Fe-MCM-41의 제조, 물성조사 및 촉매적 응용 연구

Synthesis, Characterization, and Catalytic Applications of Fe-MCM-41

  • 윤상순 (인하대학교 공과대학 화학공학과) ;
  • 최정식 (인하대학교 공과대학 화학공학과) ;
  • 최형진 (인하대학교 공과대학 고분자공학과) ;
  • 안화승 (인하대학교 공과대학 화학공학과)
  • 투고 : 2004.09.22
  • 심사 : 2004.12.10
  • 발행 : 2005.04.30

초록

실리카계 메조 물질인 MCM-41의 합성시 $Fe^{3+}$ 염을 합성 기질에 직접 도입하여 구조 내의 Si를 Fe로 일부 치환시킨 Fe-MCM-41(4 mol% Fe)을 합성하였다. XRD, $N_2$ 흡착법, TEM 등으로 합성한 메조 세공 물질의 구조적 특성을 조사하였으며, UV-Vis 및 FT-IR 등의 분광분석을 통하여 철의 상태를 확인하였다. 촉매적 활성 연구를 위하여 과산화수소를 산화제로 이용한 phenol hydroxylation을 수행하였으며, 물을용매로 반응 온도 $50^{\circ}C$, phenol:$H_2O_2$=1:1 조건에서 ca. 60%의 전화율을 얻었다. 또한, 구조 중 Fe 활성점을 이용한 탄소 나노 튜브의 성장 가능성을 확인하기 위하여, 아세틸렌가스를 탄소원으로 사용한 thermal-CVD 반응기를 이용하였으며, 다중벽 탄소 나노 튜브를 제조할 수 있었다.

A Fe-containing mesoporous silica (Fe-MCM-41) in which part of Si in the framework was replaced by Fe(Si-O-Fe) has been successfully prepared using $Fe^{3+}$ salt by a direct synthesis route. Physical properties of the material were characterized by XRD, $N_2$ adsorption, SEM/TEM, UV-vis and FT-IR spectroscopies. Fe-MCM-41 exhibited high catalytic activity in phenol hydroxylation using $H_2O_2$ as oxidant, giving phenol conversion of ca. 60% at $50^{\circ}C$ [phenol : $H_2O_2$ = 1:1, water solvent]. Fe-MCM-41 was also applied to the growth of CNTs, utilizing a thermal-CVD reactor using acetylene gas, which demonstrated that multi-wall CNTs could be prepared efficiently using the Fe-MCM-41 catalyst.

