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Organic-inorganic hybrid mesoporous silicas—— functionalization, pore size, and morphology control

SUNG SOO PARK, CHANG-SIK HA

National Research Laboratory of Nano-Information Materials, Department of Polymer Science and Engineering, Pusan National University, Busan 609-735, Korea

Received 1 November 2005; Revised 9 December 2005; Accepted 3 December 2005

ABSTRACT:T opological design of mesoporous silica materials, pore architecture, pore size, and morphology are currently major issues in areas such as catalytic conversion of bulky molecules, adsorp-tion, host–guest chemistry, etc. In this sense, we discuss the pore size-controlled mesostructure, frame-work functionalization, and morphology control of organic–inorganic hybrid mesoporous silicas by which we can improve the applicability of mesoporous materials. First, we explain that the sizes of hexagonal- and cubic-type pores in organic–inorganic hybrid mesoporous silicas are well controlled from 24.3 to 98.0? by the direct micelle-control method using an organosilica precursor and surfac-tants with different alkyl chain lengths or triblock copolymers as templates and swelling agents incorporated in the formed micelles. Second, we describe that organic–inorganic hybrid mesoporous materials with various functional groups form various external morphologies such as rod, cauli?ower,?lm, rope, spheroid, monolith, and ?ber shapes. Third, we discuss that transition metals (Ti and Ru)and rare-earth ions (Eu 3+and Tb 3+) are used to modify organic–inorganic hybrid mesoporous silica materials. Such hybrid mesoporous silica materials are expected to be applied as excellent catalysts for organic reactions, photocatalysis, optical devices, etc. ? 2006 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 6: 32–42; 2006: Published online in Wiley InterScience (https://www.sodocs.net/doc/a77316995.html,) DOI 10.1002/tcr.20070

Key words:organic–inorganic hybrid mesoporous silicas; periodic mesoporous organosilica;functionalization; pore size; morphology control

The Chemical Record, Vol. 6, 32–42 (2006)

?Correspondence to :Chang-Sik Ha; e-mail: csha@pusan.ac.kr

Contract grant sponsor: The National Research Laboratory Program of the Ministry of Science and Technology (MOST)/Korea Science and Engineering Foundation (KOSEF)]; Contract grant number: R11-2000-070-05004-0

Introduction

Periodic mesoporous materials have gained much interest in recent years because of the possibility of tailoring the pore structure, framework composition, and morphologies over a wide range.1Many potential applications arise from the poten-tial properties of these high surface area materials, including separation technology (chromatography, membranes, etc.),catalysis, nanoelectronics, sensors, and spatially de?ned host materials for substances or reactions.2The excitement began with the discovery of mesoporous silicates using ionic surfac-tants as templates for the assembly of inorganic frameworks 3(Fig. 1). Mesoporous silica materials with high levels of control

of the channel diameter between 20 and 100? have been pro-duced by ionic surfactants with various alkyl chain lengths and swelling agents.4,5Pore-enlarged mesoporous materials synthe-sized with nonionic poly(ethylene oxide) (PEO)–poly(propy-lene oxide) (PPO)–PEO block copolymers (EO–PO–EO) as

O r g a n i c –I n o r g a n i c H y b r i d M e s o p o r o u s S i l i c a s

templates have recently been shown to have a high degree of organization, high porosity, and large pore diameters (20–300?)6,7(Fig. 1). The structural features of the mesoporous materials—very high surface areas (>1000m 2g ?1), ordered nanopore structures, narrow pore size distributions, and hydroxyl-covered surfaces—make them excellent candidates for the development of new functional materials (Fig. 2).

