이원금속 촉매의 구조와 반응성

이재의

Journal of the Korean Industrial and Engineering Chemistry, Vol.3, No.1, 24-34, March, 1992

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이원금속 촉매의 구조와 반응성

Structure and Reactivity of Bimetallic Catalyst

이재의

초록

이원금속 촉매의 작용원리와 응용에 대한 최근의 연구를 고찰하였다. 이원금속 촉매는 납사접촉개질반응, CO 수소환원반응 및 자동차 3원촉매 전환반응 등에 공업적으로 크게 영향을 미쳤다. 이들 반응에 대찬 이원금속 촉매의 작용은 "ensemble", 전자적인 영향 및 표면 구조적인 면으로 설명될 수 있다. 첨가 금속의 작용을 잘 평가하기 위하여 다양한 금속쌍 조합이 고려되었다. 또한 촉매의 선택성을 조절하기 위해서는 표면에 한 금속이 더 편중되는 것이 밝혀졌다. 일반적으로 담지촉매 제조과정상의 여러 요인들의 영향에 대해서도 특별히 TPR법같은 방법에 의해 명확해졌다. 이원금속 촉매의 구조에 관한 정보는 화학흡착이나 반응속도 측정같은 화학적 방법이나 EXAFS, STEM 및 Xe-NMR 같은 물리적 방법에 의해서 얻어지고 있다

Recent studies dealing with the fundamental understanding and applications of bimetallic catalysts are discussed. Bimetallic catalysts have had a major industrial impact, specifically for the reforming of petroleum naphtha, for the hydrogen reduction of carbon monoxide, and for the three way catalytic converter system. The action of the bimetallic catalysts in these reactions may be interpreted in terms of ensembles, electronic influences and surface structure. Various combinations of metal pairs have been considered in order to evaluate the role played by the added metals. For catalyst selectivity control, the possibility of surface enrichment of one element has been recognised. More generally, the influence of preparative variables on the formation of supported catalysts has been clarified, In particular by temperature programmed reduction (TPR) . Information on the structure of bimetallic catalysts has been obtained with chemical probes, such as chemisorption and reaction rate measurement and physical probes, such as extended X-ray absorption fine structure (EXAFS), scanning transmission electron microscopy (STEM) and Xe-NMR.

[References]

