Abstract
Ab initio cluster quantum chemical calculations at the Hartree–Fock and second-order Møller–Plesset perturbation theory levels were carried out to mimic the interactions of water and methanol with a mixture of Cu and Zn metals. It was shown that both molecular and dissociative adsorption of methanol on a mixture of Cu and Zn metal catalyst are preferred over the corresponding adsorptions of water. Estimated transition-state structures for dissociation of methanol into CH·3 and OH· lie about 9.0 and 22.0 kcal/mol higher compared to the dissociated (forward reaction) and molecular adsorption (reverse reaction) complexes, respectively. Based on distinct radicals' bond energies with the active sites of the catalyst considered, it is suggested that hydrogen molecules could be formed through a chain of homogeneous reactions of methyl radicals released into the gas phase with the water and/or methanol molecules.
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REFERENCES
N.Y. Topsøe, J.A. Dumesic and H. Topsøe, J.Catal. 151, 241 (1995).
R.Q. Long and R.T. Yang, J.Am.Chem.Soc. 121, 5595 (1999).
M. Iwamoto, S. Yokoo, S. Sakai and S. Kagawa, J.Chem.Soc., Faraday Trans. 77, 1629 (1981).
M. Anpo, Catal.Surv.Jpn. 1, 169 (1997).
M. Shelef, Chem.Rev. 95, 209 (1995).
Y. Li and N. Armor, J.Appl.Catal. 76, L1 (1991).
N.U. Zhanpeisov, M. Matsuoka, H. Mishima, H. Yamashita and M. Anpo, J.Mol.Struct.(Theochem) 454, 201 (1998).
N.U. Zhanpeisov, M. Matsuoka, SH. Yamashita and M. Anpo, J.Phys.Chem.B 102, 6915 (1998).
N.U. Zhanpeisov, S. Higashimoto and M. Anpo, Int.J.Quant.Chem. 84, 677 (2001).
D.R. Lide (Ed.), CRC Handbook of Chemistry and Physics,79th edn. CRC Press, Boca Raton, FL (1999).
S.V. Didziulis, K.D. Butcher and S.L. Cohen, J.Am.Chem.Soc. 111, 7110 (1989).
M. Saito, T. Fujitani and T. Watanabe, Appl.Catal.A: Gen. 138, 311 (1996).
J.L. Li and T. Inui, Appl.Catal.A: Gen. 137, 105 (1996).
Z. Qian, Z. Xu and H. Hattori, Bull.Chem.Soc.Jpn. 64, 3432 (1991).
B.N. Kuznetsov, M.G. Chudinov and V.I. Yakerson, Kinet.Catal. 39, 207 (1998).
T.P. Minyukova, L.M. Plyasova and T.M. Yur'eva, Kinet.Catal. 30, 356 (1989).
H. Itoh, T. Saito and M. Shizuta, Chem.Lett., 699 (1989).
L. Lapidus and A.Yu. Krylova, Rus.Chem.Rev. 67, 941 (1998).
M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, V.G. Zakrzewski, J.A. Montgomery, R.E. Stratmann, J.C. Burant, S. Dapprich, J.M. Millam, A.D. Daniels, K.N. Kudin, M.C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G.A. Petersson, P.Y. Ayala, Q. Cui, K. Morokuma, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J. Cioslowski, J.V. Ortiz, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.A. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, J.L. Andres, C. Gonzalez, M. Head-Gordon, E.S. Replogle and J.A. Pople, Gaussian 98, Revision A.5.Gaussian, Pittsburgh, PA (1998).
N.C. Handy, P.J. Knowles and K. Somasundran, Theor.Chim.Acta 68, 87 (1985).
D.J. Tozer, N.C. Handy, R.D. Amos, J.A. Pople, R.H. Nobes, X. Yaoming and H.F. Schaefer, Mol.Phys. 79, 777 (1993).
S.F. Boys and F. Bernardi, Mol.Phys. 19, 553 (1970).
I. Mayer and P.R. Surjan, Chem.Phys.Lett. 191, 497 (1992).
P.M. Mayer, J.Phys.Chem.A 103, 5905 (1999).
M. Mavrikakis, L.B. Hansen, J.J. Mortensen, B. Hammer and J.K. Norskov, in: Transition State Modeling for Catalysis, D.G. Truhlar and K. Morokuma (Eds), Chapter 19, p.245.American Chemical Society, Washington,DC (1999).
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Zhanpeisov, N.U., Miyamoto, A. Interactions of water and methanol with a mixture of copper and zinc metals: a theoretical ab initio study. Research on Chemical Intermediates 29, 417–428 (2003). https://doi.org/10.1163/156856703765694354
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DOI: https://doi.org/10.1163/156856703765694354