키워드

과제정보

연구 과제 주관 기관 : 한국과학재단

참고문헌

  1. Kresge, C. T., Leonowicz, M. E., Roth, W. J., Vartuli, J. C. and Beck, J. C., 'Ordered Mesoporous Molecular Sieves Synthesized by a Liquid-crystal Template Mechanism,' Nature, 359, 710-712(1992)
  2. 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. and Schlenker, J. L., 'A New Family of Mesoporous Molecular Sieves Prepared with Liquid Crystal Templates,' J. Am. Chem. Soc., 114(27), 10834-10843(1992) https://doi.org/10.1021/ja00053a020
  3. Kang, T. G., Kim, J. H., Seo, G. and Park, H. C., 'Hydrothermal Stabilities and Adsorption Properties of Titania Loaded on MCM-41 and KIT-1 Mesoporous Materials,' HWAHAK KONGHAK, 36(3), 364- 368(1998)
  4. Pei-Shing, E. D., 'Zeolite Catalysis for a better Environment,' Catal. Today, 26(1), 3-11(1995) https://doi.org/10.1016/0920-5861(95)00069-R
  5. Corma, A., Martinez, A., Martinez-Soria, V. and Monton, J. B., 'Hydrocracking of Vacuum Gasoil on the Noble Mesoporous MCM-41 Aluminosilicate Catalyst,' J. Catal., 153, 25-31(1995) https://doi.org/10.1006/jcat.1995.1104
  6. Zhao, D., Feng, J., Huo, Q., Melosh, N., Fredrickson, G. H., Chmelka, B. F. and Stucky, G. D., 'Triblock Copolymer Synthesis of Mesoporous Silica with Periodic 50 to 300 Angstrom Pores,' Science, 279(23), 548-552(1998)
  7. Bagshaw, S. A., Prouzet, E. and Pinnavaia, T. J., 'Templating of Mesoporous Molecular Sieves by Nonionic Polyethylene Oxide Surfactants,' Science, 269, 1242-1245(1995)
  8. Lee, J. W., Yoon, S. H., Hyeon, T. H., Oh, S. M. and Kim, K. B., 'Synthesis of a New Mesoporous Carbon and Its Application to Electrochemical Double-layer Capacitors,' Chem. Commun., (21), 2177- 2178(1999)
  9. Ryoo, R., Joo, S. H. and Jun, S. A., 'Synthesis of Highy Ordered Carbon Molecular Sieves via Template-Mediated Structural Transformation,' J. Phys. Chem. B, 103(27), 7743-7746(1999) https://doi.org/10.1021/jp991673a
  10. Han, Y., Xiao, F. S., Wu, S., Sun, Y., Meng, X., Li, D. and Lin, S., 'A Novel Method for Incorporation of Heteroatoms into the Framework of Ordered Mesoporous Silica Materials Synthesized in Strong Acidic Media,' J. Phys. Chem. B, 105(33), 7963- 7966 (2001) https://doi.org/10.1021/jp011204k
  11. Bharat, L. N., Johnson, O. and Sridhar, K., 'Direct Synthesis of Titanium-Substituted Mesoporous SBA-15 Molecular Sieve under Microwave-Hydrothermal Conditions,' Chem. Mater., 13(2), 552-557(2001) https://doi.org/10.1021/cm000748g
  12. Suvanto, S., Hukkamaki, J., Pakkanen, T. T. and Pakkanen, T. A., 'High-Cobalt-Loaded MCM-41 via the Gas-Phase Method,' Langmuir, 16(9), 4109-4115(2000) https://doi.org/10.1021/la991176l
  13. Samanta, S., Giri, S., Sastry, P. U., Mal, N. K., Manna, A. and Bhaumik, A., 'Synthesis and Characterization of Iron-Rich Highly Ordered Mesoporous Fe-MCM-41,' Ind. Eng. Chem. Res., 42(3), 3012-3018(2003) https://doi.org/10.1021/ie020905g
  14. Kim, S. W., Son, S. U., Lee, S. S., Hyeon, T. W. and Chung, Y. K., 'Colloidal Cobalt Nanoparticles: a Highly Active and Reusable Pauson-Khand Catalyst,' Chem. Commun., (21), 2212-2213 (2001)
  15. Xiao, F. S., Sun, J., Meng, X., Yu, X., Yuan, H., Jiang, D., Qui, S. and Xu, R., 'A Novel Catalyst of Copper Hydroxyphosphate with High Activity in Wet Oxidation of Aromatics,' Appl. Catal. A: General, 207(1-2), 267-271(2001) https://doi.org/10.1016/S0926-860X(00)00609-8
  16. Sun, J., Meng, X., Shi, Y., Wang, R., Feng, S., Jiang, D., Xu, R. and Xiao, F. S., 'A Novel Catalyst of Cu-Bi-V-O Complex in Phenol Hydroxylation with Hyrogen Peroxide,' J. Catal., 193(2), 199-206(2000) https://doi.org/10.1006/jcat.2000.2901
