J. Am. Chem. Soc. 1999, 121, 9611-9614
9611
Novel Mesoporous Materials with a Uniform Distribution of Organic
Groups and Inorganic Oxide in Their Frameworks
Shinji Inagaki,*,† Shiyou Guan,† Yoshiaki Fukushima,† Tetsu Ohsuna,‡ and
Osamu Terasaki§
Contribution from Toyota Central R&D Laboratories, Inc., Nagakute, Aichi 480-1192, Japan, the Institute
for Materials Research, Tohoku UniVersity, Sendai 980-8577, Japan, and the Department of Physics,
Graduate School of Science and CREST, JST, Tohoku UniVersity, Sendai 980-8578, Japan
ReceiVed May 19, 1999
Abstract: Novel organic-inorganic hybrid mesoporous materials have been synthesized, in which organic
and inorganic oxide moieties are distributed homogeneously at the molecular level in the framework, forming
a covalently bonded network. They are highly ordered at the mesoscale, with two- and three-dimensional
hexagonal symmetries and well-defined external morphologies. Nitrogen adsorption measurements show a
uniform pore-size distribution with pore diameters of 31 and 27 Å, and high surface areas of 750 and 1170
m2/g. The synthetic procedure to polymerize the organosilane monomer containing two trialkoxysilyl groups
in the presence of surfactant can be applied to the synthesis of a variety of highly ordered organic-inorganic
hybrid mesoporous materials.
Introduction
porous materials12,13 has attracted much attention because new
catalytic and adsorption functions can be introduced onto the
internal pore surfaces through the direct design of organic
functional groups. These organic-functionalized mesoporous
materials have a heterogeneous structure composed of an
inorganic main framework with an organic layer grafted onto
the framework. Generally, they exhibit poorer structural ordering
than nonfunctionalized inorganic mesoporous materials, evi-
denced by less-distinct X-ray diffraction patterns. On the other
hand, many kinds of amorphous inorganic oxides, containing
organic groups in their framework, have been derived by the
sol-gel polymerization method.14,15 Although these amorphous
materials have a homogeneous distribution of organic groups
and inorganic oxide in the framework,15 they have disordered
structures and scattered pore-size distributions.
Here we report the syntheses of novel organic-inorganic
hybrid mesoporous materials with a homogeneous distribution
of organic fragments and inorganic oxide within the framework,
rather than end-grafted, exhibiting a highly ordered structure
of uniform pores, which are quite different from the conventional
organic-functionalized ordered mesoporous materials and sol-
gel-derived porous hybrid organic-inorganic materials.
Since the discovery of ordered mesoporous silicates M41S1
and FSM-162 in 1992-93, a variety of ordered mesoporous
materials have been synthesized by a template method, using
supramolecular assembly of surfactant molecules. These materi-
als have a range of framework compositions, morphologies, and
pore structures. The framework composition has been studied
extensively, since that governs catalysis and adsorption proper-
ties. Mesoporous materials now include a variety of inorganic
materials, e.g., non-Si transition-metal oxides with high thermal
stability3 and metallic platinum.4 Recently, functionalization with
organic groups of ordered inorganic mesoporous5-11 and micro-
* To whom correspondence should be addressed. E-mail: inagaki@
mosk.tytlabs.co.jp.
† Toyota Central R&D Laboratories, Inc.
‡ Institute for Materials Research, Tohoku University.
§ Department of Physics, Graduate School of Science and CREST, JST,
Tohoku University.
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Experimental Section
Starting Material. The hybrid mesoporous materials can be
synthesized using organometallic compounds with two or more metal
alkoxyl groups as a starting material. In this study, we selected the
organosilane compound 1,2-bis(trimethoxysilyl)ethane (BTME) in
which an ethane (-CH2CH2-) fragment is attached to two trimethoxy-
silyl groups [Si(OCH3)3] at both ends. This organosilane compound
has been used for the synthesis of amorphous porous hybrid materials
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10.1021/ja9916658 CCC: $18.00 © 1999 American Chemical Society
Published on Web 10/04/1999