comprehensive inorganic chemistry ii || mesoporous silica

Co

5.06 Mesoporous SilicaT Kimura, National Institute of Advanced Industrial Science and Technology (AIST), Nagoya, JapanK Kuroda, Waseda University, Tokyo, Japan

ã 2013 Elsevier Ltd. All rights reserved.

5.06.1 Introduction 1335.06.2 Preparation of Mesoporous Materials Using Surfactants 1335.06.3 Structural Characterization of Mesoporous Silica 1365.06.4 Morphological Control of Periodic Mesoporous Silica 1425.06.5 Applications Using Periodic Mesoporous Silica 1445.06.6 Conclusion 147References 149

5.06.1 Introduction

Porous materials are categorized on the basis of pore size. Meso-

porousmaterials possess a large number of pores ranging from 2

to 50 nm in size. Periodic mesostructures of various composi-

tions, including inorganic oxides and metal phosphates, are

successfully replicated by using amphiphilic organic molecules

possessing a self-assembling property. It is essential for the

preparation of periodic mesoporous materials to generate the

interactions between soluble inorganic species and amphiphilic

organic molecules.1,2 Amphiphilic organic molecules, whose

hydrophilic headgroups are interacted with inorganic species,

are self-assembled with gradual condensation of inorganic spe-

cies, being called as ‘cooperative organization’ for the formation

of periodic mesostructures.3,4 Materials with uniform meso-

pores can then be prepared after the removal of surfactant

assemblies. Such periodic mesoporous materials have been

expected as reaction vessels showing high selectivity for rela-

tively large organic molecules and thus increasingly and widely

investigated.

Through the investigations on the reactions between sur-

factants and layered polysilicate, the formation of mesostruc-

tured silica and importance of surfactant assemblies on the

formation of uniform mesopores were disclosed.5,6 Mobil

researchers reported the simple hydrothermal synthesis of

silica-based mesoporous materials reflecting the liquid-crystal

phases of surfactants.7,8 Usefulness of the self-assembling abil-

ity of surfactants for the mesostructural control of materials has

been indicated by beautiful transmission electron microscopic

(TEM) images showing periodic mesopore arrangements.

Representative TEM images of two-dimensional (2D) hexago-

nal mesoporous silica (MCM-41) with different pore diame-

ters are shown in Figure 1. Different periodic mesostructures

(cubic MCM-48, lamellar MCM-50, etc.) in silica were also

reported,9–19 and then, the surfactant-assisted synthesis of

materials and their applications has been surveyed all over

the world, and there have been a huge number of papers

describing compositional and morphological controls of

periodic mesoporous materials, which has resulted in many

strong expectations on practical applications not only due

to porous features for adsorbents and catalysts but also due

to electronic, magnetic, and optical properties for advanced

devices.

mprehensive Inorganic Chemistry II http://dx.doi.org/10.1016/B978-0-08-09777

5.06.2 Preparation of Mesoporous MaterialsUsing Surfactants

Initially, the preparative methods of mesoporous materials

using surfactants were mainly focused on silica-based

materials.20 Periodic mesoporous materials can generally be

prepared by the addition of an inorganic source to solutions

containing surfactants. When the kind of surfactants is appro-

priately selected as cationic, anionic, or nonionic one, the

interactions between inorganic and organic species are gener-

ated in solutions. Mesoporous silicas with a wide variety of

periodicities have been synthesized, and each material is

named by using three alphabetical codes, such as FSM, MCM,

and SBA. Representative periodic mesoporous silicas are sum-

marized in Figure 2. Actual synthetic procedures should be

referred to the contents of the original papers listed in this

section.

MCM-41, MCM-48, and MCM-50 are prepared using cat-

ionic alkyltrimethylammonium (CnTMA) surfactants.7,8 All

the mesostructures reflect the liquid-crystal phases of CnTMA

surfactants in the concentrated solutions. They are synthesized

by mixing silica and alumina sources with aqueous solutions

of surfactants under basic conditions. In addition, cage-type

mesoporous silicas are generally obtained using cationic sur-

factants with large headgroups, such as alkyltriethylammo-

nium (CnTEA) and gemini-type diammonium surfactants,

under acidic conditions.10,11 Formation of the mesostructures

is interpreted by using packing parameters (g¼V/a0l), which is

calculated by using the total volume of surfactant chains (V)

and kinetic length of hydrophobic alkyl chain (l) and effective

area of hydrophilic headgroup (a0) of the surfactant molecules.

Thus, judging from the molecular structures of surfactants

used, the structural ordering of formed mesoporous silica is

predictable to some extent. The validity of the aforementioned

explanation using the packing parameters is demonstrated for

some mesoporous silicas having sufficient structural informa-

tion. However, it is well known that the mesostructure varies

according to not only the packing parameter of surfactant but

also the reaction temperature, reaction time, pH of precursor

solution, and hydrothermal posttreatment. Accordingly, it is

crucial for the precise control of formed mesostructures to

take an account of the packing parameters affected due to the

presence of inorganic species interacting with hydrophilic

4-4.00507-6 133

http://dx.doi.org/10.1016/B978-0-08-097774-4.00507-6

134 Mesoporous Silica

headgroups of surfactant geometrically. In addition, the size

of the hydrophilic part is easily varied according to the con-

densation degree of silicate species, possibly leading to the

variation of resultant mesostructure. Phase transformation

between mesostructured silicas is a good example of the valid-

ity to consider the packing parameters containing attached

inorganic parts.3,21

Neutral and nonionic surfactants, such as alkylamine (CnA)

and poly(oxyethylene) alkyl ether (CnEOm), are also useful

for obtainingmesostructuredmaterials through hydrogen bond-

ing between silicate species and the headgroups of the sur-

factants.12–19 Mesostructural orderings are very low in the

beginning, but the ordering is improved according to the syn-

thetic conditions selected appropriately for controlling the inter-

actions from hydrogen bonding to ionic ones. Nonionic

10 nm

(c) (d)

(b)(a)

Figure 1 TEM images of MCM-41 with pore diameters of (a) 2.0nm,(b) 4.0nm, (c) 6.5nm, and (d) 10nm. Reproduced from Figure 2 in Beck,J. S.; Vartuli, J. C.; Roth, W. J.; Leonowicz, M. E.; Kresge, C. T.; Schmitt,K. D.; Chu, C. T.-W.; Olson, D. H.; Sheppard, E. W.; McCullen, S. B.;Higgins, J. B.; Schlenker, J. L. J. Am. Chem. Soc. 1992, 114, 10834.

