Materials Transactions, Vol. 47, No. 8 (2006) pp.

2103 to 2105 #2006 The Japan Institute of Metals

RAPID PUBLICATION

Syntheses and Characterization of Bulky Mesoporous Silica MCM-41 by Hydrothermal Hot-Pressing Method
Hidezumi Nagata1; *1 , Mari Takimura2; *2 , Yuki Yamasaki3 and Atsushi Nakahira1; *3
1 2

Department of Materials Science, Graduate School of Engineering, Osaka Prefecture University, Sakai 599-8531, Japan Division of Chemistry and Materials Technology, Kyoto Institute of Technology, Kyoto 606-8585, Japan 3 Osaka Prefectural College of Technology, Neyagawa 572-857, Japan
Dense MCM-41 bulks were successfully synthesized by a hydrothermal hot-pressing (HHP) method. Adsorption/desorption behaviors were evaluated by nitrogen adsorption/desorption technique. Their microstructural features for dense MCM-41 bulks were observed by SEM. As a result, it was found that these dense MCM-41 bulks possessed a high surface area of over 1300 m2 /g and signicantly uniform mesopores. [doi:10.2320/matertrans.47.2103] (Received June 1, 2006; Accepted June 29, 2006; Published August 15, 2006) Keywords: mesoporous, silica, bulk, hydrothermal, hydrothermal hot-pressing

1.

Introduction

Mesoporous materials has nanosize pores whose size in the range 250 nm in structure has been expected for applications of adsorbent, catalyst carrier, separation membrane, xing agent for biomolecule and semiconductor cluster, functional electronics and photonics materials.13) Especially, mesoporous silica such as MCM and FSM had been studied early in the mesoporous materials.47) Mesoporous silica MCM and FSM are highly ordered mesoporous molecular sieve with a hexagonal array of uniform channels. They have a huge specic surface area more than 1000 m2 /g and range of relatively uniform pore size from 1 to 2 nm, although their structure itself is amorphous. In general, mesoporous silica is obtained as a powder after removing the template of surfactant. It has been numerous studied about mesoporous silica because of increase in expectations for new applications such as adsorbent and catalyst carrier. Its application was, however, restricted because these mesoporous silica are obtained as a powder only and was not able to obtain a solidied body. Thus, many researchers have tried to make powder consolidation and thin lm for expansion of applications of mesoporous silica.8,9) However, there is still a problem that mesoporous structure was not able to be retained for bulky or lmy mesoporous silica synthesized in conventional method, because they contain a lot of parts of amorphous and portion of mesopores structure were lled with amorphous phase. For example, thin lm synthesized by spin coating method can not obtain a large part of uniform mesoporous structures.8,9) Mesoporous structures in bulk body solidied with silicate binder were collapsed during the calcination and lled with amorphous phase due to the existence of residual amorphous. Therefore, practical use of mesoporous materials has not been achieved yet. Hence, the purpose of this study is to attempt powder consolidation of mesoporous material using HHP method developed by Yamasaki et al.10) HHP method is focused attention to production of sedimentary rock, and developed
*1Graduate *2Graduate

for the purpose of obtaining solidied substance like sedimentary rock in the laboratory. It is possible to densify oxide ceramics and glasses because of dissolution and deposition mechanism by means of increasing rate of dissolution and solubility of particles into water under hydrothermal condition.10) Nakahira et al. reported that densied and translucent bulky Y-Zeolite was synthesized using HHP.11) They showed that the dense bulks of mesoporous materials such as FSM and microporous materials such as zeolite were successfully synthesized through a HHP process. Here, the rst purpose of this study is to synthesize MCM powder and subsequently attempt consolidation of MCM powder by using HHP process. The second purpose is to evaluate microstructure and characteristics of bulk obtained by this HHP process. From these results, our aim is to clarity optimum synthetic condition for obtaining the bulk with connected mesopores as a whole. 2. Experimental Procedures

Student, Osaka Prefecture University Student, Kyoto Institute of Technology *3Corresponding author, E-mail: nakahira@mtr.osakafu-u.ac.jp

Mesoporous MCM-41 powder was prepared by the synthesis procedures by Mou and Lin.12) 0.060 g of sodium aluminate (54% Al2 O3 ) was dissolved in 3.0 g of water and mixed with 30.0 g of a 12% C17 TMABr (cetyltrimethylammonium bromide, 99%) aqueous solution. Then 5.3 g of sodium silicate (27% SiO2 and 14% NaOH) was added to the solution. After the resulting mixture was stirred for 10 min at room temperature, 6.0 g of 1.0 M H2 SO4 solution was added quickly. The gel mixture formed after this acidication was aged for 20 min and then was heated at 100 C for 48 hours in an autoclave. The solid product recovered by ltration was washed with deionized water, dried at ambient conditions, and some powders were calcined at in air for 6 hours to remove the template. Two types of MCM powders, MCM with calcination at 540 C and MCM without calcination, were prepared as starting materials. Figure 1 showed an autoclave for HHP in this study. Mixture of powder and water was heated at 110170 C with uniaxial pressing under 40 MPa and kept constant for 2 hours. The bulk prepared by HHP of as-synthesized powder was removed the template of surfactant by calcination at 540 C for 6 hours. Obtained bulks were identied by X-Ray

