TY - JOUR
T1 - Direct synthesis, characterization and solid-state NMR spectroscopy of large-pore vinyl-functionalized cubic mesoporous silica FDU-12
AU - Kao, Hsien Ming
AU - Chang, Pai Ching
AU - Wu, Jyun Da
AU - Chiang, Anthony S.T.
AU - Lee, Chiou Hwang
N1 - Funding Information:
The financial support of this work by the National Science Council and Industrial Technology Research Center of Taiwan is gratefully acknowledged.
PY - 2006/12/29
Y1 - 2006/12/29
N2 - Large-pore vinyl-functionalized cubic mesoporous silica FDU-12 materials have been synthesized through the room temperature co-condensation of tetraethoxysilane (TEOS) and trimethoxyvinylsilane (TMVS) under acidic conditions templated with triblock copolymer Pluronic F127. The materials thus obtained were characterized by a variety of techniques including powder X-ray diffraction, multinuclear (1H, 13C, 29Si) solid-state NMR, two-dimensional (2D) 13C{1H} and 29Si{1H} HETCOR NMR, IR, thermogravimetric analysis, and nitrogen sorption measurements. Direct evidence of the presence of chemically attached vinyl moieties was provided by solid-state 1H, 29Si, and 13C NMR. The 2D 13C{1H} and 29Si{1H} HETCOR NMR experiments correlated the well-known vinyl 13C and 29Si T group resonances with their corresponding 1H NMR peak at 5.8 ppm, respectively. In particular, 29Si{1H} HETCOR NMR established that the vinyl groups were cross-linked to the mesoporous silica framework, instead of forming a separate phase. This provides direct molecular-level evidence for the co-condensation of TMVS and TEOS in the synthesis of mesoporous organosilicas. The vinyl functional groups were stable to at least up to 300 °C. The accessibility and the reactivity of the vinyl groups in the mesopores were demonstrated by the formation of a polymer/silica composite through in situ polymerization of vinyl groups with adsorbed methyl methacrylate monomer.
AB - Large-pore vinyl-functionalized cubic mesoporous silica FDU-12 materials have been synthesized through the room temperature co-condensation of tetraethoxysilane (TEOS) and trimethoxyvinylsilane (TMVS) under acidic conditions templated with triblock copolymer Pluronic F127. The materials thus obtained were characterized by a variety of techniques including powder X-ray diffraction, multinuclear (1H, 13C, 29Si) solid-state NMR, two-dimensional (2D) 13C{1H} and 29Si{1H} HETCOR NMR, IR, thermogravimetric analysis, and nitrogen sorption measurements. Direct evidence of the presence of chemically attached vinyl moieties was provided by solid-state 1H, 29Si, and 13C NMR. The 2D 13C{1H} and 29Si{1H} HETCOR NMR experiments correlated the well-known vinyl 13C and 29Si T group resonances with their corresponding 1H NMR peak at 5.8 ppm, respectively. In particular, 29Si{1H} HETCOR NMR established that the vinyl groups were cross-linked to the mesoporous silica framework, instead of forming a separate phase. This provides direct molecular-level evidence for the co-condensation of TMVS and TEOS in the synthesis of mesoporous organosilicas. The vinyl functional groups were stable to at least up to 300 °C. The accessibility and the reactivity of the vinyl groups in the mesopores were demonstrated by the formation of a polymer/silica composite through in situ polymerization of vinyl groups with adsorbed methyl methacrylate monomer.
KW - Large-pore mesoporous organosilica
KW - Two-dimensional HETCOR NMR
KW - Vinyl functionalization
UR - http://www.scopus.com/inward/record.url?scp=33751316758&partnerID=8YFLogxK
U2 - 10.1016/j.micromeso.2006.08.002
DO - 10.1016/j.micromeso.2006.08.002
M3 - 期刊論文
AN - SCOPUS:33751316758
SN - 1387-1811
VL - 97
SP - 9
EP - 20
JO - Microporous and Mesoporous Materials
JF - Microporous and Mesoporous Materials
IS - 1-3
ER -