Periodic mesoporous organosilicas with organic groups inside the channel walls

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Surfactant-mediated synthesis methods have attracted much interest for the production of inorganic mesoporous materials, which can, on removal of the surfactant template, incorporate polymeric, organic, inorganic and organometallic ‘guests’ in their pores1,2. These materials—initially made of silica3,4,5, but now also available in the form of other oxides6,7,8,9, sulphides10,11, phosphates12 and metals13—could find application in fields ranging from catalysis, adsorption and sensing technology to nanoelectronics. The extension of surfactant-mediated synthesis to produce inorganic–organic hybrid material (that is, materials that contain organic groups as an integral part of their framework structure) promises access to an even wider range of application possibilities. Such hybrid materials have been produced in the form of amorphous silicates (xerogels) that indeed display unique properties different to those of the individual components14,15,16,17,18,19,20, but their random networks with broad pore-size distributions severely limit the shape and size selectivity of these materials. Mesoporous hybrid materials with periodic frameworks have been synthesized, but the organic groups are all terminally bonded to the pore surface, rather than incorporated into the pore walls21,22,23,24,25,26. Here we describe a periodic mesoporous organosilica containing bridge-bonded ethene groups directly integrated into the silica framework. We are able to solvent-extract and ion-exchange the surfactant templates to create a stable and periodic mesoporous ethenesilica with high surface area and ethene groups that are readily accessible for chemical reaction. Recent syntheses of similar periodic mesoporous organosilicas27,28 and the ability to incorporate a variety of bridging organic and organometallic species raise the prospect of being able to fuse organic synthesis and inorganic materials chemistry to generate new materials with interesting chemical, mechanical electronic, optical and magnetic properties.

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Figure 1: Powder X-ray diffraction patterns and TEM images of mesoporous ethenesilica. (See Figs 6–8 in Supplementary Information.) a, Powder X-ray diffraction (PXRD) patterns for as-synthesized samples containing different proportions of BTE and TEOS.
Figure 2: Differential thermogravimetric analysis (DTGA) of mesoporous ethenesilica.
Figure 3: Raman spectra of mesoporous ethenesilica.
Figure 4: Solid-state NMR spectra of mesoporous ethenesilica, BTE100. (See Figs 10, 11 in Supplementary Information.) a, 1H MAS NMR spectra (3 s recycle delay, 10 scans): trace A, as-synthesized; B, solvent-extracted; and C, ion-exchanged.


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We thank C. Y-Ishii for technical assistance with the synthesis and characterization of a wide range of periodic mesoporous organosilicas. This work was supported by the Natural Sciences and Engineering Research Council (NSERC) of Canada. M.J.M. was supported by an NSERC post-graduate scholarship (1995–99); G.A.O. thanks the Isaac Walton Killam Foundation for a research fellowship (1995–97).

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Correspondence to Geoffrey A. Ozin.

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Asefa, T., MacLachlan, M., Coombs, N. et al. Periodic mesoporous organosilicas with organic groups inside the channel walls. Nature 402, 867–871 (1999) doi:10.1038/47229

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