MCM-41, 48 메조포러스 물질 및 SiO<sub>2</sub>에 담지한 헤테로 폴리산의 특성 및 촉매적 활성

박정우; 김범식; 이정민; 이관영

Journal of the Korean Industrial and Engineering Chemistry, Vol.10, No.7, 1020-1027, November, 1999

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MCM-41, 48 메조포러스 물질 및 SiO₂에 담지한 헤테로 폴리산의 특성 및 촉매적 활성

Property and Catalytic Activity of Heteropoly Acid Supported on MCM-41, 48 Mesoporous Material and SiO₂

박정우, 김범식, 이정민, 이관영

초록

헤테로폴리산(HPW)을 표면적이 서로 다른 담체인 SiO₂ MCM-41, MCM-48에 담지농도와 소성온도를 달리하며 담지시켰다. X-선 회절분석, 질소 흡착법,적외선 흡수 스펙트럼, ³¹P 고체 핵자기 공명을 통해서 이 담지촉매의 특성을 조사하였다. IR과 NMR의 결과로부터 HPW가 탐체안에서 케긴 구조를 유지하면서 존재함을 확인할 수 있었다. MCM-41의 경우에는 35 _wt%, MCM-48의 경우에는 65 _wt%로 담지시킨 경우에도 X-선 회절패턴에서 HPW 고유의 피크가 나타나지 않았으며, 이와 같은 특성을 통해서 HPW가 고분산 되어 있음을 알 수 있었다. Di, bis, tri-pentaerythritol의 가수분해 반응에서 이들 담지 촉매는 높은 촉매 활성을 보였으며 HPW, HPW/SiO₂보다 HPW/MCM-41, 48의 촉매 활성이 더 우수하였다.

Heteropoly acid(HPW) catalysts supported on three different carriers, an amorphous silica, MCM-41 and MCM-48 , with different loadings and calcination temperatures have been prepared and characterized by X-ray diffraction, nitrogen physorption, infrared spectroscopy, and ³¹P magic angle spinning NMR. From the result of IR and NMR, it was shown that HPW retains the Keggin structure on the supported catalysts, No HPW crystal phase was developed even at HPW loadings as high as 35 wt % on the MCM-41 and 65 wt % MCM-48. Thus HPW appeared to form finely dispersed species. In the hdrolysis reaction of di, bis, tri-pentaerythritol, HPW/MCM-41, 48 exhibited higher catalytic activity than HPW/SiO₂ or HPW.

Keywords:heteropoly acid (H₃PW₁₂O₄₀);MCM-41;MCM-48;supported catalysts;hydroysis;pentaerythritol

[References]

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[1] Corma A, Martinez A, Catal. Rev.-Sci. Eng., 4, 483 (1993)

[2] Kirsch FW, Potts JD, Barmby DS, J. Catal., 27, 142 (1972)

[3] Liang CH, Anthony RG, Prep. Am. Chem. Soc. Div. Petr. Chem., 38, 892 (1993)

[4] Misono M, Catal. Rev.-Sci. Eng., 29, 269 (1987)

[5] Misono M, Mizuno N, Katamura K, Kasai A, Konishi Y, Sakata K, Okuhara T, Yoneda Y, Bull. Chem. Soc. Jpn., 55, 400 (1982)

[6] Gregg SJ, Tayyab MM, J. Chem. Soc.-Faraday Trans., 174, 348 (1978)

[7] Nowinska K, Fiedorow R, Adamiec J, J. Chem. Soc.-Faraday Trans., 87, 749 (1991)

[8] Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC, Beck JS, Nature, 359, 710 (1992)

[9] Dai PS, Catal. Today, 26(1), 3 (1995)

[10] Liu CB, Ye XK, Wu Y, Catal. Lett., 36(3-4), 263 (1996)

[11] Corma A, Martinez A, Martinezsoria V, Monton JB, J. Catal., 153(1), 25 (1995)

[12] Jozefowicz LC, Karge HG, Vasilyeva E, Moffat JB, Microporous Mater., 1, 313 (1993)

[13] Schwegler MA, Bekkum HV, de Munck NA, Appl. Catal., 74, 191 (1991)

[14] Kozhevnikov IV, Sinnema A, Jansen RJ, Pamin K, Vanbekkum H, Catal. Lett., 30(1-4), 241 (1995)

[15] Ryoo R, Jun S, J. Phys. Chem. B, 101(3), 317 (1997)

[16] Kim JM, Kim SK, Ryoo R, J. Chem. Soc.-Chem. Commun., 2, 259 (1998)

[17] Kozhevnikov IV, Sinnema A, Jansen RJ, Vanbekkum H, Catal. Lett., 27(1-2), 187 (1994)

[18] Rocchiccioli-Deltcheff C, Fournier M, Frank R, Thouvenot R, Inorg. Chem., 22, 207 (1983)

[19] Kanda Y, Lee KY, Nakada S, Asaoka S, Misono M, Chem. Lett., 1, 139 (1988)

[20] Lee KY, Arai T, Nakata S, Asaoka S, Okuhara T, Misono M, J. Am. Chem. Soc., 114, 2836 (1992)

[21] Lefebvre F, J. Chem. Soc.-Chem. Commun., 10, 756 (1992)

[22] Blasco T, Corma A, Martinez A, Martinez-Escolano P, J. Catal., 177(2), 306 (1998)

[23] Kozhevnikov IV, Kloestra KR, Sinnema A, Zandbergen HW, Bekkum HV, J. Mol. Catal., 114, 287 (1996)

[24] Chu WL, Yang XG, Shan YK, Ye XK, Wu Y, Catal. Lett., 42(3-4), 201 (1996)

[25] Izumi Y, Hayashi K, Chem. Lett., 7, 787 (1980)