Organic–Inorganic Hybrid Mesoporous Silica Materials

Preparation of the functionalized mesoporous silicas with organic moieties soon became a major topic of research because it offered a further possibility of tailoring the physical and

chemical properties of the porous materials. One important method of modifying the physical and chemical properties of mesoporous silicates has been the incorporation of organic components, either on the silicate surface, as part of the sili-cate wall, or trapped within the channels.8,9The organic func-tionalization of these solids permits the tuning of the surface properties (hydrophilicity, hydrophobicity, and binding to guest molecules); alteration of surface reactivity; protection of the surface from attack; and modi?cation of the bulk proper-ties (e.g., mechanical or optical properties) of the material.10We call these materials “hybrid mesoporous silica materials.”They are also often called by their more conventional name,“periodic mesoporous organosilicas (PMOs).” Organic moi-eties containing hybrid mesoporous silica materials facilitate the chemistry of the channels and provide new opportunities

T H E C H E M I C A L R E C O R D

for controlling the chemical, physical, mechanical, and dielec-tric properties of the materials.11–14

In this paper, we discuss pore size-controlled mesostruc-ture, framework functionalization, and morphology control of organic–inorganic hybrid mesoporous silicas by which we can advance the applicability of mesoporous materials.

Pore Size-Controlled Organic–Inorganic Hybrid Mesoporous Silica

The topological design of mesoporous silica materials, pore architecture, and pore size are currently major issues in areas such as catalytic conversion of bulky molecules, adsorption,and host–guest chemistry. Successful methods of enlarging

pore size include post-synthesis treatment 15and the use of sur-factants of different chain lengths,16triblock copolymers,6,17–20and alkyl ethylene oxide 21,22as templates or swelling agents 23–28in the formed micelles.

Among the variety of research subjects related to organic–inorganic hybrid mesoporous silicas, we have been mostly interested in pore size and morphology-control engi-neering for their future application versatility. The sizes of

hexagonal and cubic pores in the organic–inorganic hybrid mesoporous silicas can be controlled by a method of direct-micelle control and proper reaction conditions. In previous research, the pore diameter was controlled by adding an auxiliary hydrocarbon such as trimethylbenzene 29as well as by adjusting the initial pH of the system.30Based on our back-ground in polymer research, we wanted to use a polymeric swelling agent to enlarge the pore size of a well-known meso-porous silica (i.e., SBA [Santa Barbara]-15). First, we prepared organic–inorganic hybrid mesoporous SBA-15 containing a vinyl group called “vinyl–SBA-15”31and used polypropylene glycol (PPG) as a polymer-swelling agent.32Unlike low-mole-cular weight surfactants whose hydrophobic chain lengths can be ?nely adjusted, the length of the block segment in the amphiphilic triblock copolymer EO–PO–EO cannot be readily and subtly controlled without the use of delicate and painstaking synthetic skills. Furthermore, it is not easy to obtain commercially available block copolymers that have a range of de?ned block lengths. In this regard, PPG was expected to behave as an external swelling agent because it has the same structure as one of the comonomers of the parent tri-block copolymer and, thus, the addition of external PPG may play a role in controlling the length of the hydrophobic block segment. We used P123 (EO 20PO 70EO 20) as a template, HCl as the catalyst for hydrolytic condensation, and a mixture of tetraethoxysilane and triethoxyvinylsilane of a certain mole

O r g a n i c–I n o r g a n i c H y b r i d M e s o p o r o u s S i l i c a s ratio (Table 1) as co-precursors. Table 1 summarizes the tex-

tural properties of the solvent-extracted vinyl–SBA-15 samples

prepared using different amounts of PPG at pH 3.0. We can

see that the d spacing and pore sizes of the solvent-extracted

vinyl–SBA-15 samples also increase with the amount of PPG,

but there is not much difference in the thicknesses of their

walls. The control of pore size could be accomplished at low

concentrations of the swelling agent (below 2wt %) without

any major posttreatment procedure (e.g., separation of the

organic swelling agent, etc.).