Lamellar

KIT

FAMS-8

AMS-10

FDU-1SBA-16

SBA-3MCM-41

SBA-15

FSM-16 AMS-3

p6mm

SBA-8

AMS-9

FDU-11 FDU-13

KSW-2

c2mm

P42/mnm

P4/mmm Pmmm

Pn-3m

Im-3m

Fd-

AMCM

(KSW-L)

Figure 2 Mesostructures and abbreviations of periodic mesoporous silicas.

surfactants are very important because they are easily extracted

in solvents, recycled, and reused. In particular, CnEOm and

poly(oxyethylene)-block-poly(oxypropylene)-block-poly(oxyethy-

lene) triblock copolymer (EOnPOmEOn) are low cost, non-

toxic, and biodegradable. In those cases, because of the week

interactions between silicate species and the EO moieties, thick

silica walls surround mesopores, and therefore, mesoporous

silica, possessing enough thermal, hydrothermal, andmechanical

stabilities, is obtained. As the most special case, MSU-G synthe-

sized using gemini-type alkyl amines is ultrastable due to

extremely high condensation degree in the silicate frameworks

(Q4/Q3¼�7),16 being related to the relatively low specific

surface areas. As shown in Figure 3, vesicular MSU-G has an

intermediate mesostructure between lamellar (La) and lyotropic

L3 phase and thus would be formed by phase transition from the

La phase. The mesopore size of calcined MSU-G is controlled by

changing the alkyl chain lengthof the surfactants.However, itwas

reported that surfactant assembly-mediated porous silica was

already replicated by using lyotropic L3 phase of hexadecylpyr-

idinium chloride (C16PyCl).22 Interestingly, continuous pore size

control is possible in a wide range of 6–35 nm by changing

the volume fraction of solvent (water) without the removal of

C16PyCl (see Figure 3(c)).

Considering the interactions between inorganic and

organic species, it is impossible to synthesize mesoporous

silica using anionic surfactants because both silicate species

and surfactants are charged as anionic under both acidic and

basic conditions. Nevertheless, a synthetic strategy of periodic

mesoporous silica even using anionic surfactants has also been

developed by using another interaction of silicate species with

amino and ammonium groups in organosilanes as extra silica

sources.23,24 Because the possibility to use general anionic

surfactants is proposed for the preparation of periodic meso-

porous silica (AMS-n), amino acid-type surfactants are also

used, and the method is occasionally directed to the creation

of silica with modulated and chiral mesopore arrangements.25

Although it is explained that chiral and/or helical mesopores

are formed on the basis of the molecular structures with

-6

FDU-5

SBA-2 AMS-1

SBA-11

DU-2

AMS-2

SBA-1

SBA-6SBA-12 KIT-5

FDU-12

Fm-3mPm-3n

3m

P63/mmc

KSW-1

HMS KIT-1

MSU-n

Wormhole

Disorder

AMS-6

MCM-48

MS-5-50

Ia-3d

Intermediate L3 phase

Water

Silicate

Silicate

Water

TEOS

H2O

Lα phase

d d

d

MSU-G mesostructureGemini Lα

(a)

(c)(b)

∼− d

Figure 3 (a) Phase transition from La to L3 phases of surfactant and (b) related formation mechanism of mesostructured precursor of MCU-G ((a andb) reproduced from Figure 1 in Kim, S. S.; Zhang, W.; Pinnavaia, T. J. Science 1998, 282, 1302) with (c) schematic structure at the interface ofsilicate frameworks (reproduced from Figure 1 in McGrath, K. M.; Dabbs, D. M.; Yao, N.; Aksay, I. A.; Gruner, S. M. Science 1995, 269, 1242).

Mesoporous Silica 135

asymmetric carbons in headgroups of anionic surfactants, it is

proposed that cylindrical mesopores are finally twisted by

transition from 2D hexagonal to helical structures in order to

minimize the surface free energy. As a new formation mecha-

nism of chiral and/or helical mesopores, the curvature of the

helical mesopores is suggested to be defined by the increase of

the energy to organize the curved surfaces.26 On the basis of the

same route to obtain AMS-type mesoporous silica, 2D square

(p4mm) symmetry is also organized using anionic DNA with a

double-helix structure.27

The preparation of 2D hexagonal (MCM-41, FSM-16) and

3D cubic mesoporous silicas (MCM-48)7–9 was the first to

discuss the relation between molecular structures of surfactants

and mesostructures in various ways.10,11 It was reported that

3D hexagonal (P63/mcm) mesoporous silica (IBN-9) with a

tricontinuous mesopore network was obtained using a unique

surfactant, such as (S)-(1-tetradecylcarbomyl-2-phenylethyl)

dimethyethylammonium bromide.28 Silica pore walls in the

mesostructure, which follow a hexagonal minimal surface, are

analyzed mathematically as a mesophase between bicontinu-

ous mesopore network of MCM-48 and 2-D hexagonal meso-

pore arrangement of MCM-41.

The synthetic methods from layered polysilicates (mainly

kanemite composed of single silicate sheets) are exceptionally

interesting,5,6,9,29–33 and unusual mesoporous silica named as

KSW-2 can be synthesized using common CnTMA surfactants.32

Square-shape mesopores in the mesostructure (c2mm) has never

been found in periodic mesoporous silicas formed through

cooperative organization of surfactant molecules attaching to

silicate species. As shown in Figure 4, formed mesostructures

from layered polysilicates are simply understood by illustrating

possible surfactant assemblies in 2D limited spaces provided

from layered polysilicates.34 Lamellar, rodlike, and spherical

assemblies of surfactants are considered to be present in the

limited space. In general, lamellar phases are preferentially

formed by restriction of the sheet structure. However, it is

possible to accommodate rodlike micelles in mesostructures

(FSM-16 and KSW-2) formed under the conditions that allow

fragmentation and bending of silicate sheets, respectively. It is

quite difficult to wrap spherical micelles with flat silicate sheets,

leading to the formation of disordered mesopore arrangements.

Structural design from different layered polysilicates35–37 has

also been developed so far with incorporation of metal species

in the silicate frameworks.38–40 The periodicity of the original

layered polysilicates can be retained in the silicate frameworks by

surface modification of a mesostructured precursor of KSW-2-

type silica using organosilanes with appropriate molecular

structures.41 Previously synthesized mesoporous silicas are con-

structed by amorphous frameworks, being strongly related that

metal species doped in the mesoporous silicas do not generally

show high catalytic properties. Accordingly, KSW-2-based meso-

porous silica having periodic species in the silicate frameworks

has been investigated and expected as high-performance

catalysts.42

Facile pore size control of mesoporous silica is one of the

significant features of the synthetic method using surfactants,

which is quite important for applications of mesoporous silicas

as catalysts and catalytic supports. The pore diameter is variable

from 1.5 to 10 nm by changing alkyl chain length of surfac-

tants with auxiliary organic additives.7,8 In the synthesis using

EOmPOnEOm, it is reported that the pore diameter of periodic

mesoporous silica can be expanded up to 30 nm.18,19 Foamlike

mesoporous silica (the average pore diameter; 30 nm), named

as mesocellular foam (MCF), is also obtained from diluted

acidic aqueous solutions of (EO)20(PO)70(EO)20 (Pluronic

P123) containing trimethylbenzene (TMB) as an organic

additive.43 Without the addition of organic additives, silica

with relatively uniform pores (�100 nm) can be prepared in

a buffer solution (pH 5, 35 �C) containing Pluronic P123.44

Siliceous vesicles are regularly deposited, being similar to the

formation mechanism of diatoms (biosilica) under the mild

acidic conditions. This kind of researches on the formation of

Formation route of ordered phases

Sur

face

cur

vatu

re

C16−3−16

C16−5−16

C16TMA

C16TEA

C16−3−1

3D Hexagonal(P63Immc)

Lamellar2D hexagonal

Possible assemblies

Lamellar

(Intralayer condenzation) ‘Bending’

(Less condensed)

2D Orthorhombic(KSW-2)

Disordered phase

‘Transformation’(Fragmentation)

2D Hexagonal(FSM-16)

Within 2D Limited space

2D Hexagonal(Lamellar)

Lamellarcubic (la-3d)2D Hexagonal

Cubic (Pm-3n)

