dispersion of 1H and 2H nuclei in water and alkanes was studied in mesoporous SBA-15 silica in its native state and with modified internal surfaces. By comparison with silica gel of comparable characteristic pore size, a qualitative agreement of the relaxation dispersion was found. In the absence of detectable amounts of paramagnetic centers, intramolecular relaxation is approximated by the model of Reorientations Mediated by Translational Displacements (RMTD), which assumes rigid molecules diffusing along curved surfaces and experiencing long-term memory of their relative orientation due to their polarity. For all liquids, significant relaxation dispersion is found so that the vanishing polarity of alkanes does not allow the assumption of a negligible surface interaction. The difference in dispersion shape between 1H and 2H nuclei, relaxing by dipolar and quadrupolar mechanisms, respectively, allows the reconstruction of the intermolecular contribution to relaxation, which has not yet been studied systematically in porous media. A model based on the relative contributions of intra- and intermolecular interactions as well as hydrogen exchange with OH- and NH2-groups is presented.