abstract
Propylsulfonic acid-functionalized periodic mesoporous benzenesilica (Ph-PMO-SO3H, 1) has been shown to be exceptional solid catalysts in the acid-catalyzed condensation of indole on benzaldehyde. The reasons for this distinct behavior are so far not completely understood. Here, we present a study involving the combination of advanced high-resolution solid state magic-angle spinning (MAS) NMR characterization with the results of the application of hydrated and dehydrated 1 with different acid loadings in the acid-catalyzed condensation of indole on benzaldehyde attempting an explanation of the higher performance of these materials when compared with the conventional solid catalysts. H-1 MAS NMR investigations show the displacement of the propylsulfonic -SO3H protons to higher H-1 chemical shifts with increase of the sulfonic acid strength suggesting the formation of hydrogen bonds involving neighboring -SO3H groups. The acid strength of 1 is lowered by the presence of water. At low sulfonic acid loading the catalytic activity is surprisingly high and independent of the water presence. The 2D H-1-H-1 recoupling MAS NMR experiments indicate that the phenyl rings may protect the acidic sites against water solvation, thus affording a plausible explanation for the negligible effect of water on the catalytic activity of 1 with low acid loading. For a proton loading higher than 0.40 mmol g(-1), we observed a linear relationship between the catalyst TOF and the chemical shift value of the -SO3H proton, thus showing that solid H-1 NMR appears to be a convenient tool to predict the catalytic activity of 1 in water.
keywords
MOLECULAR-SCALE PERIODICITY; ORGANIC-REACTIONS; SILICA; WATER; ORGANOSILICAS; SBA-15; WALLS
subject category
Chemistry; Materials Science
authors
Siegel, R; Domingues, E; De Sousa, R; Jerome, F; Morais, CM; Bion, N; Ferreira, P; Mafra, L
our authors
Eddy Michael Pedro Domingues
Post-Doc Fellowship
Luís Mafra
Principal Researcher
Paula Celeste da Silva Ferreira
Coordinating Researcheracknowledgements
The authors thank FCT and FEDER (QREN-COMPETE) for funding the project PTDC/QUI-QUI/113678/2009 and FCT/CNRS exchange program. LM and RS acknowledge FCT for financing the Portuguese NMR Network (RNRMN), ref. REDE/1517/RMN/2005 and the project PTDC/QUI-QUI/100998/2008 and also the Post-Doc grant SFRH/BPD/44355/2008 (to R. S.). LM also greatly acknowledges the Campus de Excelencia Internacional Ad Futurum de la Universidad de Oviedo (FUTTALENT Program) and the Spanish Ministerio de Ciencia e Innovacion (MAT2010-15094).