Formation route of disordered phases

Figure 4 Formation mechanisms of mesostructured materials derived by the reactions between layered polysilicates and alkylammonium-typesurfactants. Reproduced from Scheme 2 in Kimura, T.; Itoh, D.; Shigeno, T.; Kuroda, K. Bull. Chem. Soc. Jpn. 2004, 77, 585.


biosilica and the morphological variation is also important for

further understanding biomineralization in the presence of

peptides as structure-directing agents.45–49 Otherwise, poly

(isoprene)-block-poly(oxy ethylene) (PI-b-PEO)50 and ionic

poly(ethyl ethylene)-block-poly(styrene sulfonate)51,52 are uti-

lized for the synthesis of silica with extremely large pores. In

another way, spherical mesopores are preferentially formed

using poly(styrene)-block-poly(oxyethylene) (PS-b-PEO).53–57

Although inorganic–organic composite spheres are well orga-

nized, the spherical pores are isolated and/or connected

through micropores after complete removal of PS-b-PEO by

calcination. Accordingly, appropriate applications, excluding

catalysts and adsorbents, should be found on the basis of the

unique porous structures.

In the synthesis of periodic mesoporous silica using PI-b-

PEO, disassembly of the mesostructures was also investigated

as one of the interesting methods to fabricate new nanobuilding

units, as shown in Figure 5, which is beyond the common

discussion that nanosized composites of silicate species and

PI-b-PEO molecules are assembled for the formation of

mesostructures.58 Advanced synthetic methods of porous silica

using a wide variety of organic compounds have been proposed

for further structural controls. In the syntheses using common

triblock copolymers, the copolymers behave as amphiphilic

molecules because they consist of hydrophobic and hydrophilic

units. Then, such copolymers whose hydrophilic moieties are

interacted with silicate species are cooperatively self-assembled

with condensation of silicate species, affording precursors for

periodic mesoporous silica. In contrast, the utilization of hydro-

philic–hydrophilic diblock copolymers, such as poly

(ethylene oxide)-block-poly(methacrylic acid) (PEO-b-PMAA)

and poly(ethylene oxide)-block-poly(acrylic acid) (PEO-b-PAA),

was proposed as an ecofriendly synthetic route.59 In the pres-

ence of oligochitosan lactate as a weak acid source, PEO-b-PMAA

and PEO-b-PAA were self-assembled and dissociated reversibly

by changing pH only. Accordingly, they can be recovered and

reused for the synthesis ofmesoporous silica. Organic molecules

for the preparation of mesoporous silica have not been limited

to surfactants; supramolecular assemblies induced by p–p inter-

action of organic molecules are useful for obtaining periodic

mesoporous silica.60,61 The synthetic method is very important

for the arrangement and alignment controls of functional

organic molecules in silica matrix, rather than for the formation

of periodic structures.

The synthesis using oil-in-water emulsions stabilized by

surfactants led to the formation of hierarchically porous struc-

tures with pores larger than 50 nm that were surrounded by

surfactant-templated mesopores.62,63 Hollow nanospheres of

silica are also prepared using poly(diisopropylamino)ethyl

methacrylate-block-poly(dimethylamino)ethyl methacrylate

(PDPA-b-PDMA).64 Poly(N-isopropylacrylamide) (PNIPAAm)

was useful for the formation of micrometer-scaled silica hol-

low spheres, and ordered mesopores can be introduced in the

silica walls using C16TMABr.65 In this case, the hydrophilicity

and hydrophobicity of the product can easily be controlled by

the presence of thermosensitive PNIPAAm.

5.06.3 Structural Characterizationof Mesoporous Silica

x-Ray diffraction (XRD) measurements, TEM observations,

nitrogen adsorption measurements, etc., are useful for struc-

tural characterization of periodic mesoporous materials.

Figure 5 Assembly and disassembly of inorganic–organic hydride mesostructures. Reproduced from Figure 1 in Warren, S. C.; Disalvo, F. J.; Wiesner,U.; Nat. Mater. 2007, 6, 156.


Structural information of inorganic frameworks can be col-

lected by using several characterization techniques. Typical

analytical results by using XRD, TEM, and N2 sorption are

introduced here.

In the typical XRD patterns of periodic mesoporous mate-

rials, diffraction peaks related to the presence of mesostructural

orderings are observed in low 2y regions, while such diffraction

peaks are not observed in the scattering angles that are used for

characterization of conventional crystal structures. Such diffrac-

tion peaks are generally broadened with lowering in the mesos-

tructural orderings, and then, only one diffraction peak is

observed in low 2y regions for materials named as disordered

and wormhole-like mesoporous materials.12,13,17 However,

even when diffraction peaks seem to be broad, such materials

should be evaluated carefully, because a possibility to contain

several diffraction peaks located very closely in low 2y regions

cannot be excluded. Representative XRD patterns of periodic

mesoporous silicas are shown in Figures 6 and 7. Depending

on each mesostructural ordering, corresponding XRD patterns

are observed in low scattering angles.9,11,30,32,66,67 Indexes due

to each mesostructure are shown in the figure, which would be

helpful for structural assessment.

It is quite important for the determination of mesostructures

to utilize electron diffraction (ED) patterns. TEM is powerful for

direct observation of periodic mesostructures. Overlapping and

tilting of specimens may lead to misunderstanding of periodic

mesostructures, so it is necessary to observe a thin part of

samples and confirm the symmetry of ED patterns. The diffi-

culty to interpret TEM images comes from the dimensions of

periodic mesostructures, such as lamellar, 2D hexagonal, and

3D cubic ones. In each mesostructural ordering, representative

TEM images are shown in Figures 8–11. Striped patterns are

observed for lamellar materials and the repeated distances

should be consistent with d-spacings confirmed by XRD. Tilting

of the specimens would occasionally lead to disappearance of

striped patterns. Both striped patterns and honeycomb images

are observed for 2D hexagonal mesoporous materials, such as

MCM-41, FSM-16, and SBA-15. The distances of the striped

patterns are changed according to the directions of electron

beam, which should be paid attention for their understanding.

In addition, the presence of micropores is confirmed in the

silicate frameworks of SBA-15 by high-magnification TEM

observation.68 Mesostructures with 3D periodicities are more

complicated for the structural evaluation, and then, it should

be required to observe them from three different directions

at least.69–72 It is recommended to observe such materials

while referring to typical TEM images that are observed for

each mesostructure.

Considering the accumulation of cage-type mesopores,

simple understanding of 3D mesostructures has been tried by

using polyhedra as spherical cage-type mesopores with differ-

ent sizes.73,74 Because cubic close-packed (ccp, Fm-3m) and

hexagonal close-packed (hcp, P63/mmc) structures have the

same packing density, the difference in the mesostructural

orderings between Fm-3m and P63/mmc is only the stacking

direction of cage-type mesopores. They are just constructed by

‘a b c a b c packing along with [111]’ and ‘a b a b a b packing

along with [001],’ respectively. Other periodicities of cage-type

mesoporous silicas are also understood by using accumulation

of several polyhedra. Im-3m (body-centered cubic, bcc), Fm-3m,

and P63/mmc structures are close-packed by one kind of poly-

hedron. Pm-3n and Fd-3m structures are composed of two

kinds of polyhedra, while P42/mmm structure is constructed

by three kinds of polyhedra. A method to understand the

earlier mentioned periodic structures has been proposed

by illustration using 12- (512), 14- (51262), 15- (51263), and

16-hedra (51264). As identified by coloring in Figure 12,

the Pm-3n structure is constructed by four 12-hedra and six

0

Inte

nsity

(a.u

.)