  17. Ribera, A., Arends, I. W. C. E., de Vries, S., Perez-Ramirez, J. and Sheldon, R. A., 'Preparation, Characterization, and Performance of FeZSM-5 for the Selective Oxidation of Benzene to Phenol with $N_2O$,' J. Catal., 195(2), 287-297(2000) https://doi.org/10.1006/jcat.2000.2994
  18. Han, Y., Meng, X., Guan, H., Yu, Y., Zhao, L., Xu, X., Yang, X., Wu, S., Li, N. and Xiao, F. S., 'Stable Iron-incorporated Mesoporous Silica Materials (MFS-9) Prepared in Strong Acidic Media,' Micropor. Mesopor. Mater., 57(2), 191-198(2003) https://doi.org/10.1016/S1387-1811(02)00590-5
  19. Wang, D., Liu, Z., Liu, F., Ai, X., Zhang, X., Cao, Y., Yu, J., Wu, T., Bai, Y., Li, T. and Tang, X., '$Fe_2O_3/macroporous$ Resin Nanocomposites: Some Novel Highly Efficient Catalysts for Hydroxylation of Phenol with $H_2O_2$,' Appl. Catal. A: General, 174(1-2), 25-32(1998) https://doi.org/10.1016/S0926-860X(98)00156-2
  20. Liu, C., Shan, Y., Yang, X., Ye, X. and Wu, Y., 'Iron(II)-8-quinolinol/ MCM-41-catalyzed Phenol Hydroxylation and Reaction Mechanosm,' J. Catal., 168(1), 35-41(1997) https://doi.org/10.1006/jcat.1997.1612
  21. Kim, W. J. and Ahn, W. S., 'Synthesis of Ti Containing Molecular Sieves using a Diethoxysiloxane-ethyltitanate Polymer,' Catal. Lett., 94(3-4), 187-191(2004)
  22. Zhang, R. Y., Amlani, I., Baker, J., Tresek, J., Tsui, R. K. and Fejes, P., 'Chemical Vapor Deposition of Single-Walled Carbon Nanotubes using Ultrathin Ni/Al Film as Catalyst,' Nano Lett. (Communication), 3(6), 731-735(2003) https://doi.org/10.1021/nl034154z
  23. Lim, S. Y., Ciuparu, D., Pak, C. H., Dobek, F., Chen, Y., Harding, D., Pfefferle, L. and Haller, G., 'Synthesis and Characterization of Highly Ordered Co-MCM-41 of Production of Aligned Single Walled Carbon Nanotubes (SWNT),' J. Phys. Chem. B, 107(40), 11048-11056(2003) https://doi.org/10.1021/jp0304778
  24. Duxiao, J., Nongyue, H., Yuanying, Z., Chunxiang, X., Chunwei, Y. and Zuhong, L., 'Catalytic Growth of Carbon Nanotubes from the Internal Surface of Fe-loading Mesoporous Molecular Sieve Materials,' Mater. Chem. Phys., 69(1-3), 246-251(2001) https://doi.org/10.1016/S0254-0584(00)00304-7
  25. Iijima, S., 'Helical Microtubes of Graphitic Carbon,' Nature, 354, 56-58(1991)
  26. Soh, H. T., Quate, C. F., Morpurgo, A. F., Marcus, C. M., Kong, J. and Dai. H., 'Integrated Nanotube Circuits: Controlled Growth and Ohmic Contacting of Single-Walled Carbon Nanotubes,' Appl. Phys. Lett., 75(5), 627-629(1999) https://doi.org/10.1063/1.124462
  27. Mo, Y. H., Park, K. S., Park, S. H. and Nahm K. S., 'Growth of Carbon Nanotubes using Ni Catalysts in RTCVD Reactor,' HWAHAK KONGHAK, 38(5), 683-690(2000)
  28. Li, W. Z., Xie, S. S., Qian, L. X., Chang, B. H., Zou, B. S., Zhow, W. Y., Zhao, R. A. and Wang, G., 'Large-Scale Synthesis of Aligned Carbon Nanotubes,' Science, 274(5293), 1701-1703 (1996)
  29. Yuan, Z. Y., Liu, S. Q., Chen, T. H., Wang, J. Z. and Li, H. X., 'Synthesis of Iron-containing MCM-41, ' J. Chem. Soc. Chem. Commun., (9), 973-974(1995)
  30. Laurent, C., Flahaut, E., Peigney, A. and Rousset, A., 'Metal Nanoparticles for the Catalytic Synthesis of Carbon Nanotubes,' New J. Chem., 22(11), 1229-1237(1998) https://doi.org/10.1039/a801991f
  31. Terrones, M., Hsu, W. K., Kroto, H. W. and Walton D. R. M., 'Nanotubes: A Revolution in Materials Science and Electronics,' Top. Curr. Chem., 199, 189-234(1999) https://doi.org/10.1007/3-540-68117-5_6