Schwab GM, Disc. Faraday Soc., 8, 166 (1950)
Sinfelt JH, Adv. Chem. Eng., 5, 37 (1964)
Rodriguez JA, Campbell RA, Goodman W, J. Phys. Chem., 95, 5716 (1981)
VanDelft FCMJM, Siera K, Vreeburg RJ, VanCroos MJK, vanLangeveld AD, Nieuwenhuys BE, Phillips MJ, Ternan M, Proceedings, 9th International Congress on Catalysis, The Chemical Institute of Canada, Ottawa, 1114 (1988)
Paffet MT, Gebhard SC, Windham RG, Koel BE, J. Phys. Chem., 94, 6831 (1990)
Overloury SH, Mullins DR, Paffet MT, Koel BE, Surf. Sci., 245, 45 (1991)
He YL, Zuo JK, Wang GC, How JJ, Surf. Sci., 269 (1991)
Siera J, Rutten F, Nieuwenhuys BE, Catal. Today, 10, 353 (1991)
Sinfelt JH, Bimetallic Catalysis-Discoveries, Concepts, and Application, New York (1983)
Moss RL, Whalley L, Adv. Catal., 22, 115 (1972)
Clarke JKA, Creaner ACM, Ind. Eng. Chem. Prod. Res. Dev., 20, 574 (1981)
Sinfelt JH, Via GH, Lytle FW, J. Chem. Phys., 76(6), 15 (1982)
Meitzer G, Via GH, Lytle FW, Sinfelt JH, J. Chem. Phys., 78(5), 1 (1983)
Meitzner G, Via GH, Lytle FW, Sinfelt JH, J. Chem. Phys., 87(11), 1 (1987)
Oh SH, Carpenter JE, J. Catal., 98, 178 (1986)
Tzou MS, Kusunok M, Asakura K, Kuroda H, Moretti G, Sachtler WMH, J. Phys. Chem., 95, 5120 (1991)
Henriques C, Dufresne P, Marcilly C, Ribeiro FR, Appl. Catal., 21, 169 (1986)
Sachdev A, Phillips MJ, Ternan M, Proceedings, 9th International Congress on Catalysis, The Chemical Institute of Canada, Ottawa, 1275 (1988)
Ziemecki SB, Michel JB, Jones GA, "Reactivity of Solids," 2, 187 (1986)
McVicker GB, Ziemiak JJ, Appl. Catal., 14, 229 (1985)
Graham AG, Wanke SE, J. Catal., 68, 1 (1981)
Wang XK, Schwarz JA, Appl. Catal., 18, 147 (1985)
Huang YJ, Fung SC, Gates WE, McVicker GB, J. Catal., 118, 192 (1989)
Bacaud R, Bussiee P, Figueras F, J. Catal., 69, 399 (1981)
Burch R, J. Catal., 71, 384 (1981)
Baronetti GT, deMiguel SR, Scelza OA, Fritzler MA, Casro AA, Appl. Catal., 19, 77 (1985)
Meitzner G, Via GH, Lytle FW, Fung SC, Sinfelt JH, J. Phys. Chem., 92, 2925 (1988)
Sinfelt JH, Via GH, Lytle FW, Greegor RB, J. Chem. Phys., 75(11) (1981)
Ceitzner G, Via GH, Lytle FW, Sinfelt JH, J. Chem. Phys., 78, 15 (1983)
Gomez G, Fuentes S, Fernandez FJ, Camperio A, Ferreira J, J. Catal., 38, 47 (1975)
Sinfelt JH, J. Catal., 29, 308 (1973)
Chen M, Schmidt LD, J. Catal., 56, 198 (1979)
Grill CM, Gonzalez RD, J. Catal., 64, 487 (1980)
DeMencttal LC, Fraissard JP, Ito TJ, Faraday Trans. 1, 78, 403 (1982)
Schapt EW, Crecely RW, Gates BC, Dybowski C, J. Phys. Chem., 90, 9 (1986)
Boudart M, Samant MG, Ryoo R, Ultramicroscopy, 20, 15 (1986)
Ahn DH, Lee JS, Momura M, Sachtler WM, Moretti G, Woo SI, Ryoo R, J. Catal., in press
Carter JL, McVicker GB, Weissman W, Kmak WS, Sinfelt JH, Appl. Catal., 3, 327 (1982)
Duir JM, Hydrocarb. Process., 46(9), 127 (1967)
Verbeek M, Sachtler WMH, J. Catal., 42, 256 (1976)
Burch R, Mitchell AJ, Appl. Catal., 6, 121 (1983)
Yermakov YI, Kuznetsov BV, Zakharov VA, "Catalysis by Supported Complex," Elsevier, Amsterdam-Oxford, New York, p. 345 (1981)
Tri TM, Candy JP, Gallezot P, Massardier J, Primet M, Vedrine JC, Imelik B, J. Catal., 79, 396 (1983)
Yashu Y, Xiexitan G, Huimin L, Maicun D, Zhiyin L, Delmon, Grange, Jacobs, Poncelet (eds.): Preparation of Catalysts IV, Elsevier, Amsterdam-Oxford-New York-Tokyo, 701 (1989)
Satterfield CN, "Heterogeneous Catalysis in Practice," McGraw-Hill, New York (1980)
Mills GA, Steffgen FW, Catal. Rev.-Sci. Eng., 8, 159 (1973)
Schuit GCA, Gates BC, Chem. Tech., 556 (1983)
Ramachandran A, Chakrrabarty DK, Appl. Catal., 42, 229 (1988)
Foley HC, Hong AJ, Brinen JS, Allard SF, Garratt-Reed AJ, Appl. Catal., 61, 351 (1990)
Loof P, Kasemo B, Bjomkvist L, Andersso S, Frested A, "Catalysis and Automotive Pollution Control II," Amsterdam, 253-273 (1991)
Mecker WC, Wardinsky MD, Clemmer PC, Breneman RB, Phillips MJ, Terman M, Proceedings, 9th International Congress on Catalysis, The Chemical Institute of Canada, Ottawa, 1106 (1988)
Anderson JA, Rochester CH, Catal. Today, 10, 275 (1991)
McClory MM, Gonzalez RD, J. Phys. Chem., 90, 628 (1986)
vanDelft FCMJ, Vurens GH, Angevaare-gruter MC, Nieuwenhuys BE, Crucq A, Frennet A, Catalysis and Automotive Pollution Control, 229 (1987)