Before 2003, there were no reports on large-pore PMOs

under acidic conditions, although there have been a few reports

on the success of large-pore PMOs under basic conditions. In

this regard, we reviewed previous literature on the use of

inorganic salts to improve hydrothermal stability, control

morphology, extend synthesis domains, and tailor framework

porosity during the formation of mesoporous materials via the

self-assembly interaction between surfactant headgroups and

inorganic species.33–37We found a simple method for the syn-

thesis of high-quality PMO materials with enlarged pores

using commercially available EO–PO–EO triblock copoly-

mers with two different PEO and PPO block lengths [P123

(EO20PO70EO20) and F127 (EO106PO70EO106)] as the template (designated as PMO–SBA-15 and PMO–SBA-16, respec-tively) under strongly acidic media in the presence of inorganic salts. PMO–SBA-15 was synthesized at 80°C for 24h in a Te?on-lined autoclave with a reactant molar composition of 1,2-bis(trimethoxysilyl)ethane (BTME)/P123/HCl/NaCl/ H2O=0.5:0.017:5.07:5.07:178.36Similarly, PMO–SBA-16 was synthesized with a reactant molar composition of BTME/F127/HCl/K2SO4/H2O=0.5:0.004:4.51:2.61: 116.37The template was removed using a solution of HCl–EtOH–water at 50°C. The small-angle X-ray scattering (SAXS) pattern of the solvent-extracted PMO–SBA-15 (Fig. 3C) shows three well-resolved peaks, which can be assigned to (100), (110), and (200) re?ections, respectively, of the two-dimensional hexagonal space group (p6mm).36Analogously, three well-resolved peaks at very small scattering angles are observed in the SAXS pattern of the solvent-extracted PMO–SBA-16 (Fig. 3D). These three peaks can be indexed as (110), (200), and (211) re?ections, respectively, corresponding to the body-centered cubic space group (Im3m).37T ransmis-sion electron microscopy (TEM) images shown in Figure 4A,B,D,E provide direct visualization of the PMO pore struc-tures. The TEM images of the solvent-extracted PMO–SBA-15 (Fig. 4A,B) further corroborate well-ordered hexagonal p6mm arrays of one-dimensional mesoporous channels. The pore diameter; Brunauer, Emmett, and T eller (BET) surface

Table 1.Molar ratios of precursors and textural properties for solvent-extracted vinyl–SBA-15 samples synthesized with polypropylene glycol (PPG) as a swelling agent (adapted with permission from reference [32]; copyright 2003, Elsevier).

Precursors

Average Wall (molar ratio)

d100Surface area Pore volume pore size a0[a]thickness[b] Symbol TEOS TEVS PPG(?)(m2g?1)(cm3g?1)(?)(?)(?)

E2P3H0.90.1080———93—

E2P3HP10.90.10.001876210.203810163

E2P3HP30.90.10.001886820.224110261

E2P3HP50.90.10.001906860.224210462

E2P3HP70.90.10.001925810.174310763

[a]a0=2d100/.

[b]Wall thickness=a0–average pore size.

TEOS=tetraethoxysilane, TEVS=triethoxyvinylsilane, PPG=polypropylene glycol.

Fig. 3.Small-angle X-ray scattering patterns of solvent-extracted samples:

(a) F127 blank, (b) P123 blank, (c) periodic mesoporous organosilica

(PMO)–SBA-15, and (d) PMO–SBA-16 (adapted with permission from ref-

Society of Chemistry).

T H E C H E M I C A L R E C O R D

area; and pore volume of the solvent-extracted PMO–SBA-15were 6.5nm, 737m 2g ?1, and 0.88cm 3g ?1, respectively. The TEM images of the solvent-extracted PMO–SBA-16 recorded along the (100) and (110) directions (Fig. 4D,E) clearly show a well-ordered domain of three-dimensional cubic mesostructures. This PMO material has a BET surface area of 989m 2g ?1, a pore volume of 0.65cm 3g ?1, a cell size of 9.8nm,and a window size of 5.5nm. It should be noted that the PMO materials synthesized under strongly acidic media in the pres-ence of inorganic salts have well-de?ned external morpholo-gies. The NaCl-assisted PMO–SBA-15 exhibits a rodlike morphology with a diameter of around 5μm, whereas the PMO–SBA-16 synthesized with K 2SO 4shows a cauli?ower-type morphology (Fig. 4C,F).

At present, particular interest is focused on large-pore PMO materials for the immobilization and encapsulation of large molecules. Thus, our work on PMO–SBA-15 and PMO–SBA-16 received a great deal of attention in the PMO ?eld around the world.

