제올라이트에 포획된 Rhodium Carbonyl Clusters

이태진; 김장희; 김윤갑

HWAHAK KONGHAK, Vol.29, No.6, 701-708, December, 1991

Export Citation

제올라이트에 포획된 Rhodium Carbonyl Clusters

Zelite-entrapped Rhodium Carbonyl Clusters

이태진, 김장희, 김윤갑

초록

제올라이트에 포획된 rhodium carbonyl clusters를 NaN₃로 처리된 염기성 제올라이트 Y의 세공내부에 흡착한[Rh(CO)₂(acac)]으로부터 제조하였다. 강한 염기성 제올라이트에 포획된 rhodium carbonyl clusters가 형성 되었으며 그 촉매는 CO 수소화반응에 활성을 가지며 저분자 올레핀과 메탄올을 선택적으로 합성하였다. 촉매는 300℃, 20 기압, H₂/CO 몰비 1의 조건에서 2주일 이상 활성도와 선택도의 현저한 감소없이 안정하였다. 촉매의 활성성분은 제올라이트의 cages 내부에 포획된 rhodium carbonyl clusters로 추정된다.

Zeolite-entrapped rhodium carbonyl clusters were prepared by converting adsorbed[Rh(CO)₂-(acac)]in the pores of zeolite Y made basic by treatment with NaN₃. In a strongly basic zeolite, entrapped rhodium carbonyl clusters were formed, and the catalyst was active for CO hydrogenation and selective for low-molecular-weight olefins and methanol. The catalyst was stable, operating at 300℃ and 20atm with H₂/CO molar ratio 1 for more than two weeks with no significant loss in activity and selectivity. The catalytical-ly active species are suggested to be rhodium carbonyl clusters trapped in the zeolite cages.

[References]

Fraenkel D, Gates BC, J. Am. Chem. Soc., 102, 2478 (1980)
Nazar LF, Ozin GA, Hugues F, Godber J, Rancourt D, J. Mol. Catal., 21, 313 (1983)
Zhou PL, Gates BC, J. Chem. Soc.-Chem. Commun., 347 (1989)
Zhou PL, Maloney SD, Gates BC, J. Catal., to be published
Ichikawa M, Bull. Chem. Soc. Jpn., 51, 2268 (1978)
Ichikawa M, Bull. Chem. Soc. Jpn., 51, 2273 (1978)
Whyman R, Phil. Trans. R. Soc. London, Ser. A, 308, 131 (1982)
Dombek DD, Adv. Catal., 32, 325 (1983)
Mantovani E, Palladino N, Zanovi A, J. Mol. Catal., 3, 285 (1978)
Primet M, Vedrine JC, Naccache C, J. Mol. Catal., 4, 411 (1978)
Hartley FR, "Supported Metal Complexes," D. Reidel Publishing Company, Boston (1985)
Gates BC, Guczi L, Knozinger H, "Metal Clusters in Catalysis," Elsevier, Amsterdam (1986)
Watanabe E, Murayama K, Hara Y, Kobayashi Y, Wada K, Onoda T, J. Chem. Soc.-Chem. Commun., 227 (1986)
Horlenko T, Murphy MA, Aguilo A, Voorhoeve RJH, Proc. 8th Int. Congr. Catal., 2, 195 (1984)
Lee TJ, Gates BC, Catal. Lett., 8, 15 (1991)
Lee TJ, Proc. 7th ROK/ROC Symp. Catal., 173 (1990)
Martens LRM, Grobet PJ, Jacobs PA, Nature, 315, 568 (1985)
Martens LRM, Grobet PJ, Vermeiren WJM, Jacobs PA, Stud. Surf. Sci. Catal., 28, 935 (1986)
Botani F, Wilkinson G, J. Chem. Soc., 3156 (1964)
King RB, King AD, Iqbal MZ, J. Am. Chem. Soc., 101, 4893 (1979)
Lee DK, Ihm SK, J. Catal., 106, 386 (1987)
Lee DK, Ihm SK, Appl. Catal., 32, 85 (1987)
Anderson RB, "The Fischer-Tropsch Synthesis," Academic Press, Orlando (1984)
Lefebvre F, Gelin P, Naccache C, BenTaarit Y, Proc. 6th Int. Zeolite Conference, 435 (1983)
Rao LF, Fukuoka A, Ichikawa M, J. Chem. Soc.-Chem. Commun., 458 (1988)
Lamb HH, Krause TR, Gates BC, Proc. 9th Int. Congr. Catal., 3, 1378 (1988)
Takahashi N, Mijin A, Suematsu H, Shinohara S, Matsuoka H, J. Catal., 117, 348 (1989)
Shannon RD, Vedrine JC, Naccache C, Lefebvre F, J. Catal., 88, 431 (1984)
Gelin P, BenTaarit Y, Naccache C, J. Catal., 59, 357 (1979)
Burkhardt I, Gutschick D, Lohse U, Miessner H, J. Chem. Soc.-Chem. Commun., 291 (1987)