[Referenced By]

[1] Schwab GM, Disc. Faraday Soc., 8, 166 (1950)

[2] Sinfelt JH, Adv. Chem. Eng., 5, 37 (1964)

[3] Rodriguez JA, Campbell RA, Goodman W, J. Phys. Chem., 95, 5716 (1981)

[4] VanDelft FCMJM, Siera K, Vreeburg RJ, VanCroos MJK, vanLangeveld AD, Nieuwenhuys BE, Phillips MJ, Ternan M, Proceedings, 9th International Congress on Catalysis, The Chemical Institute of Canada, Ottawa, 1114 (1988)

[5] Paffet MT, Gebhard SC, Windham RG, Koel BE, J. Phys. Chem., 94, 6831 (1990)

[6] Overloury SH, Mullins DR, Paffet MT, Koel BE, Surf. Sci., 245, 45 (1991)

[7] He YL, Zuo JK, Wang GC, How JJ, Surf. Sci., 269 (1991)

[8] Siera J, Rutten F, Nieuwenhuys BE, Catal. Today, 10, 353 (1991)

[9] Sinfelt JH, Bimetallic Catalysis-Discoveries, Concepts, and Application, New York (1983)

[10] Moss RL, Whalley L, Adv. Catal., 22, 115 (1972)

[11] Clarke JKA, Creaner ACM, Ind. Eng. Chem. Prod. Res. Dev., 20, 574 (1981)

[12] Sinfelt JH, Via GH, Lytle FW, J. Chem. Phys., 76(6), 15 (1982)

[13] Meitzer G, Via GH, Lytle FW, Sinfelt JH, J. Chem. Phys., 78(5), 1 (1983)

[14] Meitzner G, Via GH, Lytle FW, Sinfelt JH, J. Chem. Phys., 87(11), 1 (1987)

[15] Oh SH, Carpenter JE, J. Catal., 98, 178 (1986)

[16] Tzou MS, Kusunok M, Asakura K, Kuroda H, Moretti G, Sachtler WMH, J. Phys. Chem., 95, 5120 (1991)

[17] Henriques C, Dufresne P, Marcilly C, Ribeiro FR, Appl. Catal., 21, 169 (1986)

[18] Sachdev A, Phillips MJ, Ternan M, Proceedings, 9th International Congress on Catalysis, The Chemical Institute of Canada, Ottawa, 1275 (1988)

[19] Ziemecki SB, Michel JB, Jones GA, "Reactivity of Solids," 2, 187 (1986)

[20] McVicker GB, Ziemiak JJ, Appl. Catal., 14, 229 (1985)

[21] Graham AG, Wanke SE, J. Catal., 68, 1 (1981)

[22] Wang XK, Schwarz JA, Appl. Catal., 18, 147 (1985)

[23] Huang YJ, Fung SC, Gates WE, McVicker GB, J. Catal., 118, 192 (1989)

[24] Bacaud R, Bussiee P, Figueras F, J. Catal., 69, 399 (1981)

