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Mechanism of mesoporous silica formation. A time-resolved NMR and TEM study of silica-block copolymer aggregation

Flodström, Katarina LU ; Wennerström, Håkan LU and Alfredsson, Viveka LU (2004) In Langmuir 20(3). p.680-688
Abstract
The dynamics of the synthesis of a mesoporous silica material SBA-15 is followed using time-resolved in situ H-1 NMR and transmission electron microscopy (TEM). Block copolymer-silica particles of two-dimensional hexagonal symmetry evolve from an initially micellar solution. The synthesis was carried out with the block copolymer Pluronic P123 (EO20-PO70-EO20) at 35 degreesC and using tetramethyl orthosilicate as the silica precursor. By using TEM, we can image different stages during the evolution of the synthesis. Floes of spherical micelles held together by the polymerizing silica are observed prior to precipitation. With time, the structure of these floes evolves and the transition from spherical to cylindrical hexagonally packed... (More)
The dynamics of the synthesis of a mesoporous silica material SBA-15 is followed using time-resolved in situ H-1 NMR and transmission electron microscopy (TEM). Block copolymer-silica particles of two-dimensional hexagonal symmetry evolve from an initially micellar solution. The synthesis was carried out with the block copolymer Pluronic P123 (EO20-PO70-EO20) at 35 degreesC and using tetramethyl orthosilicate as the silica precursor. By using TEM, we can image different stages during the evolution of the synthesis. Floes of spherical micelles held together by the polymerizing silica are observed prior to precipitation. With time, the structure of these floes evolves and the transition from spherical to cylindrical hexagonally packed micelles can be monitored. The signal from the methyl protons of the PO part was recorded with H-1 NMR. One observes a continuous increase in the signal width but with distinct changes in the spectral characteristics occurring in narrow time intervals. The spectral changes can be attributed to structural changes of the self-assembled aggregates. The H-1 NMR and TEM studies reveal the same mechanism of formation. It is concluded that the aggregation is caused by a micelle-micelle attraction induced by oligomeric/polymeric silica that adsorbs to the EO palisade layer of the micelles and has the ability to bridge to another micelle. This adsorption also favors the formation of cylindrical aggregates relative to spherical micelles. The sequence of NMR and TEM observations can then be interpreted as the following sequence of events: (i) silicate adsorption on globular micelles possibly accompanied with some aggregate growth, (ii) the association of these globular micelles into floes, (iii) the precipitation of these floes, and (iv) micelle-micelle coalescence generating (semi)infinite cylinders that form the two-dimensional hexagonal packing. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Langmuir
volume
20
issue
3
pages
680 - 688
publisher
The American Chemical Society
external identifiers
  • wos:000188660600024
  • pmid:15773092
  • scopus:1242288170
ISSN
0743-7463
DOI
10.1021/la030173c
language
English
LU publication?
yes
id
c4855e4e-8e52-41f9-9b13-3df191ff2c07 (old id 153836)
date added to LUP
2007-07-11 11:46:04
date last changed
2017-11-12 03:23:18
@article{c4855e4e-8e52-41f9-9b13-3df191ff2c07,
  abstract     = {The dynamics of the synthesis of a mesoporous silica material SBA-15 is followed using time-resolved in situ H-1 NMR and transmission electron microscopy (TEM). Block copolymer-silica particles of two-dimensional hexagonal symmetry evolve from an initially micellar solution. The synthesis was carried out with the block copolymer Pluronic P123 (EO20-PO70-EO20) at 35 degreesC and using tetramethyl orthosilicate as the silica precursor. By using TEM, we can image different stages during the evolution of the synthesis. Floes of spherical micelles held together by the polymerizing silica are observed prior to precipitation. With time, the structure of these floes evolves and the transition from spherical to cylindrical hexagonally packed micelles can be monitored. The signal from the methyl protons of the PO part was recorded with H-1 NMR. One observes a continuous increase in the signal width but with distinct changes in the spectral characteristics occurring in narrow time intervals. The spectral changes can be attributed to structural changes of the self-assembled aggregates. The H-1 NMR and TEM studies reveal the same mechanism of formation. It is concluded that the aggregation is caused by a micelle-micelle attraction induced by oligomeric/polymeric silica that adsorbs to the EO palisade layer of the micelles and has the ability to bridge to another micelle. This adsorption also favors the formation of cylindrical aggregates relative to spherical micelles. The sequence of NMR and TEM observations can then be interpreted as the following sequence of events: (i) silicate adsorption on globular micelles possibly accompanied with some aggregate growth, (ii) the association of these globular micelles into floes, (iii) the precipitation of these floes, and (iv) micelle-micelle coalescence generating (semi)infinite cylinders that form the two-dimensional hexagonal packing.},
  author       = {Flodström, Katarina and Wennerström, Håkan and Alfredsson, Viveka},
  issn         = {0743-7463},
  language     = {eng},
  number       = {3},
  pages        = {680--688},
  publisher    = {The American Chemical Society},
  series       = {Langmuir},
  title        = {Mechanism of mesoporous silica formation. A time-resolved NMR and TEM study of silica-block copolymer aggregation},
  url          = {http://dx.doi.org/10.1021/la030173c},
  volume       = {20},
  year         = {2004},
}