2 4(0

01)

(002

)

(003

)

6 8 102q /°

1

Inte

nsity

(a.u

.)

2 3

(211

)(2

10)

(101

)(0

02)

(101

)

(110

)(1

03)

(112

)

(211

) (220

)(2

11)

(321

)(4

00)

(420

)(3

32)

(332

)(4

31)

(200

)

4 5 62q /°

1

Inte

nsity

(a.u

.)

2 3 4 5 62q /°

1

Inte

nsity

(a.u

.)

2 3 4 5 62q /°

SBA-1

Lamellar

SBA-2 MCM-48

FSM-16 KSW-2

0

Inte

nsity

(a.u

.)

2 4

(10)

(11)

(20)

(21)

6 8 102q /°

0

Inte

nsity

(a.u

.)

2 4

(11)

(20)

(31)(2

2)

6 8 102q /°

Figure 6 Low-angle XRD patterns of periodic mesoporous silica that can be prepared using alkyltrimethylammonium surfactants. (SBA-1, MCM-48)Reproduced from Figure 1 in Kruk, M.; Jaroniec, M.; Ryoo, R.; Kim, J. M. Chem. Mater. 1999, 11, 2568; (SBA-2) Reproduced from Figure 5 in Huo, Q.;Margolese, D. I.; Stucky, G. D. Chem. Mater. 1996, 8, 1147.

0.5 1.0 1.52q /° 2q /°

2.0 0.5

Inte

nsity

(a.u

.)

Inte

nsity

(a.u

.)

Inte

nsity

(a.u

.) (011

)

(002

)

(112

)

(022

)(0

13)

(11)

(10)

(20)

(21)

1.0 1.5 2.00.5 1.0

(200

)

(Fm-3m) (Im-3m) (p6mm)

(111

)

(220

)

(400

)(3

31, 4

20)

(422

)

1.52q /°

2.0

Figure 7 Low-angle XRD patterns of periodic mesoporous silica that can be prepared using EOmPOnEOm-type triblock copolymers. Reproduced fromFigure 2 in Kleitz, F.; Kim, T.-W.; Ryoo, R. Langmuir 2006, 22, 440.

[100]

100 nm

[110]

100 nm

Figure 8 Representative TEM images of 2D hexagonal (p6mm) mesoporous silica (SBA-15) along with [100] and [110] planes.


[111]

[100] [110]

50 nm

50 nm 50 nm

50 nm

[210]

240

004

004

004

440−

330−

040−

404−

Figure 9 Representative TEM images of cubic (Pm-3n) mesoporoussilica (SBA-6) along with several [hkl] planes. Reproduced from Figure 2in Sakamoto, Y.; Kaneda, M.; Terasaki, O.; Zhao, D. Y.; Kim, J. M.;Stucky, G.; Shin, H. J.; Ryoo, R. Nature 2000, 408, 449.

[100]

[111]

022−

220−

002

002

020

202−

50 nm

50 nm

50 nm

[110]

Figure 10 Representative TEM images of cubic (Im-3m) mesoporoussilica (SBA-16) along with several [hkl] planes. Reproduced from Figure 4in Sakamoto, Y.; Kaneda, M.; Terasaki, O.; Zhao, D. Y.; Kim, J. M.;Stucky, G.; Shin, H. J.; Ryoo, R. Nature 2000, 408, 449.

[100]

100 nm

100 nm

100 nm

004

004

220

040

220022

[111]

[110]

Figure 11 Representative TEM images of cubic (Ia-3d) mesoporoussilica along with [hkl] planes. Reproduced from Figure 1 in Sakamoto, Y.;Kim, T.-W.; Ryoo, R.; Terasaki, O. Angew. Chem., Int. Ed. 2004,43, 5231.


14-hedra, and the 12-hedra are located at the position of a bcc

structure. The Fd-3m structure is also constructed by 12- and

14-hedra, but similar sheets A, B, and C of only 12-hedra are

alternatively accumulated with another sheet a, b, and g com-

posed of 12- and 14-hedra, such as ‘A a B b C g packing along

with [111].’ Such accumulations of cage-type mesopores do

not occur so ideally, and then, it is difficult to obtain pure

phases of Pm-3n and Fd-3m structures. On the basis of the

detailed TEM observations of Pm-3n and Fd-3m mesoporous

silicas, an additional method to illustrate the defects in cage-

type mesoporous silica has been proposed by using unique

polyhedra, such as 13- and 15-hedra.74 In addition, it is

reported that the stacking faults and pore connections in

cage-type mesoporous silica (FUD-12) can be observed directly

by TEM.75 Thus, it is expected that the characterization tech-

niques will be further developed by using electron beams.

Scanning electron microscopy (SEM) is used for observa-

tion of morphologies of materials, but recent development of

the instruments for high-resolution SEM observation leads to

direct observation of mesopore arrangements.76 In addition to

the periodic arrangements of mesopores that can be observed

by TEM, their connectivity can also be observed by high-

resolution SEM. As shown in Figure 13, the SEM image of 2D

hexagonal SBA-15 shows that a part of 1D mesopores are

connected at the surfaces of particles,77 which reduces the

effective use of mesopores. In order to fully utilize all meso-

pores, further development of synthetic methods controlling

the connected parts of the mesopores may be needed. In this

sense, synthesis from layered polysilicates would be considered

as an ideal reaction system33 that does not contain the forma-

tion of new siloxane networks at the entrances of mesopores.

In addition to 2D hexagonal MCM-41 and SBA-15, porous

structures of cubic (Ia-3d) mesoporous silica (KIT-6) were

also observed by high-magnification SEM that provided the

images shown in Figure 14.78 The presence of bicontinuous

mesopores is proved clearly; the size of pores connected

between individual bicontinuous mesopore networks is varied

with the synthesis temperature.

N2 adsorption–desorption measurement is a general

method to evaluate porosity, such as size of mesopores. Spe-

cific surface area and pore volume are calculated using

A(B, C)

(a) (b)

(c) (d) (e)

A

C

B

A

α

β

γ

α (β,γ)

[112][111]

[110]

−−

−

[112][111]

[110]

−−

−[111]

[112]−−

[110]−

Figure 12 (a) Pm-3n73 and (b) Fd-3m structures illustrated by polyhedra and (c, d) the sheet structures composed of polyhedra and (e) of theaccumulated Fd-3m. Reproduced from Figures 2 and 3 in Han, L.; Sakamoto, Y.; Che, S.; Terasaki, O. Chem. Mater. 2009, 21, 223.