[25] Burch R, J. Catal., 71, 384 (1981)

[26] Baronetti GT, deMiguel SR, Scelza OA, Fritzler MA, Casro AA, Appl. Catal., 19, 77 (1985)

[27] Meitzner G, Via GH, Lytle FW, Fung SC, Sinfelt JH, J. Phys. Chem., 92, 2925 (1988)

[28] Sinfelt JH, Via GH, Lytle FW, Greegor RB, J. Chem. Phys., 75(11) (1981)

[29] Ceitzner G, Via GH, Lytle FW, Sinfelt JH, J. Chem. Phys., 78, 15 (1983)

[30] Gomez G, Fuentes S, Fernandez FJ, Camperio A, Ferreira J, J. Catal., 38, 47 (1975)

[31] Sinfelt JH, J. Catal., 29, 308 (1973)

[32] Chen M, Schmidt LD, J. Catal., 56, 198 (1979)

[33] Grill CM, Gonzalez RD, J. Catal., 64, 487 (1980)

[34] DeMencttal LC, Fraissard JP, Ito TJ, Faraday Trans. 1, 78, 403 (1982)

[35] Schapt EW, Crecely RW, Gates BC, Dybowski C, J. Phys. Chem., 90, 9 (1986)

[36] Boudart M, Samant MG, Ryoo R, Ultramicroscopy, 20, 15 (1986)

[37] Ahn DH, Lee JS, Momura M, Sachtler WM, Moretti G, Woo SI, Ryoo R, J. Catal., in press

[38] Carter JL, McVicker GB, Weissman W, Kmak WS, Sinfelt JH, Appl. Catal., 3, 327 (1982)

[39] Duir JM, Hydrocarb. Process., 46(9), 127 (1967)

[40] Verbeek M, Sachtler WMH, J. Catal., 42, 256 (1976)

[41] Burch R, Mitchell AJ, Appl. Catal., 6, 121 (1983)

[42] Yermakov YI, Kuznetsov BV, Zakharov VA, "Catalysis by Supported Complex," Elsevier, Amsterdam-Oxford, New York, p. 345 (1981)

[43] Tri TM, Candy JP, Gallezot P, Massardier J, Primet M, Vedrine JC, Imelik B, J. Catal., 79, 396 (1983)

[44] Yashu Y, Xiexitan G, Huimin L, Maicun D, Zhiyin L, Delmon, Grange, Jacobs, Poncelet (eds.): Preparation of Catalysts IV, Elsevier, Amsterdam-Oxford-New York-Tokyo, 701 (1989)

[45] Satterfield CN, "Heterogeneous Catalysis in Practice," McGraw-Hill, New York (1980)

[46] Mills GA, Steffgen FW, Catal. Rev.-Sci. Eng., 8, 159 (1973)

[47] Schuit GCA, Gates BC, Chem. Tech., 556 (1983)

[48] Ramachandran A, Chakrrabarty DK, Appl. Catal., 42, 229 (1988)

[49] Foley HC, Hong AJ, Brinen JS, Allard SF, Garratt-Reed AJ, Appl. Catal., 61, 351 (1990)

[50] Loof P, Kasemo B, Bjomkvist L, Andersso S, Frested A, "Catalysis and Automotive Pollution Control II," Amsterdam, 253-273 (1991)

[51] Mecker WC, Wardinsky MD, Clemmer PC, Breneman RB, Phillips MJ, Terman M, Proceedings, 9th International Congress on Catalysis, The Chemical Institute of Canada, Ottawa, 1106 (1988)

[52] Anderson JA, Rochester CH, Catal. Today, 10, 275 (1991)

[53] McClory MM, Gonzalez RD, J. Phys. Chem., 90, 628 (1986)

[54] vanDelft FCMJ, Vurens GH, Angevaare-gruter MC, Nieuwenhuys BE, Crucq A, Frennet A, Catalysis and Automotive Pollution Control, 229 (1987)