Solvent-free dynamic nuclear polarization enhancements in organically modified mesoporous silica

High-field dynamic nuclear polarization is a powerful tool for the structural characterization of species on the surface of porous materials or nanoparticles. For these studies the main source of polarization are radical-containing solutions which are added by post-synthesis impregnation of the sample. Although this strategy is very efficient for a wide variety of materials, the presence of the solvent may influence the chemistry of functional species of interest. Here we address the development of a comprehensive strategy for solvent-free DNP enhanced NMR characterization of functional (target) species on the surface of mesoporous silica (SBA-15). The strategy includes the partial functionalization of the silica surface with Carboxy-Proxyl nitroxide radicals and target Fmoc-Glycine functional groups. As a proof of principle, we have observed for the first time DNP signal enhancements, using the solvent-free approach, for C-13{H-1} CPMAS signals corresponding to organic functionalities on the silica surface. DNP enhancements of up to 3.4 were observed for C-13{H-1} CPMAS, corresponding to an experimental time save of about 12 times. This observation opens the possibility for the DNP-NMR study of surface functional groups without the need of a solvent, allowing, for example, the characterization of catalytic reactions occurring on the surface of mesoporous systems of interest. For Si-29 with direct polarization NMR, up to 8-fold DNP enhancements were obtained. This Si-29 signal enhancement is considerably higher than the obtained with similar approaches reported in literature. Finally, from DNP enhancement profiles we conclude that cross-effect is probably the dominant polarization transfer mechanism.

Automated summary

High-field dynamic nuclear polarization is a powerful tool for structural characterization of species on porous materials or nanoparticles, with radical-containing solutions as the main source of polarization. This study presents a comprehensive strategy for solvent-free DNP enhanced NMR characterization of functional species on the surface of mesoporous silica, achieving DNP enhancements for C-13{H-1} CPMAS signals and Si-29 signals considerably higher than previous approaches, with the cross-effect identified as the dominant polarization transfer mechanism.