Next, we synthesized free-standing and oriented PMO ?lms with variable pore sizes at the air–water interface using cationic alkyltrimethylammonium surfactants [alkyl chain lengths from 12 to 18 carbon atoms, e.g.,CH 3(CH 2)11N(CH 3)3Br (C 12TA), CH 3(CH 2)15N(CH 3)3Br (C 16TA), and CH 3(CH 2)17N(CH 3)3Br) (C 18TA)], as structure-directing agents and 1,2-bis (triethoxysilyl)ethane (BTSE) as an organosilica precursor under basic conditions.38,39After hydrothermal reaction at 95°C for 8h, the pore diameter and BET surface area of C 12TA–PMO, C 16TA–PMO, and C 18TA–PMO ?lms (designated from the structure-directing agents with different alkyl chain lengths from 12 to 18 carbon atoms) were 24.3, 26.4, and 32.8?, and 890.3, 917.7, and 811.0m 2g ?1, respectively. The TEM images showed that the channels run parallel to the surfactant overlayer at the air–water interface, as shown in Figure 5A,C,E. The d spacing

A B E

C Fig. 4.T ransmission electron microscopy images of solvent-extracted periodic mesoporous organosilica (PMO)–SBA-15 recorded along the (A) (100) and (B) (110) directions, and solvent-extracted PMO–SBA-16 recorded along the (D) (100) and (E) (110) directions. Scanning electron microscopy images of as-synthesized (C) PMO–SBA-15 and (F) PMO–SBA-16 (adapted with per-mission from references [36] and [37]; copyright 2003, American Chemical Society and Royal Society of Chemistry).

Fig. 5.T ransmission electron microscopy images of as-synthesized [(A), (B)]C 12TA–, [(C), (D)] C 16TA–, and [(E), (F)] C 18TA–periodic mesoporous organosilica ?lms, showing [(A), (C), and (E)], a highly ordered periodic structure consistent with a hexagonal close-packed arrangement of channels running parallel to the surface of the ?lm, and [(B), (D), and (F)], a hexago-nal basal plane with a well-ordered hexagonal array (reprinted with permis-sion from reference [39]; copyright 2005, American Chemical Society).

O r g a n i c –I n o r g a n i c H y b r i d M e s o p o r o u s S i l i c a s

increases from 40.1 to 47.7? as the alkyl chains in the struc-ture-directing agent are longer. These peaks almost disappeared after calcination at 400°C for 2h in N 2without cracking or loss of mesostructure. On calcinating the ?lms, the intensities of the peaks increased and the anticipated contractions of the hexagonal ab -unit cell were observed due to the removal of the surfactant template from the channels, which is concomitant with the condensation of silanol (SiOH) groups in the channel walls.40

Synthesis and Morphogenesis of

Organic–Inorganic Hybrid Mesoporous Silica with Various Organic Functional Groups

The morphological control, as well as the texture of meso-porous materials, is extremely important in many applications.The morphology of materials often controls their function and utility. Mesoporous materials with morphologies including thin ?lms, monoliths, ?bers, spheres, hexagonal prisms,toroids, gyroids, ropes, discoids, spirals, dodecahedrons, and hollow tubular shapes have been synthesized.41–57

Recently, several researchers reported the synthesis of dodecahedrons, spheroids, and ?lms supported on a solid sub-

strate, and rod-shaped organic–inorganic hybrid mesoporous materials for practical applications.38,39,48–60

Organic–Inorganic Hybrid Mesoporous Silica with Bridged Organic Moiety in Frameworks

Mesoporous ?lms attract particular interest from a practical point of view because of their potential applications in elec-tronic and optical devices. Before our publication in 2004, all ?lms were prepared on solid substrates. Films supported on solid substrates, however, have several limitations. In particu-lar, few substrates have an atomically smooth surface and can sustain their structural integrity under the corrosive conditions of a synthesis, while at the same time facilitating oriented ?lm formation. T o surmount these problems, we synthesized, for the ?rst time, controllable pore size free-standing and oriented organic–inorganic hybrid mesoporous silica ?lm without a solid substrate at an air–water interface using cationic alkyltrimethylammonium surfactants (alkyl chain lengths from 12 to 18 carbon atoms) as structure-directing agents under basic conditions 38,39 (Fig. 6). The ?lms have a high-quality,well-ordered hexagonal mesostructure, with an organic moiety inside the channel wall. The ?lms are continuous over the entire bulk depending on the size of the reaction bottle. After

A D G H I

E F

B C

Fig. 6.Scanning electron microscopy images of as-synthesized, free-standing (A) C 12TA–, (D) C 16TA–, and (G)C 18TA–periodic mesoporous organosilica ?lms transferred from the air–water interface onto a copper grid, magni-?ed surface [(B), (E), and (H)], and edge part [(C), (F), and (I)] of samples (A), (D), and (G), respectively (reprinted with permission from reference [39]; copyright 2005, American Chemical Society).

