실리카 수산기의 산성에 관한 양자화학적 해석

김명철

Journal of the Korean Industrial and Engineering Chemistry, Vol.8, No.2, 262-266, April, 1997

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실리카 수산기의 산성에 관한 양자화학적 해석

Quantum Chemical Calculations of Silica Hydroxyls as Acid Site

김명철

초록

실리카 표면 수산기를 나타내는 분자모델에 대해 CNDO/2계산을 수행하여 Wiberg결합차수, 전체에너지, LUMO에너지, 쌍극자모멘느 및 형식전하를 얻었다. 제안된 모델들의 Bronsted산성도는 Wiberg결합차수를 이용하여 서술하였다. 계산된 결합차수값들은 수소결합에 따라 큰 차이를 나타내었다. 그러나 실리카 표면수산기의 Lewis산성도는 수산기의 구조와 무관하였다.

The CNDO/2 calculations have been applied on cluster models for the representative hydroxyls on silica surface to get Wiberg bond orders, total energies, LUMO energies, dipole moments, and formal charge densities. The Bronsted acidities of suggested models for the hydroxyls were explained in terms of Wiberg bond orders. The calculated bond orders of cluster models have been changed remarkably according to the hydrogen bond. However the Lewis acidities of terminal hydroxyls on silica surface were not related to the structure of hydroxyls.

[References]

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[1] Chronister CW, Drago RS, J. Am. Chem. Soc., 115, 4793 (1993)

[2] Garrone E, Kazansky VB, Kustov LM, Sauer J, Senchenya IN, Ugliengo P, J. Phys. Chem., 96, 1040 (1992)

[3] Kiselev AV, Lygin VI, "Infrared Spectra of Surface Compound," Wiley, New York (1975)

[4] Morrow BA, Mcfarlan AJ, Langmuir, 7, 1695 (1991)

[5] Tripp CP, Hair ML, Langmuir, 7, 923 (1991)

[6] Morrow BA, Gay ID, J. Phys. Chem., 92, 5569 (1988)

[7] Pfleiderer B, Albert K, Bayer E, Vande L, Hann VJ, Cramers C, J. Phys. Chem., 94, 4189 (1990)

[8] Leonardelli S, Fsccini L, Fretigny C, Toune P, Legrand AP, J. Am. Chem. Soc., 114, 6412 (1992)

[9] Fierro JLG, "Spectroscopic Characterization of Heterogeneous Catalyst Part B," Elsevier, New York (1990)

[10] 대한화학호, "화학 술어집," 4th ed., 대한화학회, 서울 (1993)

[11] Bronnimann CE, Zeigler RC, Maciel GE, J. Am. Chem. Soc., 110, 2023 (1988)

[12] Mcfarlan AJ, Morrow BA, J. Phys. Chem., 95, 5388 (1991)

[13] Chuang IS, Kinney DR, Bronnimann CE, Zeigler RC, Maciel GE, J. Phys. Chem., 96, 4027 (1992)

[14] Beran S, J. Mol. Catal., 10, 177 (1981)

[15] Ugliengo P, Sanders VR, Garrone E, J. Phys. Chem., 94, 2260 (1990)

[16] Ferrari AM, Ugliengo P, Garrone E, J. Phys. Chem., 97, 2671 (1993)

[17] Dewar MJS, Zoebisch EG, Healy EF, Stewart JJP, J. Am. Chem. Soc., 107, 3902 (1985)

[18] Levine IN, "Quantum Chemistry," 3rd ed., 499, Allyn and Bacon Inc., Boston (1983)

[19] Tsuchiya I, J. Phys. Chem., 86, 4107 (1982)

[20] Morrow BA, Stud. Surf. Sci. Catal., 57A, 161 (1990)

[21] Beran S, J. Phys. Chem., 86, 111 (1982)

[22] Harkless JA, Stillinger DK, Stillinger FH, J. Phys. Chem., 100(4), 1098 (1996)

[23] Pople JA, Beveridge DL, "Approximate Molecular Orbital Theory," McGraw-Hill, New York, 62 (1979)

[24] Dubsky J, Beran S, J. Phys. Chem., 83, 2538 (1979)

[25] Wiberg KB, J. Am. Chem. Soc., 90, 59 (1968)

[26] Roosmalen AJV, Mol JC, J. Chem. Phys., 83, 2485 (1979)