실리카지지 루테늄-철 촉매에서 일산화탄소의 흡착에 관한 적외선 분광법을 이용한 연구

박상윤; 류광선; 양성봉; 윤구식; Sang-Youn Park; Kwang-Sun Ryu; Sung-Bong Yang; Koo-Sik Yoon

Applied Chemistry for Engineering, Vol.21, No.1, 81-86, February, 2010

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실리카지지 루테늄-철 촉매에서 일산화탄소의 흡착에 관한 적외선 분광법을 이용한 연구

A Study on the Adsorption of Carbonmonoxide on Silica Supported Ru-Fe Catalyst by Infrared Spectroscopy

박상윤^†, 류광선, 양성봉, 윤구식

울산대학교 자연과학대학 화학과

Sang-Youn Park^†, Kwang-Sun Ryu, Sung-Bong Yang, and Koo-Sik Yoon

Department of Chemistry, University of Ulsan, Ulsan 680-749, Korea

E-mail:

초록

실리카 지지 루테늄과 철의 합금(Ru/Fe-SiO2) 시료에 일산화탄소(CO)를 흡착시켰을 때 Ru/Fe의 몰비 9/1 이상에서 다섯 적외선 흡수띠(2138.7∼2142.5 cm^(-1), 2067.3∼2073.1 cm^(-1), 1976.7∼2017.2 cm^(-1), 1737.9∼1799.3 cm^(-1), 1625.7 cm^(-1))를 관찰했고, Ru/Fe의 몰비 8/2 이하에서 두 적외선 흡수띠(1934.0∼1990.2 cm^(-1), 1625.7 cm^(-1))를 관찰했다. 2138.7∼2142.5cm^(-1) 흡수띠, 2067.3∼2073.1 cm^(-1) 흡수띠, 1976.7∼2017.2 cm^(-1) 흡수띠는 Ru/Fe 뭉치 표면의 Ru 원자에 선형결합한 CO의 신축진동에 의한 것으로, 1774.2∼1799.3 cm^(-1) 흡수띠는 Ru/Fe 뭉치 표면의 Ru 원자와 다리결합하거나 높은 지수평면에 있는 Ru 원자에 결합한 CO의 신축진동에 의한 것으로, 1934.0∼1990.2 cm^(-1) 흡수띠는 Ru/Fe 뭉치 표면의 Fe 원자에 선형결합한 CO의 신축진동에 의한 것으로 제시할 수 있다. Ru/Fe-SiO2에서 CO를 흡착시켰을 때 Ru/Fe 몰비가 8/2 이하에서 증가할 때 CO가 Fe에 선형결합하여 생긴 1934.0∼1990.2 cm^(-1) 흡수띠의 흡광도가 증가하였는데, 이 현상은 Ru/Fe 몰비가 8/2 이하에서 증가할 때 Ru/Fe 뭉치 표면에서 시료의 함량과 비교하여 Fe 농도가 증가했고 Fe-SiO2 시료와 비교하여 표면적이 Ru/Fe 몰비의 증가에 따라 점차 증가했기 때문으로 설명할 수 있다.

On adsorbing carbon monoxide (CO) on the silica supported ruthenium/iron alloy (Ru/Fe-SiO2) samples above mole ratio 9/1 of Ru/Fe five bands (2138.7∼2142.5 cm^(-1), 2067.3∼2073.1 cm^(-1), 1976.7∼2017.2 cm^(-1), 1737.9∼1799.3 cm^(-1), 1625.7 cm^(-1)) were observed, and in Ru/Fe-SiO2 samples below mole ratio 8/2 of Ru/Fe two bands (1934.0∼1970.9 cm^(-1), 1625.7 cm^(-1)) were observed. The 2138.7∼2142.5 cm^(-1) bands, the 2067.3∼2073.1 cm^(-1) bands, and the 1988.3∼2030.7 cm^(-1) bands may be ascribed to stretching vibrations of CO molecules lineally bonded to the Ru atoms on supported Ru/Fe cluster surface, the 1737.9∼1799.3 cm^(-1) bands to stretching vibrations of CO molecules bridge bonded to the Ru atoms on supported Ru/Fe cluster surface or to stretching vibrations of CO molecules bonded to the Ru atoms on high Miller index planes, and the 1934.0∼1990.2 cm^(-1) bands to stretching vibrations of CO molecules lineally bonded to the Fe atoms on supported Ru/Fe cluster surface. The absorbances of the 1934.0∼1990.2 cm^(-1) bands in Ru/Fe-SiO2 samples gradually increased with the increases of Ru/Fe mole ratio below the ratio of 8/2. This phenomena may be ascribed to the increases of Fe concentration of surface compared with the one of the sample and to the increases of surface area of supported Ru/Fe cluster according as increase of Ru/Fe mole ratio below the ratio of 8/2 compared with the Fe-SiO2 sample.

Keywords:CO adsorption;ruthenium-iron alloy;ruthenium-iron catalyst;silica support

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[4] Chabal YJ, Surf. Sci. Rep., 8, 211 (1988)

[5] Lynds L, Spectrochem. Acta, 20, 1369 (1964)

[6] Kulkami GU, Kannan KR, Arunakavjalli T, Rao CNR, Adv. Catal. Des., Proc. Workshop, 2, 373 (1993)

[7] Sasaki T, Aruga T, Iwasawa Y, Surf. Sci., 291, 429 (1993)

[8] Eischens RP, Pliskin WA, Adv. Catal., 10, 1 (1958)

[9] Cable JW, Sheline RK, Chem. Rev., 56, 1 (1956)

[10] Lee JW, Chang S, Pak H, Shin KJ, Kim M, Chung WI, Bull. Korean Chem. Soc., 9, 137 (1988)

[11] Herzberg G, Molecular Spectra and Molecular Structure. Volume I. Spectra of Diatomic Molecules, D. Van Nostrand Co, Inc.: Princeton, New Jersey (1950)

[12] Agnelli M, Swaan HM, Marquez-Alvarez C, Martin GA, Mirodatos C, J. Catal., 175(1), 117 (1998)

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[16] Kostov KL, Rauscher H, Menzel D, Surf. Sci., 278, 62 (1992)

[17] Hoffman FM, Weisel MD, Surf. Sci., 253, 59 (1988)

[18] Brown MF, Gonzalez RD, J. Phys. Chem., 80, 1731 (1976)

[19] Schiffer A, Jakob P, Menzel D, Surf. Sci., 389, 116 (1997)

[20] Cable JW, Sheline RK, Chem. Rev., 56, 1 (1956)

[21] Blyholder G, J. Phys. Chem., 36, 2036 (1962)

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[23] Wuff G, Benson C, Patterson D, J. Chem. Phys., 23, 670 (1955)

[24] Ahn JS, Yoon KS, Park SY, Park SK, J. Kor. Chem. Soc., 53, 233 (2009)

[25] Seip U, Tsai MC, Christmann K, Kueppers J, Ertl G, Surf. Sci., 160, 400 (1984)

[26] Moon DW, Bernas SL, Dwyer DJ, Gland JL, J. Am. Chem. Soc., 107, 4363 (1985)

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[28] Blyholder G, J. Phys. Chem., 79, 756 (1975)

[29] Hollins P, Surf. Sci. Rep., 16, 51 (1992)

[30] Bradshaw AM, Hoffman FM, Surf. Sci., 72, 513 (1978)