Engineered Complex Emulsion System: Toward Modulating The Pore Length and Morphological Architecture of Mesoporous Silicas
Engineered Complex Emulsion System: Toward Modulating The Pore Length and Morphological Architecture of Mesoporous Silicas
Engineered Complex Emulsion System: Toward Modulating The Pore Length and Morphological Architecture of Mesoporous Silicas
Engineered Complex Emulsion System: Toward Modulating the Pore Length and
Morphological Architecture of Mesoporous Silicas
He Zhang, Junming Sun, Ding Ma, Gisela Weinberg, Dang Sheng Su, and Xinhe Bao*
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian
116023, P. R. China, and Department of Inorganic Chemistry, Fritz-Haber Institute of the Max Planck Society,
Berlin D-14195, Germany
ReceiVed: September 5, 2006; In Final Form: October 18, 2006
In the complex alkane/P123/TEOS/H2O emulsion system, an emulsion engineering method to modulate pore
length and morphological architecture of mesoporous materials has been built. With fine tuning of the synthetic
parameters (e.g., the composition of the synthetic mixtures, temperature, stirring, etc.), a series of chemically
significant mesostructures (i.e., short-pore SBA-15 materials) with tunable pore length and morphological
architecture have been successfully constructed. The effects of alkane solubilizates on pore length and particle
morphology are discussed. The resulting short-pore materials would have potential applications in the fields
of adsorption/separation of biomolecules and inclusion chemistry of guest species, etc.
1. Introduction
During the past few decades, supermolecular self-assembly
has initiated a new era, in which the controlled bottom-up
construction of various functional porous materials has become
the interest of many researchers. As a promising support, the
construction of ordered mesoporous silicas is always one of the
research focuses in this newly developed field.1 Almost along
with the discovery of M41s,2 studies to control the morphology/
texture of these obtained mesoporous materials have begun,
aiming at getting good performance in the specific applications.
Due to the existence of complicated interactions among the
different species in the synthetic mixtures, a slight change in
synthetic parameters, such as temperature, shearing, components,
additives, etc., might alter the self-assembly behavior significantly. Not surprisingly, mesoporous materials with diverse
morphologies/textures resulted.3-13
The construction of chemically significant mesostructures has
long been one of the hottest issues in the supermolecular selfassembly age.6 Particularly, mesoporous materials with short
and open channels are extensively investigated because they
are more favorable for the mass transfer. For example, in the
adsorption experiments of biomolecules, due to the long, curved
mesostructures and densely packed secondary morphologies of
traditional SBA-15,14 the diffusion of large biomolecules (e.g.,
lysozyme) within their channels is suppressed, and thus, the
adsorption equilibrium was often reached on a time scale of
more than 24 h. If SBA-15 with straight pore channels and
separated rodlike morphologies was used, significant improvement in the diffusion of lysozyme molecules was observed, and
adsorption equilibrium time was shortened to a few hours.15
More recently, by using nanoscale large-pore mesoporous silicas,
the time scale for lysozyme adsorption equilibrium has been
further decreased to a few minutes.16 It was also demonstrated
that more accessible mesopores will result in a significant
increase in the amount of lysozyme adsorption. All these results
* Towhomcorrespondenceshouldbeaddressed.E-mail: xhbao@dicp.ac.cn.
Fax: 86-411-84694447.
Chinese Academy of Sciences.
Fritz-Haber Institute of the Max Planck Society.