20 nm

Figure 13 High-resolution SEM image of 2D hexagonal (p6mm)mesoporous silica (SBA-15). Reproduced from Figure 1d in Che, S.;Lund, K.; Tatsumi, T.; Iijima, S.; Joo, S. H.; Ryoo, R.; Terasaki, O. Angew.Chem., Int. Ed. 2003, 42, 2182.


adsorption data and pore size distribution and shape of meso-

pores are derived on the basis of the adsorption–desorption

isotherm. Typical N2 sorption data of SBA-15 and SBA-16 are

shown in Figures 15. N2 molecules are initially adsorbed over

the surfaces of samples, and a multilayered state is obtained

with the increase in the relative pressure (P/P0) of N2. Capillary

condensation of N2 molecules then occurs at certain P/P0values depending on pore size. Adsorption and desorption

behaviors in pores smaller than 4 nm are almost consistent,

while hysteresis loops are observed for materials with meso-

pores larger than 4 nm. When mesopores are tubular (e.g., 1D

cylinders and wormhole-like mesopores), the adsorption iso-

therm due to capillary condensation was almost parallel to

hysteresis behavior in desorption.79 In cage-type mesopores,

spherical mesopores and pore windows to connect the meso-

pores are present in the porous structures, and then, the

desorption behavior is very different from those observed for

materials with cylindrical mesopores. Sudden decrease due to

pore windows smaller than spherical mesopores is observed in

the desorption blanch.80

It is necessary to decide the periodic structures of mesopor-

ous materials totally. For SBA-15, the 2D hexagonal structure is

verified by XRD and the presence of cylindrical mesopores is

confirmed by TEM and N2 sorption measurement.18,19 High-

resolution SEM observation gives us further information

whether mesopores are open or not. In addition, the presence

of micropores inside silicate frameworks is viewed in high-

magnification TEM images.68 The presence of such micropores

was supposed to be present on the basis of N2 sorption data at

low P/P0 regions. For example, such micropores in the silicate

frameworks of SBA-15 disappeared with the increase in tem-

peratures during calcination.79,81 In cage-type mesoporous sil-

ica (FDU-12, SBA-16), pore windows are reduced and finally

closed by elevating calcination temperatures, leading to the

transformation into silica containing regularly arranged and

isolated spherical pores.82 In the case of SBA-16, the presence

of the ordered mesostructures is confirmed with shrinkage

of the ordered mesostructure by XRD even when SBA-16

is calcined at higher temperatures, as shown in Figure 16.

In contrast, the N2 adsorption–desorption isotherm of

SBA-16 calcined above 900 �C showed a nonporous behavior,

though adequate adsorption of N2 with H2 hysteresis

50 nm

(a) (b)

50 nm

Figure 14 High-magnification SEM images of cubic (Ia-3d) mesoporous silica (KIT-6) with bicontinuous mesopore networks prepared at (a) 40 �C and(b) 100 �C. Reproduced from Figure 2 in Tuysuz, H.; Lehmann, C. W.; Bongard, H.; Tesche, B.; Schmidt, R.; Schuth, F. J. Am. Chem. Soc. 2008,130, 11510.

1000

800

(a) (b)

600

400

200

00.0 0.2 0.4 0.6

Desorption

Adsorption

0.8 1.0

P/P0

500

400

300

Desorption

Am

ount

ad

sorb

ed (c

m3

g−1 )

Am

ount

ad

sorb

ed (c

m3

g−1 )

Adsorption

200

100

00.0 0.2 0.4 0.6 0.8 1.0

P/P0

Figure 15 N2 adsorption–desorption isotherms of 2D hexagonal SBA-15 and cubic (Im-3m) SBA-16. (b) Reproduced from Figure 4d in Kleitz, F.;Czuryszkiewicz, T.; Solovyov, L. A.; Linden, M. Chem. Mater. 2006, 18, 5070.

Relative pressure0.80.60.40.0

0.4 0.6 0.8 1.0

q (nm−1)

1.2 1.4 1.6

0

100

Log(

inte

nsity

)

Am

ount

ad

sorb

ed (c

m3

STP

g−1

)

200

300

400 550 �C200

200

110

211

211

220

220

310

310

200211 220 310

700 �C800 �C

900 �C950 �C

550 �C

700 �C

800 �C

900 �C

950 �C

310211

200

200

110

211 220 310

0.2 1.0

Figure 16 Low-angle XRD patterns and N2 adsorption–desorption isotherms of SBA-16 calcined at different temperatures. Reproduced from Figure 3in Kruk, M.; Hui, C. M. J. Am. Chem. Soc. 2008, 130, 1528.



is observed for SBA-16 calcined up to 800 �C. The results revealthat cage-type mesopores are isolated completely by calcina-

tion at 950 �C.

5.06.4 Morphological Control of PeriodicMesoporous Silica

The development of morphological control, including fabrica-

tion of thin films, is very important for extending the applica-

tions of mesoporous silica. Precise control of hydrolysis and

condensation of tetramethoxysilane (TMOS) with the self-

assembly of CnTMA molecules are the first example to engineer

transparent mesoporous silica films,83 and afterward, many

papers on mesoporous silica films have been reported. Clear

precursor solutions, which are prepared under acidic conditions,

are spin-coated and dip-coated, easily affording thin films of

highly ordered mesoporous silica.84,85 The fabrication process

(Self-assembly)

(Precursor solution)

Sub

stra

te

(b)(a)

(Precursor solution)

Substrate

Closed vessel

Surfactant Silicate species

(Evaporation of solvent)

Figure 17 General synthetic routes of mesostructured silica films by(a) solgel and (b) hydrothermal methods.

(a)

(d) (e)

5 μm

50 nm

(b)

Figure 18 (a–c) SEM images ofmicropatternedmesoporous silica by using dparticles prepared by spray drying,92 and optical micrographs of mesoporous(g) by UV irradiation.94 Reproduced from (a,b) Figure 2 in Trau, M.; Yao, N.; KFigure 2 in Yang, P.; Deng, T.; Zhao, D.; Feng, P.; Pine, D.; Chmelka, B. F.; WhiteFan, H.; Stump, A.; Ward, T. L.; Rieker, T.; Brinker, C. J. Nature 1999, 398, 223Schunk, R.; Perez-Luna, V.; Lopez, G. P.; Brinker, C. J.Nature 2000, 405, 56. (g)Potter, K.; Potter, B. G., Jr.; Hurd, A. J.; Brinker, C. J. Science 2000, 290, 107.

of thin films by dip coating is shown in Figure 17. Because the

self-assembly of surfactantmolecules is induced during evapora-

tion of solvents (evaporation-induced self-assembly, EISA),

highly ordered silica–surfactant composite films can be obtained

when silicate species are not condensed so excessively.85 Hydro-

thermal synthesis ofmesoporous silica films was also reported at

the almost same time.86 When a substrate is placed at the inter-

face of acidic precursor solutions containing both CnTMA sur-

factant and silicate species, CnTMA–silica composites are

deposited at the surface of the substrate. In comparison with

the aforementioned solgel process, the hydrothermal fabrication

process of thin film is also illustrated in Figure 17. The

most distinguishing point of the hydrothermal process is a pos-

sibility to obtain self-standing mesoporous silica films at the

air–water interface.87

The synthetic method of mesoporous silica films through

solgel process is highly versatile. Inorganic–organic composite

coatings, such as nacre, are possible by molecular design of

surfactants.88 By using surfactants whose hydrophobic tail con-

taining a diacetylene unit, a chromatic variation was observed

by UV irradiation to the nanocomposite films.90 Mesoporous

silicas that are morphologically controlled by various methods

are summarized in Figure 18. Elastomeric relief stamp com-

posed of poly(dimethyl siloxane) (PDMS) was placed at the

substrate surface, and then, a clear precursor solution was

poured inside the relief by capillary force, leading to the facile

formation of micropatterned precursor films of mesoporous

silica.90,91 Spherical nanoparticles of mesoporous silica can be

prepared by spray drying of clear precursor solution.92 Direct

formation of nanocomposite spheres containing fluorescent

organic molecules, organic metal nanoparticles, and polymers

also occurred during the aerosol-assisted self-assembly process.