T H E C H E M I C A L R E C O R D

a hydrothermal reaction at 95°C for 8h, C 12TA–PMO,C 16TA–PMO, and C 18TA–PMO ?lms grown at the air–water interface have a uniform thickness of ca. ～350, ～670, and ～400nm, respectively (Fig. 6C,F ,I). With reaction times from 30min to 24h, the C 18TA–PMO ?lms, with thicknesses from 180 to 740nm, have been grown at the air–water interface.Yang et al.41reported that the formation of a mesoporous silica ?lm involves collective interactions between silicate building blocks, micellar solution species, and a surfactant “hemi-micellar” overstructure localized at the air–water interface. The PMO ?lm growth is probably regulated by matching the

charge and geometry between micellar aggregates, and organosilica precursors at a surfactant-structured air–water interface, as suggested for a silica ?lm.

T o expand the potential applications of PMO, we syn-thesized high-quality, transparent, and oriented PMO monoliths through a solvent-evaporation process using a wide range of mole ratios of the following components:

0.17–0.56 BTSE :0.2 cetyltrimethylammonium chloride (CTACl):0–1.8×10?3HCl :0–80 EtOH :5–400 H 2O (Fig.7).61The mesoporous channels within the monolith samples were oriented parallel to the ?at external surface of the PMO monolith and possessed a hexagonal symmetry lattice (p 6mm ).The PMO monolith synthesized from a reactant composition of 0.35 BTSE :0.2 CTACl :1.8×10?6HCl :10 EtOH :10H 2O had a pore diameter and surface area—obtained from an N 2sorption isotherm—of 25.0? and 1231m 2g ?1, respectively.This PMO monolith possesses interesting optical properties,which will be discussed later.

Bifunctionalized Organic–Inorganic Hybrid Mesoporous Silica

The functionalization of hybrid mesoporous silicas was also one of the principal research interests in my laboratory, as well as in other laboratories for further applications.61–66The organic–bifunctionalized mesoporous silica materials were syn-thesized by co-condensation of BTSE with various trialkoxysi-lanes or bridged silanes such as bridged amino, isocyanate,1-[3-(trimethoxysilyl)propyl]urea (uredo), vinyl, ethyl, glyci-doxypropyl, and cyanopropyl units (Fig. 8) via a hydrothermal reaction at 80°C using mixed surfactant systems under basic conditions [cetyltrimethylammonium bromide (CTAB)/poly-yethylene glycol dodecyl ether =5.74, w/w; surfactant/6M NaOH =0.73, w/w; water/6M NaOH =12.4, w/w; BTSE =

Fig. 7.Photograph of an optically transparent as-synthesized periodic meso-porous organosilica monolith (diameter: 3cm; thickness: 0.16cm), which was prepared in the reactant volume of 10mL (reactant composition: 0.2cetyltrimethylammonium chloride :0.35 1,2-bis (triethoxysilyl)ethane :1.8×10?6HCl :10 EtOH :10 H 2O).

American Chemical Society).

O r g a n i c–I n o r g a n i c H y b r i d M e s o p o r o u s S i l i c a s

10mmol; co-organosilica precursor=10(1?x), x= 0.05–0.25 for PMO–3-cyanopropyltriethoxysilane (cps), PMO–amine, PMO–vinyl, PMO–ethyltriethoxysilane, PMO–(3-glycidoxypropyl)trimethoxysilane, PMO–3-(tri-ethoxysilyl)propyl isocyanate, and PMO–uredo.63The PMO materials have well-de?ned rope-based and ?ber-shaped mor-phologies (Fig. 9), as well as ordered pore structures. The pore arrangement in the functionalized PMOs revealed well-ordered hexagonal mesopores at certain loadings.

