산, 염기 이원기능 금속-유기 구조체 촉매를 이용한 알돌 축합반응

정영민; Young-Min Chung

Clean Technology, Vol.20, No.2, 116-122, June, 2014

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산, 염기 이원기능 금속-유기 구조체 촉매를 이용한 알돌 축합반응

Aldol Condensation over Acid-Base Bifunctional Metal-Organic Framework Catalysts

정영민 ^†

군산대학교 나노화학공학과, 573-701 전북 군산시 미룡동 대학로 558

Young-Min Chung^†

Department of Nano & Chemical Engineering, 558 Daehak-ro, Miryong-dong, Kunsan, Jeonbuk 573-701, Korea

E-mail:

초록

수열합성 또는 후처리 방법을 통해 산 또는 염기능을 나타내는 다양한 종류의 이원기능 금속-유기 구조체 물질을 제조하여 대표적인 방향제 원료 중 하나인 자스민알데하이드(jasminaldehyde)를 합성하기 위한 벤즈알데하이드(benzaldehyde, C6H5CHO)와 헵탄알(heptanal, C6H13CHO)의 알돌 축합반응의 촉매로 활용하였다. 실험 결과, 산 또는 염기점 모두에서 축합 반응이 진행되었으며, 촉매 성능은 기능기의 도입 여부 및 종류와 금속-유기 구조체의 물리적인 특성에 크게 의존하였다. Jasminaldehyde 선택도는 황산 기능기를 도입한 경우에는 금속-유기 골격체의 종류에 상관없이 감소하였으나, 아민 기능기를 도입한 경우에는 금속-유기 골격체의 종류에 따라 상반된 경향을 나타내었다. 평가한 촉매 중 MIL-101의 촉매 성능이 가장 우수하였는데, 이러한 결과는 MIL-101이 알돌 축합반응의 촉매로 작용하기에 충분한 산량과 적당한 산세기를 가지고 있으며, 세공 크기가 넓어 크기가 큰 생성물의 물질이동 측면에서 유리하기 때문인 것으로 판단된다.

Various types of MOFs (metal-organic frameworks) were prepared via hydrothermal and post-grafting methods and applied as catalysts for the synthesis of jasminaldehyde, one of the representative perfume intermediates, by Aldol condensation of benzaldehyde with heptanal. Although both acid and base sites could catalyze the reaction, the catalytic performance was strongly dependent on the physical properties as well as the nature of functionalization on MOFs. While the use of sulfonated MOF catalysts led to decrease of jasminaldehyde selectivity regardless of MOFs used, the selectivity change was found to rely on the MOF types in the case of the amine-functionalization. Among the catalysts tested, MIL-101 shows the best catalytic performance, which may suggest that MIL-101 has suitable acid properties to promote the Aldol condensation and the large pore of MIL-101 is also advantageous to alleviate the diffusion problem of bulky products.

Keywords:Metal-organic framework;Aldol condensation;Heterogeneous catalyst;Bifunctional catalyst

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Chung YM, Kim HY, Ahn WS, Catal. Lett., 144, 817 (2014)
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[1] Sumida K, Rogow DL, Mason JA, McDonald TM, Bloch ED, Herm ZR, Bae TH, Long JR, Chem. Rev., 112(2), 724 (2012)

[2] Li JR, Sculley J, Zhou HC, Chem. Rev., 112(2), 869 (2012)

[3] Cohen SM, Chem. Rev., 112(2), 970 (2012)

[4] Corma A, Garcia H, Xamena FXL, Chem. Rev., 110(8), 4606 (2010)

[5] Lee J, Farha OK, Roberts J, Scheidt KA, Nguyen ST, Hupp JT, Chem. Soc. Rev., 38, 1450 (2009)

[6] Alaerts L, Seguin E, Poelman H, Thibault-Starzyk F, Jacobs PA, De Vos DE, Chem. Eur. J., 12, 7353 (2006)

[7] Henschel A, Gedrich K, Kraehnert R, Kaskel S, Chem. Commun., 4192 (2008)

[8] Kurfirtova L, Seo YK, Hwang YK, Chang JS, Cejka J, Catal. Today, 179(1), 85 (2012)

[9] Srirambalaji R, Hong S, Natarajan R, Yoon M, Hota R, Kim Y, Ko YH, Kim K, Chem. Commun., 48, 11650 (2012)

[10] Akiyama G, Matsuda R, Sato H, Takata M, Kitagawa S, Adv. Mater., 23(29), 3294 (2011)

[11] Vermoortele F, Ameloot R, Vimont A, Serrec C, DeVos D, Chem. Commun., 47, 1521 (2011)

[12] Prabhu A, Palanichamy M, Micro. Meso. Mater., 168, 126 (2013)

[13] Climent MJ, Corma A, Garcia H, Guil-Lopez R, Iborra S, Fornes V, J. Catal., 197(2), 385 (2001)

[14] Yadav GD, Aduri P, J. Mol. Catal. A: Chem., 355, 142 (2012)

[15] Zlotea C, Phanon D, Mazaj M, Heurtaux D, Guillerm V, Serre C, Horcajada P, Devic T, Magnier E, Cuevas F, Ferey G, Llewellyn PL, Latroche M, Dalton Trans., 40, 4879 (2011)

[16] Chung YM, Kim HY, Ahn WS, Catal. Lett., 144, 817 (2014)

[17] Kim J, Lee YR, Ahn WS, Chem. Commun., 49, 7647 (2013)

[18] Jiang D, Keenan LL, Burrows AD, Edler KJ, Chem. Commun., 48, 12053 (2012)

[19] Chung YM, Lee YR, Ahn WS, RSC Adv., 4, 23064 (2014)

[20] Sharma SK, Patel HA, Jasra RV, J. Mol. Catal. A-Chem., 280(1-2), 61 (2008)