Micropatterning of ordered mesoporous silica was also extended

by micropen lithography and ink-jet printing.93 Micropatterning

(f) (g)

(c)

5 μm 5 μm

200 μm3 mm

1 mm

esigned PDMS stumps,90,91 (d) TEM image of spherical mesoporous silicasilica patterned by (e) micropen lithography and, (f) ink-jet printing 93 andim, E.; Xia, Y.; Whitesides, G. M.; Aksay, I. A. Nature 1997, 390, 674. (c)sides, G. M.; Stucky, G. D. Science 1998, 282, 2244. (d) Figure 2b in Lu, Y.;. (e,f) Figures 2a and 3b in Fan, H.; Lu, Y.; Stump, A.; Reed, S. T.; Baer, T.;Figure 2B in Doshi, D. A.; Huesing, N. K.; Lu, M.; Fan, H.; Lu, Y.; Simmons-


of mesoporous silica was possible by area-selective UV

irradiation.94 When UV light was irradiated over mesostructured

silica film through photomask, silicate frameworks in unmasked

regions were condensed by UV irradiation.94 Because silicate

frameworks in themasked region are not condensed, themasked

region is selectively leached for micropatterning. After micropat-

terning of mesostructured films of (EO)106(PO)70 (EO)106(Pluronic F127) containing an organic acid by lithography, the

micropatterning can be replicated with mesoporous silica by

infusion of silicon alkoxide using supercritical CO2 and the selec-

tive condensation.95 Freestanding mesoporous silica films are

obtained by slow evaporation of solvent (water) from suspen-

sions of nanocrystalline cellulose that organizes a tunable chiral

nematic structures.96

Alignment control of mesopores is also very interesting for

a variety of applications. As a main purpose, 1D mesopores in

2D hexagonal mesoporous silica are aligned over substrates.

As rodlike micelles of surfactants are oriented to flow direction,

it has been reported that 1D mesopores of 2D hexagonal

mesoporous silica are oriented to flow direction during

coating.97,98 However, the entire alignment of 1D mesopores

strongly depends on the coating conditions. Accordingly, it is

demanded for precise alignment of 1D mesopores. The align-

ment control in strong magnetic fields was also reported,99 but

the direction of 1D mesopores over the entire films has not

been controlled. The process by using powerful magnetic field

may not be a final goal for alignment control of mesoporous

silica. Although there is a possibility to orient 1D mesopores

over a particular crystal plane of a silicon substrate,100 the use

of polymer-coated substrates is proposed for the alignment

control of 1D mesopores. A fabrication process of fully aligned

mesoporous silica film by using polyimide is shown in

Figure 19.101 Polyimide is coated over a glass substrate and

the polymer chains are aligned to the same direction by a

rubbing treatment. When a mesostructured precursor film

was prepared over the polyimide-coated substrate, it was

Not aligned

Rubbing

10 μm

Polyimido coating

O

O O

NN

n

O

Substrate

Coating

Figure 19 Alignment control of tubular mesopores by using polyimide-coatKuroda, K. Chem. Mater. 1999, 11, 1609.

found that 1D mesopores were fully aligned perpendicular to

the rubbing direction. The orientation of the mesopores can be

proved by in-plane and out-of-plane XRD. The interaction

between the part of alkyl chains and polyimide chains is

important for the uniaxial alignment. It is reported that single

crystal-like 3D hexagonal (P63/mmc) mesoporous silica films

are formed by phase transition over a polyimide-coated

substrate.102 Photo alignment of 1D mesopores is also

reported.103 Monolayer of poly(vinyl alcohol) with photosen-

sitive azobenzene side chains was constructed by the Lang-

muir–Blodgett method over a substrate, and the azo groups

are oriented perpendicular to the substrate by UV irradiation.

Silica with 1D mesopores aligned parallel to the polymer-

coated substrate is obtained after covering with poly(di-n-

hexylsilane).

Vertical alignment of 1D mesopores is required to easily

locate nanomaterials in a hexagonal order. Although the syn-

thesis of mesoporous silica was carried out in strong magnetic

fields, a part of 1D mesopores were vertically aligned to a low

extent. The synthesis inside trenches is not expected for full

alignment of 1D mesopores because the planes parallel to a

substrate must be present in the trenches. The development of

the strategies to synthesize vertically aligned mesoporous sil-

icas is summarized in Figure 20. When mesoporous silica is

synthesized inside columnar pores of alumina membrane, 1D

mesopores are oriented parallel to the columnar pores (per-

pendicular to the substrate).104 However, the alignment

and orientation of 1Dmesopores are almost defined according

to the relation between diameter of the 1D cylinders of porous

anodic alumina (PAA) membranes and size of 1D

mesopores.105 Accordingly, to change the size of 1D meso-

pores within the confined space is not so simple. It was

reported that surfactant-assisted mesoporous silica was synthe-

sized inside the cylindrical pores of polycarbonate (PC)

membranes.106 It was found that 1D mesopores were aligned

inside cylinders of PC membranes through the introduction of

Aligned

Coating 20 nm

10 μm

ed substrate. Reproduced from Figures 2a, 2b, 7, 8b in Miyata, H.;

50 nm 200 nm

(b) (c)

(f)(e)(d)

(a)

50 nm

50 nm

20 nm20 nm

Figure 20 (a) Top and (b) side view by SEM observations of silica with aligned tubular mesopores in PAA membrane (reproduced from Figure 3b, 3c inYamaguchi, A.; Uejo, F.; Yoda, T.; Uchida, T.; Tanamura, Y.; Yamashita, T.; Teramae, N. Nat. Mater. 2004, 3, 337), (c) TEM image of silica with tubularmesopores aligned by shear flow in porous polycarbonate membrane (reproduced from Figure 2c in Yamauchi, Y.; Suzuki, N.; Kimura, T. Chem.Commun. 2009, 5689), (d) top and (e) side view by TEM observations of silica with electrochemically aligned tubular mesopores (reproduced fromFigure 1c, 1d in Walcarius, A.; Sibottier, E.; Etienne, M.; Ghanbaja, J. Nat. Mater. 2007, 6, 602), and (f) silica with vertically aligned mesopores that aregrown epitaxially over cubic mesoporous titania film (reproduced from Figures 1c, 2a in Richman, E. K.; Brezesinski, T.; Tolbert, S. H. Nat. Mater. 2008,7, 712).


clear precursor solution by aspiration.107 It is considered that

the alignment control of 1D mesopores is achieved in PC

membrane by shear flow because the mesostructured precursor

interacts with PC surfaces weakly rather than PAA surfaces.

Vertically aligned 1D mesopores are fabricated through

electrochemically assisted self-assembly,108 but the method

can only be adapted over conductive substrates. Although

perfect synthetic methods to align 1D mesopores vertically

have not been reported so far, a synthetic method developed

on the basis of the concept using epitaxial growth would be

one of the most flexible ones for obtaining vertically oriented

2D hexagonal mesoporous silica films.109 When a cubic meso-

porous titania film is synthesized over a substrate, a hexagonal

arrangement of mesopores is expected to be exposed on the

film surface. Then, 1D mesopores of a mesoporous silica film

can be vertically oriented when the lattice constants are con-

sistent with those of the titania film. A PAA membrane with

designed conical spaces was engineered electrochemically,

which was useful for standing of 1D mesopores because spher-

ical mesopores can be formed inside the conical spaces.110

Although rodlike micelles are strongly interacted with the sur-

faces of substrates and then reclined parallel to substrates,

discotic lyotropic liquid crystal of nonsurfactant supramolecu-

lar assemblies is useful for achieving vertical alignment of 1D

mesopores,111 which will be very helpful if the concept is

widely applicable for the synthesis of mesoporous silica films.