[Referenced By]

[1] Fraenkel D, Gates BC, J. Am. Chem. Soc., 102, 2478 (1980)

[2] Nazar LF, Ozin GA, Hugues F, Godber J, Rancourt D, J. Mol. Catal., 21, 313 (1983)

[3] Zhou PL, Gates BC, J. Chem. Soc.-Chem. Commun., 347 (1989)

[4] Zhou PL, Maloney SD, Gates BC, J. Catal., to be published

[5] Ichikawa M, Bull. Chem. Soc. Jpn., 51, 2268 (1978)

[6] Ichikawa M, Bull. Chem. Soc. Jpn., 51, 2273 (1978)

[7] Whyman R, Phil. Trans. R. Soc. London, Ser. A, 308, 131 (1982)

[8] Dombek DD, Adv. Catal., 32, 325 (1983)

[9] Mantovani E, Palladino N, Zanovi A, J. Mol. Catal., 3, 285 (1978)

[10] Primet M, Vedrine JC, Naccache C, J. Mol. Catal., 4, 411 (1978)

[11] Hartley FR, "Supported Metal Complexes," D. Reidel Publishing Company, Boston (1985)

[12] Gates BC, Guczi L, Knozinger H, "Metal Clusters in Catalysis," Elsevier, Amsterdam (1986)

[13] Watanabe E, Murayama K, Hara Y, Kobayashi Y, Wada K, Onoda T, J. Chem. Soc.-Chem. Commun., 227 (1986)

[14] Horlenko T, Murphy MA, Aguilo A, Voorhoeve RJH, Proc. 8th Int. Congr. Catal., 2, 195 (1984)

[15] Lee TJ, Gates BC, Catal. Lett., 8, 15 (1991)

[16] Lee TJ, Proc. 7th ROK/ROC Symp. Catal., 173 (1990)

[17] Martens LRM, Grobet PJ, Jacobs PA, Nature, 315, 568 (1985)

[18] Martens LRM, Grobet PJ, Vermeiren WJM, Jacobs PA, Stud. Surf. Sci. Catal., 28, 935 (1986)

[19] Botani F, Wilkinson G, J. Chem. Soc., 3156 (1964)

[20] King RB, King AD, Iqbal MZ, J. Am. Chem. Soc., 101, 4893 (1979)

[21] Lee DK, Ihm SK, J. Catal., 106, 386 (1987)

[22] Lee DK, Ihm SK, Appl. Catal., 32, 85 (1987)

[23] Anderson RB, "The Fischer-Tropsch Synthesis," Academic Press, Orlando (1984)

[24] Lefebvre F, Gelin P, Naccache C, BenTaarit Y, Proc. 6th Int. Zeolite Conference, 435 (1983)

[25] Rao LF, Fukuoka A, Ichikawa M, J. Chem. Soc.-Chem. Commun., 458 (1988)

[26] Lamb HH, Krause TR, Gates BC, Proc. 9th Int. Congr. Catal., 3, 1378 (1988)

[27] Takahashi N, Mijin A, Suematsu H, Shinohara S, Matsuoka H, J. Catal., 117, 348 (1989)

[28] Shannon RD, Vedrine JC, Naccache C, Lefebvre F, J. Catal., 88, 431 (1984)

[29] Gelin P, BenTaarit Y, Naccache C, J. Catal., 59, 357 (1979)

[30] Burkhardt I, Gutschick D, Lohse U, Miessner H, J. Chem. Soc.-Chem. Commun., 291 (1987)