Mesoporous Silicas
none
hexadecane
dodecane
decane
nonane
octane
heptane
hexane
pentane
315 ( 2
316 ( 2
313 ( 2
308 ( 2
300 ( 2
298 ( 2
293 ( 2
288 ( 2
285 ( 2
10.1
11.6
11.6
11.6
12.3
13.0
13.4
14.2
14.6
11.7
13.4
13.4
13.4
14.2
15.0
15.5
16.4
16.8
9.7
12.0
12.0
12.0
13.4
659
539
600
560
637
15.0
15.7
620
614
to mesoporous free-standing films and monoliths with shortpore SBA-15 units, have been successfully constructed. At the
same time, the effects of alkanes on pore length and particle
morphology are discussed, and possible mechanisms for the
formation of these short-pore materials are proposed. Significantly, most of these short-pore mesoporous silicas have shown
superiority against traditional SBA-15 in the fields of biomolecular adsorption, separation, and inclusion of guest species.16,26
2. Experimental Methods
2.1. Synthesis. As a typical synthesis procedure, 2.4 g of
EO20PO70EO20 (P123) was dissolved in 84 mL HCl solution
(1.20 M), followed by the addition of 0.027 g of NH4F. The
mixture was then stirred at a given temperature (from 285 to
315 K) until the solution became clear. Different alkanes (from
pentane to hexadecane) and TEOS were premixed and then
introduced into the solution under mechanical stirring (300360 rpm) (final P123/HCl/NH4F/H2O/TEOS/alkane molar ratios
) 1/261/1.8/11278/x/y; x ) 48-110, y ) 0-755). The above
mixture was stirred at the given temperature (Table 1) for 20 h,
and then transferred into an autoclave for further reaction at
373 K for 48 h. The products were collected by filtration, dried
in air, and calcined at 813 K for 5 h to remove the templates.
2.2. Characterization. SEM was done on the Hitachi S4800
field-emisson scanning electron microscope. The TEM images
were obtained with a Philips CM 200 transmission electron
microscope equipped with a CCD camera.
XRD patterns were collected on a Rigaku D/MAX 2400
diffractometer equipped with a Cu KR X-ray source operating
at 40 kV and 50 mA. The N2 adsorption-desorption isotherms
were recorded on an ASAP 2000 instrument.
3. Results
3.1. Effect of Alkane Solubilizates on the Pore Length of
SBA-15. Various alkanes from pentane to hexadecane (final
P123/HCl/NH4F/H2O/TEOS/alkane molar ratio ) 1/261/1.8/
11278/60/235) have been used in the synthesis. Figure 1 shows
SAXD patterns of the samples prepared with different alkanes.
It is clear that all the samples show four well-resolved peaks
that can be indexed as (100), (110), (200), (210) diffractions
associated with a 2-D hexagonal symmetry (p6mm), characteristic of highly ordered SBA-15 silicas. In addition, shift of the
(100) diffraction to a low angle with the decrease of alkane
chain length indicates the increase of SBA-15 unit cell.25 More
physical parameters of the obtained SBA-15 materials can be
found in Table 1.
Low magnified SEM images (Figure S1) show that the
morphological architectures of the obtained SBA-15 are different
depending on the alkane solubilizates used. Most importantly,
HRSEM images at higher magnification demonstrate that the
pore length of the obtained SBA-15 could be modulated by using
different alkanes (Figure 2). Without alkane, the obtained
materials have a bundle morphology, which consists of long
Figure 1. Small-angle X-ray diffraction patterns of the obtained SBA15 synthesized by using (a) hexane, (b) octane, (c) nonane, (d) dodecane,
(e) no alkane.
Zhang et al.
Figure 2. HRSEM images of the obtained SBA-15 mesoporous silicas resulting from the use of different alkanes as solubilizates: (a) no alkane,
(b) dodecane, (c) decane, (d) nonane, (e) octane, (f) hexane.
heptane to decane) in the synthesis has led to a series of shortpore SBA-15 with chemically significant morphologies.
3.2. Effect of the Amount of Decane on Particle Morphology. Keeping the TEOS/P123 molar ratio at 60, the effect of
the amount of decane on the particle morphology is also
investigated (final P123/HCl/NH4F/H2O/TEOS/decane molar
ratios ) 1/261/1.8/11278/60/x, x ) 0-755). Small-angle X-ray
diffraction patterns (Figure S2) of mesoporous silicas prepared
with different decane/P123 molar ratios show four well-resolved
Mesoporous Silicas
Figure 4. SEM images of mesoporous silicas prepared with a 60 TEOS/P123 molar ratio and different decane/P123 molar ratio: (a) 134, (b) 235,
(c, d) 755.