5.06.5 Applications Using Periodic MesoporousSilica

There have been enormous papers concerning the incorpora-

tion of different metal species in silicate frameworks that are

quite effective for the generation of unique functions.112,113

Functions coming from mesoporous structures themselves have

rarely been reported so far. Toward applications of ordered

mesoporous silica to catalysts, there have been several methods

to introducemetal species insidemesopores. In addition to imp-

regnation and ion exchange of metal species, metal complexes

are fixed at the surfaces of the silicate frameworks 114 and con-

structed inside ordered mesopores.115,116 It is also possible to

encapsulate metal species into micelles during the synthesis

of mesostructured precursors.117 As another case, metal nano-

particles are coated with ordered mesoporous silica, affording

core–shell mesoporous silica nanoparticles.118

Much attention was initially paid to the possibilities of

periodic mesoporous materials for applications in catalytic

reactions dealing with large organic molecules that cannot be

handled inside micropores as found for zeolites.112 Because

there have often been problems on low catalytic activities due

to amorphous silica-based frameworks, crystallization of silica-

based frameworks has strongly been demanded. On the other

hand, the presence of uniform mesopores is quite attractive as

particular nanovessels involving catalytic reactions. Here, sev-

eral reactions are described as successful examples due to shape

selectivity of uniform mesopores.

The synthesis of fine chemicals was firstly reported using

acidity of Al-FSM-16 in 1995.119 As shown in Figure 21, this

reaction is directed to the formation of a bulky organic mole-

cule (meso-tetraporphyrin) and optimal pore diameter for the

reaction was found in mesopore region. In the enrichment of

Taxol (a very small amount of Taxol is recovered as an anti-

tumor agent from the stem bark of western yew), in addition to

the shape selectivity by different mesopores of FSM-16, the

affinities of functional groups in Taxol to both silicate surfaces

and solvents are important for the separation.120 Although

H N

HNN

NHN Al-FSM-16

CH2Cl2 (RT) (reflux)p-chloranil

+

OH

Figure 21 Synthetic scheme of meso-tetraporphyrin.119

2.51.5

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.03.5 4.5

Pore diameter (nm)

Rea

ctio

n ra

te c

onst

ant

(ms−

1 g-

cat−

1 )

Figure 22 Variation of reaction rate constant relating acetalization ofcyclohexanone with methanol over siliceous MCM-41. Reproduced fromFigure 1 in Iwamoto, M.; Tanaka, Y.; Sawamura, N.; Namba, S. J. Am.Chem. Soc. 2003, 125, 13032.


periodic mesoporous silica does not show noticeable acidity

without incorporating other metal units, such as Al into silicate

frameworks, several reactions proceed over siliceous mesopore

surfaces. As shown in Figure 22, in acetalization of cyclohexa-

none with methanol over siliceous MCM-41, the reaction

rate constant varies depending on the mesopore size.121 Con-

sidering the small molecular size of cyclohexanone, this result

cannot be explained only by shape selectivity. Accordingly,

future elucidation of the peculiar phenomenon provided by

mesospaces is expected.

Inclusion chemistry in uniform mesopores has increa-

singly been developed since the discovery of ordered meso-

porous silica.122 Polymer syntheses in uniform mesopores

are a typical example. Conductive polyaniline filaments and

carbon wires were fabricated in 1D mesopores of MCM-41 by

oxidation and radical polymerizationwith subsequent pyrolysis,

respectively.123,124 Polymerization of ethylene in 2D hexagonal

mesoporous silica fiber containing a titanocene catalyst led to

the formation of crystalline linear polyethylene nanofibers.125

In these cases, the direction of mesochannels in mesoporous

silica fibers should be carefully characterized. Device appli-

cations using mesoporous silica films for photoelectric conver-

sion are summarized in Figure 23. Energy transfer from a

semiconducting polymer depending on the orientation of poly

[2-methoxy-5-(20-ethylhexyloxy)-1,4-phenylene vinylene]

(MEH-PPV) was investigated by using 1D mesopores.126 The

orientation of polymer chains is controlled by using a fully

aligned mesoporous silica film, and then, amplified spontane-

ous emission is reduced 20 times lower than that in random

polymer chains.127

When micropatterned mesostructured silica was fabricated

over a mesoporous silica film showing low reflectance, the

mesostructured silica film worked as waveguides, and then,

mirrorless lasing was observed by doping rhodamine 6G in

the mesostructured silica film.128 It was reported that the sep-

aration of biomolecules was possible through oriented 1D

mesopores in PAA membranes.104 Although rodlike mesopor-

ous silica fabricated inside columnar pores was detached from

PAA surfaces during the removal of surfactant molecules, there

was a possibility for complete separation of biomolecules

using mesoporous membranes in nanometer scale. Otherwise,

there have been a large number of papers describing encapsu-

lation of intelligent biomolecules inside uniform and periodic

mesopores.129 Pluronic P123-assisted mesoporous silica films

were aligned by dip coating and used as proton-conductive

films.98 For example, a gate effect was observed at the isoelec-

tric point of silica when hydrochloric acid was poured into the

film; proton was not transported below the isoelectric point.

Modification of silicate surfaces with organic functional

groups has widely been extended for applications using meso-

porous silica. When mercapto groups are anchored by silyla-

tion of MCM-41, toxic heavy metal ions, such as mercury, are

selectively adsorbed over the organic groups and removed

from the aqueous solutions.130 Partial organic modification

only at the entrance of mesopores is also possible by direct

modification of mesostructured silica.131,132 Mesostructured

precursor of MCM-41 is modified with an organosilane com-

pound possessing coumarin group is at the end of the organic

chain. Photosensitive mesoporous silica using reversible

dimerization of coumarin groups is obtained (open or closed

at the entrance of mesopores) after the extraction of surfactant

molecules accommodated inside the mesopores. The sche-

matic illustration of the reaction is shown in Figure 24.

Although this finding is actually an epoch-making study for

drug delivery system (DDS) applications, appropriate and real-

istic stimulation method should be discussed for practical

applications in human body because dimerization of couma-

rin molecules requires UV irradiation. In the synthesis of chiral

mesoporous silica prepared using anionic surfactants, in

4000

0.2

MeO n

O

0.4

0.6Ab

sorb

ance

(OD

)

0.8

1.2

1.4

1.6

1

450 500 550 600 650n = 3.5n∼1.15

n = 1.43

HCl or KCl

Mesoporous film

Excitation

To detector

Wavelength (nm)

V

Photoresist

(c)

100

10

1.0

0.110−8 10−6 10−4 10−2 100

[H+] (M)

Con

duc

tanc

e (n

S)

(d)

(a) (b)

⊥||

Figure 23 Device applications using mesoporous silica films due to (a) optical property of encapsulated semiconducting polymer (reprodued fromFigure 1a, 1c in Martini, I. B.; Craig, I. M.; Molenkamp, W. C.; Miyata, H.; Tolbert, S. H.; Schwartz, B. J. Nat. Nanotechnol. 2007, 2, 647), (b) mirrorlesslasing frommesostructured waveguides (reproduced from Figure 5 in Yang, P.; Wirnsberger, G.; Huang, H. C.; Cordero, S. R.; McGehee, M. D.; Scott, B.;Deng, T.; Whitesides, G. M.; Chmelka, B. F.; Buratto, S. K.; Stucky, G. D. Science 2000, 287, 465), and (c) proton conductivity (reproduced fromFigure 2a, 2c in Fan, R.; Huh, S.; Yan, R.; Arnold, J.; Yang, P. Nat. Mater. 2008, 7, 303).

