NMR provides checklist of generic properties for atomic-scale models of periodic mesoporous silicas.
MCM-41 and SBA-15 silicas were studied by (29)Si solid-state NMR and (15)N NMR in the presence of (15)N-pyridine with the aim to formulate generic structural parameters that may be used as a checklist for atomic-scale structural models of this class of ordered mesoporous materials. High-quality MCM-41 silica constitutes quasi-ideal arrays of uniform-size pores with thin pore walls, while SBA-15 silica has thicker pore walls with framework and surface defects. The numbers of silanol (Q(3)) and silicate (Q(4)) groups were found to be in the ratio of about 1:3 for MCM-41 and about 1:4 for our SBA-15 materials. Combined with the earlier finding that the density of surface silanol groups is about three per nm(2) in MCM-41 (Shenderovich, et al. J. Phys. Chem. B 2003, 107, 11924) this allows us to discriminate between different atomic-scale models of these materials. Neither tridymite nor edingtonite meet both of these requirements. On the basis of the hexagonal pore shape model, the experimental Q(3):Q(4) ratio yields a wall thickness of about 0.95 nm for MCM-41 silica, corresponding to the width of ca. four silica tetrahedra. The arrangement of Q(3) groups at the silica surfaces was analyzed using postsynthesis surface functionalization. It was found that the number of covalent bonds to the surface formed by the functional reagents is affected by the surface morphology. It is concluded that for high-quality MCM-41 silicas the distance between neighboring surface silanol groups is greater than 0.5 nm. As a result, di- and tripodical reagents like (CH(3))(2)Si(OH)(2) and CH(3)Si(OH)(3) can form only one covalent bond to the surface. The residual hydroxyl groups of surface-bonded functional reagents either remain free or interact with other reagent molecules. Accordingly, the number of surface silanol groups at a given MCM-41 or SBA-15 silica may not decrease but increase after treatment with CH(3)Si(OH)(3) reagent. On the other hand, nearly all surface silanol groups could be functionalized when HN(Si(CH(3))(3))(2) was used.
Shenderovich
Ilja G
IG
Institut für Chemie und Biochemie, Freie Universität Berlin, Takustrasse 3, Berlin, D-14195, Germany. shender@chemie.fu-berlin.de
Mauder
Daniel
D
Akcakayiran
Dilek
D
Buntkowsky
Gerd
G
Limbach
Hans-Heinrich
HH
Findenegg
Gerhard H
GH
D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D008956:Models, Chemical; D008958:Models, Molecular; D016062:Porosity; D012821:Silanes / Q000737:chemistry; D012822:Silicon Dioxide / Q000737:chemistry*; D013499:Surface Properties
C509968:MCM-41; C509969:SBA-15; D012821:Silanes; C082343:silanol; D012822:Silicon Dioxide