3.3. Effect of the Amount of TEOS on Particle Morphology. Fixing the decane/P123 molar ratio at 235, the effect of
the TEOS/P123 molar ratio on particle morphology is investigated (final P123/HCl/NH4F/H2O/TEOS/alkane molar ratios )
1/261/1.8/11278/y/235; y ) 48-110) in the current study. Figure
5 shows the small-angle X-ray diffraction patterns of the
samples. All the samples show diffraction peaks associated with
a 2-D hexagonal symmetry (p6mm), which is consistent with
the N2 adsorption results (Figure S4). For the sample with the
TEOS/ P123 molar ratio of 48, although it gives only two broad
peaks, it still possesses a well-ordered mesostructure, and fits a
minimum hexagonal mesostructure arrangement of ultrafine
particles, which could be verified by TEM experiments (Figure
6b).16 Corresponding SEM demonstrates a fiberlike bundle
morphology (Figure 6a). The TEM image in Figure 6b shows
the products are well-aligned nanofibers (50-75 nm), and each
of the fibers is indeed in a hexagonal arrangement. When the
TEOS/P123 molar ratio equals 60 (Scheme 1), uniform meso-
porous columns are obtained (Figure 1c). Furthermore, the crosssection TEM image (Figure S5) shows that the obtained
materials have hexagonal arrangements, which is consistent with
the SAXD results. Further increasing the molar ratio of TEOS
to P123 (e.g., 77, Scheme 1), interestingly, large amounts of
well-defined hexagonal-shaped SBA-15 slices are observed,
which are similar to the slice-shaped organosilicas29 (Figure 6c,
more pictures could be found in Figure S7). HRSEM images
(Figure S6) show that the ordered parallel pore channels are
vertical to the (100) planes of the slices, and the length of the
pore channels is about 200 nm, which is shorter than that of
the SBA-15 columns prepared with a TEOS/P123 molar ratio
of 60, while the dimension along the (100) plane has increased
to ca. 1 m. Microtome technique has also been used to confirm
the nanostructures of SBA-15 slices. Figure 6d gives the crosssection image vertical to the (100) planes. It can be clearly seen
that the ordered parallel channels are running along the [001]
direction. Another TEM image in Figure S6 shows the
hexagonal pore arrays of SBA-15 slices taken along the pore
direction ([001] direction). At the same time, it is observed that
the aspect ratio (the ratio of the particle dimension along the
parallel channels to that vertical to the parallel channels) of
obtained particles decreases with the increase of the TEOS/
P123 molar ratio.
Further increasing the amount of TEOS (e.g., TEOS/P123 )
110), large amounts of free-standing films (more than 50% in
yields) are observed in the obtained products (Figure 6e,f). The
formation of the films could be attributed to the oil droplets
directed macroscale growth in the synthetic mixtures. However,
HRSEM images (more images can be found in Figure S7) show
that the orientation of the pore channels is running parallel to
the surface of the films, which is different from that obtained
with CTAB surfactant.30 This difference is possibly related to
the different interactions between oil and surfactants. Besides
Zhang et al.
Figure 6. SEM images (a, c, e, f) and TEM images (b, d) of mesoporous silicas prepared with a 235 decane/P123 molar ratio but different
TEOS/P123 molar ratios: (a, b) 48, (c, d) 77, (e, f) 110.
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Figure 7. TEM images of mesoporous silicas prepared at 313 K with different alkanes: (a) dodecane, (b) heptane, (c) hexane.
Zhang et al.
Figure 8. SEM images of SBA-15 materials prepared in the absence of alkane solubilizates at a TEOS/P123 molar ratio of (a) 48, (b) 60, (c) 77.
Mesoporous Silicas
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