250–260 nm

Storage

Coumarindimer

Photo irradiation>310 nm

Release

∼1.3 nm

∼2.62 nm

Figure 24 Conceptual scheme of photo-switched drug release by coumarin-modified MCM-41. Reproduced from Figure 15 in Mal, N. K.; Fujiwara, M.;Tanaka, Y.; Taguchi, T.; Matsukata, M. Chem. Mater. 2003, 15, 3385.


Extraction

CMS

Loading

B-DNA

TPPS

PPAS

Slower loading

L-CMS R-CMS

N+

N+

N+

N+

N+

N+

N+

−OOC

−OOC

−OOC

R

R

R

O

O

O

HN

HN

HN

N+

N+

−ooc−ooc

−ooc−oocNa

Na

−ooc

Faster loading

Figure 25 Mesoporous silica with the helical arrangement of surface organic groups and corresponding packing of functional organic molecules.Reproduced from Figure 1 in Qiu, H.; Inoue, Y.; Che, S. Angew. Chem., Int. Ed. 2009, 48, 3069.


addition to simple silica sources, such as silicon alkoxides,

organosilanes containing ammonium groups must be utilized

to generate interactions between anionic surfactant molecules

and frameworks.25 Although chiral mesoporous silica is

obtained after complete removal of organic fractions by calci-

nation, the ammonium groups can remain at the surfaces of

the silicate frameworks by extraction of surfactant molecules

only. As shown in Figure 25, when several kinds of anionic

functional molecules were adsorbed over the surfaces, the

chiral conformation of polymer chains, chiral stacking of por-

phyrin compound, and recognition of DNA chirality were

observed over the organic group remaining chiral mesoporous

silica,133 revealing a possibility of the imprinting of chiral

arrangement at the silicate surfaces.

A wide variety of particle morphologies have been reported as

the synthesis of orderedmesoporous silica.134–138 It is possible to

synthesize mesoporous silica nanoparticles by controlling con-

densation rate of silicate species and different strength of interac-

tions between silicate species and surfactantmolecules.139–143 The

fabrication ofmesoporous silica nanoparticles is a key technology

for realizing smooth diffusion of reactants and products during

catalytic reactions. Mesoporous silica nanoparticles with a high

density of amino groups144 and core–shell-type mesoporous sil-

ica nanoparticles were also prepared by controlled procedures.145

The synthetic method in cylindrical pores of PC membranes is

interesting to obtain mesoporous silica rods because PC mem-

branes and surfactant molecules can be eliminated at the same

time by calcination.106,107 There have been many attempts

to fabricate mesoporous silica using fibrous bacteria and sponge-

like polyurethane for incorporation of macrospaces inside

materials.146,147 The macrospaces are helpful for effective diffu-

sion in the research fields of catalysts and adsorbents.

DDS systems using mesoporous silica nanoparticles have

been increasingly investigated by utilizing organic modification

techniques.148 Photo-controlled reversible release of guest mol-

ecules was reported using selective anchoring of organic

groups.131,132 DNA and chemicals were successfully delivered

into plants using organically modified mesoporous silica

nanoparticles.149 The entrances of mesopores can be capped

with Au nanoparticles. The schematic reaction process is shown

in Figure 26. Mesoporous silica nanoparticles pass through cell

membranes by covering with DNA, transporting DNA and che-

micals. Visualization ofmesoporous silica nanoparticles in plant

cells was achieved by labelingwith fluorescent dyemolecules.149

Likewise, such visualization methods were widely applied in

various areas investigating cell viability extended by cell-directed

assembly of silica–lipid nanocomposites,150 diffusion of mole-

cules inside mesopores,151 diffusion of molecules during cata-

lytic reactions,152 distribution of organic functional groups by

silylation,153,154 and so on.

5.06.6 Conclusion

It is no doubt that a family of surfactant-assisted mesoporous

silica is extremely useful for applications because of fine tuning

of mesopores with compositional and morphological varia-

tions. Mesoporous silica-based materials applicable for cata-

lytic reactions can also be prepared through incorporation of

Freedplasmid

Cell membrane

Type-IV

Type-III

Gold

Gold

Gold

Gold

Gold Gold

Type-II

Type-IV

Plasmid DNA

Type-II

Type-II

Type-II

Type-IV

= Fluorescein

= β-oestradiol

Figure 26 Use of organically modified mesoporous silica nanospheres for plant cell internalization. Reproduced from Figure 1a in Torney, F.; Trewyn,B. G.; Lin, V. S.-Y.; Wang, K. Nat. Nanotechnol. 2007, 2, 295.


other metal units into silicate frameworks and fabrication of

metal nanoparticles inside mesopores.

Extension of applications utilizing mesoporous materials

can be expected, which is strongly related to further progress

of synthetic methods of mesoporous materials. Crystallization

of silica-based mesoporous materials is being realized steadily,

as for the cases of mesoporous zeolites by hard templating in a

replicated mesoporous carbon155 and by tiling of zeolite

nanocrystals.156 Another type of mesoporous zeolites prepared

in the presence of organosilane with long alkyl chain is also

known.157 Further design of the molecular structure of orga-

nosilane compounds leads to the successful synthesis of zeolite

nanosheets.158 Nevertheless, silicate frameworks basically lack

in rich functions; thus, combination of silica-based mesopor-

ous materials with organic functionalities will be extremely

promising hereafter. A number of periodic mesoporous silica

synthesized from only organosilanes with long alkyl chain

have been reported, and the molecular structures of both

inorganic units and organic groups can be designed.159,160 In

fact, the applications of mesoporous silica modified with orga-

nosilane coupling agents have been developed by using uni-

form mesopores and features arising from designable organic

functional groups. A rapid extension of studies on hybrid

mesoporous materials (periodic mesoporous organosilica,

PMO) prepared from organically bridged silane compounds

(bridged silsesquioxanes)161–165 also supports the significance

of the use of organically modified mesoporous silica. A wide

variety of organic groups can be embedded164,165 in the frame-

works, and conjugated organic groups are arranged in the

hybrid frameworks regularly under the appropriate synthetic

conditions.166,167 In PMO-type materials, uniform mesopores

that are defined by the exact size of surfactant assemblies are

utilized effectively. Artificial photosynthesis systems con-

structed inside mesopores of PMO is a typical example.168

When ordered mesoporous materials are chosen for ap-

plied studies, the following points should be considered:


understanding of functions directed to applications, the

essential/required role of silica-based frameworks, full utiliza-

tion of uniform mesospaces (if applicable), selection of appro-

priate morphologies, and so on. These key factors should

be further investigated to understand the total feature of meso-

porous silica. For related chapters in this Comprehensive,

we refer to Chapters 5.10 and 7.10.

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comprehensive inorganic chemistry ii || mesoporous silica

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