In contrast, spherical-shaped organic–inorganic hybrid mesoporous silica materials were synthesized using a sol–gel procedure by co-condensation of BTSE and [3-(cps) or bis[(3-trimethoxysilyl)propyl]amine (amine) under basic conditions (an aqueous ammonia solution), using CTAB as the structure-directing agent.64

Bifunctionalized Mesoporous Silica Materials for Improved Applications

For further speci?c applications of hybrid mesoporous silica materials, we performed research on the synthesis of organic–inorganic hybrid mesoporous silica incorporated with transition metals, rare-earth ions, or complexes of both. As previously stated, the general synthesis of organic–inorganic hybrid mesoporous materials can be useful for the incorpora-tion of transition metals. We synthesized PMOs modi?ed with transition metals (Ti and Ru), (Ti–PMO65and Ru–PMO66), in a framework by direct synthesis from co-condensation of BTSE and titanium isopropoxide or ruthenium chloride hydrate via hydrothermal reaction using CTAB as a template. The materials were produced with well-ordered mesostructures (Fig. 10). The transition metal–PMO materials can be used as excellent catalysts for organic reactions and photocatalysis, etc. As previously stated, PMO monoliths were produced based on the hydrolytic polycondensation of an alkoxysilane with a bridging organic group using surfactant-templated self-assembly. In addition, rare-earth ions (Eu3+and Tb3+) can easily be doped into the monoliths based on the synthesis method of transparent and highly ordered PMO monoliths. T ranspar-ent and as-synthesized rare-earth-ion (Eu3+and Tb3+)-doped PMO monoliths exhibited red and green emissions of the inherent Eu3+and Tb3+by UV irradiation (λ=254nm), respectively (Fig. 11). Due to the quantum-con?nement effect, the intensity of the emission was stronger than that of the rare-earth ions. We are now investigating detailed optical proper-ties of such doped PMOs.

Before conclusions are drawn, it should be noted that the framework of hybrid mesoporous materials is not limited to silica, but can be extended to a variety of inorganic materials as well as metals. We expect that many practical applications can be found for hybrid mesoporous materials for environ-mental, electro-optical, and biological systems, etc. within the next decade, regardless of the type of framework. Conclusions

The organic functionalization of mesoporous silicas permits the tuning of the surface properties (hydrophilicity, hydropho-bicity, and binding to guest molecules); alteration of surface reactivity; protection of the surface from attack; and modi?-cation of the bulk properties (e.g., mechanical or optical properties) of the material. We successfully controlled pore size

E F G

B C D

Fig. 9.Scanning electron microscopy images of (A) periodic mesoporous organosilica (PMO)–3-cyano-propyltriethoxysilane 15, (B) PMO–vinyl 15, (C) PMO–amine 15, (D) PMO–ethyltriethoxysilane 15, (E) PMO–(3-glycidoxypropyl)trimethoxysilane 15, (F) PMO–3-(triethoxysilyl)propyl isocyanate 15, and (G) PMO–1-[3-(trimethoxysilyl)propyl]urea 15 (adapted with permission from reference [63]; copyright 2005, American Chemical Society).

T H E C H E M I C A L R E C O R D

using an organosilica precursor and surfactants with different alkyl chain lengths, triblock copolymers as templates, and swelling agents incorporated in the formed micelles. Various organic functional groups containing organic–inorganic hybrid mesoporous materials were synthesized to form various external morphologies such as rod, cauli?ower, ?lm, rope,spheroid, monolith, and ?ber shapes. We synthesized transi-tion metals (Ti and Ru) and rare-earth ions (Eu 3+and Tb 3+) to

modify organic–inorganic hybrid mesoporous silica materials.Such materials are expected to be applied as excellent catalysts for organic reactions, photocatalysis, pH sensors, optical devices, etc.

We thank our past and present coworkers whose names

appear in the references for their invaluable contributions to this work. Financial support from the Center for Integrated Molecular Systems [Science Research Centers/Engineering Research Centers of the MOST/KOSEF; Grant number;R11-2000-070-05004-0], and the Brain Korea 21 Project is gratefully acknowledged.

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20 degrees

I n t e n s i t y (A U )

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110

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100100

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110110

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E u

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M O

l =

4 n m l =

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