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H. Nagata, M. Takimura, Y. Yamasaki and A. Nakahira

Fig. 1

Autoclave for hydrothermal hot-pressing.

diraction (XRD, XD-D1w, Shimadzu) with Cu-K radiation. The samples were scanned from 1 to 40 (2). Surface and cross-section of samples were observed by eld emission scanning electron microscopy (FE-SEM, S-4500, Hitachi). Nitrogen adsorption/desorption isotherms and a specic surface area data were collected by an automatic gas adsorption measure apparatus (BELSORP-18PLUS-SPL, Japan BEL), and the technique for estimating specic surface area was used by Brunauer, Emmet and Teller (BET) method.13) Bulk density was evaluated with density measurement from their weight and the apparent volume. 3. Results and Discussion

Fig. 2 XRD patterns of (a) MCM-41 powder with surfactant before calcination, (b) bulk prepared by HHP of MCM-41 powder with surfactant, (c) HHPed sample-(b) bulk prepared by calcination, (d) bulk prepared by HHP of MCM without surfactant.

The eect of water contents and treatment temperature by HHP on the microstructure of sample for two MCM powders was examined. Under various synthetic conditions of HHP, MCM bulks were obtained. Strong MCM bulks obtained with 1040 mass% water content on HHP, although MCM bulk with more than 50 mass% water content could not be obtained. It is likely that the addition of excessive water content could not led to hydrothermal conditions. Thus, on HHP inhibited solidication of MCM, appropriate water contents range in HHP are existed for MCM. Properties of the bulk obtained by HHP were evaluated for MCM-41 powder with and without surfactant in the pores. Figure 2 shows the XRD patterns the samples prepared by HHP for two MCM powders. Sample (b) obtained by HHP using as-synthesized MCM powder is observed to be indexed on a hexagonal unit cell with distinct (100), (110), (200) peaks. And sample (c) obtained by calcination of sample (b) at 540 C showed the same hexagonal peaks as MCM-41 as a starting material. On the other hand, peaks of sample (d) obtained by HHP using synthesized MCM-41 powder not having surfactant in the pores was vanished, which are attributable to the presence of hexagonal unit cell. These results revealed that the pores of the bulk prepared by HHP was retained in the case of using as-synthesized MCM powder as a starting material. And the sample after calcination could have the mesopores. Because the bulk prepared by HHP using synthesized MCM powder without

surfactant in the pores was not able to be obtained, the mesopores on HHP was collapsed. As a result, it is believed that surfactant plays a role of a pillar for MCM bulk retained the mesopores on HHP process. Figure 3 shows the results of cross section of MCM bulk prepared by HHP. The bulk from as-synthesized powder had a smooth surface without pinholes. It was also found that the bulk had no huge voids. Hence it is obvious that MCM meso particles are successfully densied by HHP. The results of nitrogen adsorption/desorption measurement of the calcined bulk prepared by HHP using as-synthesized powder. The isotherms showed the curve attributable to the structure of the mesopores reported by IUPAC.14) Furthermore, the pore size distribution of MCM-41 raw powder and the calcined sample obtained by HHP using as-synthesized MCM-41 powder was examined. The results of the measurement are showed in Fig. 4. MCM bulks had the average pore size of 1.32 nm, although average pore size of MCM powder was 1.06 nm. A BET specic surface area for MCM powder and bulk was 1246 and 1339 m2 /g, respectively. It was thought that a little increasing of a specic surface area was attributable to dissolution and deposition of residual amorphous lled with the mesopores in HHP. Therefore, it was found that the increase in amounts of the mesopores was obtained by HHP. Figure 5 showed the values of bulk density with various conditions. The density of bulk prepared by uniaxial pressing was 9:7 102 kg/m3 , although bulks obtained by HHP before calcination had 20% higher bulk density compared to that of compaction. These results in this study showed that the bulk by HHP using mesoporous silica powder was

Syntheses and Characterization of Bulky Mesoporous Silica MCM-41 by Hydrothermal Hot-Pressing Method

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Fig. 3

SEM images of bulky product prepared by HHP at cross section (a) before calcination (b) after calcination.

Fig. 4 Pore size distributions of MCM-41 powder and bulk prepared by HHP after calcination, where Rp , Vp and dVp /dRp are pore radious, pore volume and pore distribution, respectively.

Fig. 5 Bulk density (kg/m3 ) of bulk prepared by hydrothermal hotpressing at 130 C with various conditions.

obtained for the rst time. These bulky mesoporous silica had dense micro structures with mesopores connected in the bulk as a whole. 4. Conclusion

We succeeded in obtaining the dense MCM-41 bulk with mesopores by HHP of as-synthesized MCM-41 powder with surfactant in the mesopores. After calcination for removal of the template, bulky MCM bodies with mesopores connected in the bulk were obtained and possessed a high specic surface area over 1300 m2 /g. It was seemed that the bulk could possess the mesopores because surfactant plays a role of like a pillar in HHP. Moreover, the bulk becomes more uniform pore size distribution and had a huge specic surface area more than 1300 m2 /g. Consequently, HHP method has some advantages in densication of various meso- and microporous materials and is possible for many materials to densify. REFERENCES
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