Conversion of N2O to N2 on MgO (001) surface with vacancy: A DFT study
Yi-Jun Xu
Chemistry Department, Fuzhou University, Fuzhou, Fujian 350002, China State Key Laboratory of Structural Chemistry, Fuzhou, Fujian 350002, China
Search for more papers by this authorJun-Qian Li
Chemistry Department, Fuzhou University, Fuzhou, Fujian 350002, China State Key Laboratory of Structural Chemistry, Fuzhou, Fujian 350002, China
Search for more papers by this authorYong-Fan Zhang
Chemistry Department, Fuzhou University, Fuzhou, Fujian 350002, China State Key Laboratory of Structural Chemistry, Fuzhou, Fujian 350002, China
Search for more papers by this authorYi-Jun Xu
Chemistry Department, Fuzhou University, Fuzhou, Fujian 350002, China State Key Laboratory of Structural Chemistry, Fuzhou, Fujian 350002, China
Search for more papers by this authorJun-Qian Li
Chemistry Department, Fuzhou University, Fuzhou, Fujian 350002, China State Key Laboratory of Structural Chemistry, Fuzhou, Fujian 350002, China
Search for more papers by this authorYong-Fan Zhang
Chemistry Department, Fuzhou University, Fuzhou, Fujian 350002, China State Key Laboratory of Structural Chemistry, Fuzhou, Fujian 350002, China
Search for more papers by this authorAbstract
The adsorption and decomposition of N2O at regular and defect sites of MgO (001) surface have been studied using cluster models embedded in a large array of point charges (PCs) by DFT/B3LYP method. The results indicate that the MgO (001) surface with oxygen vacancies exhibits high catalytic reactivity toward N2O adsorptive-decomposition. It is different from the regular MgO surface or the surface with magnesium vacancies. Much elongation of O-N bond of N2O after adsorption at oxygen vacancy site with O end down shows that O-N bond has been broken with concurrent production of N2, leaving a regular site instead of the original oxygen vacancy site (F center). The MgO (001) surface with magnesium vacancies hardly exhibits catalytic reactivity. It can be concluded that N2O dissociation likely occurs at oxygen vacancy sites of MgO (001) surface, which is consistent with the generally accepted viewpoint in the experiments. The potential energy surface (PES) reflects that the dissociation process of N2O does not virtually need to surmount a given energy barrier.
References
- 1 Stem, A. C; Boubel, W; Turner, D. B; Fox, D. L., Fundamentals of Air Pollution, 2nd ed., Academic Press, Orlando, 1984, p. 1.
- 2 Taylor, K. C., Catal. Rev.-Sci. Eng. 1993, 35, 457.
- 3 Overbury, S. H; Mullins, D. R; Hundey, D. R; Kundakovic, L., J. Catal. 1999, 186, 296.
- 4 Shelef, M; McCabe, R. W., Catal. Today 2000, 62, 35.
- 5 Parvulescu, V. I; Grange, P; Delmon, B., Catal. Today 1998, 46, 233.
- 6 Sorescu, D. C; Rusu, C. N; Yates, J. T., J. Phys. Chem. B 2000, 104, 4408.
- 7 Armor, J. N., Catal. Today 1995, 26, 99.
- 8 Fritz, A; Pitchion, V., Appl. Catal., B 1997, 13, 1.
- 9 Rodriguez, J. A; Jirsak, T; Freitag, A; Larese, J; Maiti, A., J. Phys. Chem. B 2000, 104, 7439.
- 10 Rodriguez, J. A; Jirsak, T; Dvorak, J; Rischer, D., J. Phys. Chem. B 2000, 104, 319.
- 11 Yudanov, I; Pacchioni, G; Neyman, K; Rösch, N., J. Phys. Chem. B 1997, 101, 2786.
- 12 Yanagisawa, Y; Kuramoto, K; Yamabe, S. I., J. Phys. Chem. B 1999, 103, 11078.
- 13 Lu, X; Xu, X; Wang, N. Q; Zhang, Q. E., J. Phys. Chem. B 1999, 103, 5657.
- 14 Rodriguez, J. A; Jirsak, T; Kim, J. Y; Larese, J. Z; Maiti, A., Chem. Phys. Lett. 2000, 330, 475.
- 15 Lu, X; Xu, X; Wang, N. Q; Zhang, Q. E., J. Phys. Chem. B 1999, 103, 3373.
- 16 Freund, J. J., Faraday Discuss. 1999, 114, 1.
- 17 Valentin, C. D; Pacchioni, G; Bredow, T; Dominguez-Ariza, D; Illas, F., J. Chem. Phys. 2002, 117, 1199.
- 18 Dickinson, R. E; Cicerone, R. J., Nature 1986, 319, 109.
- 19 Arai, N. J., Inst. Energy 1994, 67, 61.
- 20 Satsuma, A; Maeshima, H; Watanabe, K; Hattor, T., Energy Convers. Manage. 2001, 42, 1997.
- 21 Kapteijn, F; Rodriguez-Mirasol, J; Moulijn, J. A., Appl. Catal., B 1996, 9, 25.
- 22 Snis, A; Miettinen, H., J. Phys. Chem. B 1998, 102, 2555.
- 23 Nakamura, M; Mitsuhashi, H; Takezawa, N., J. Catal. 1992, 138, 686.
- 24 Karlsen, E. J; Nygren, M. A; Pettersson, L. G. M., J. Phys. Chem. A 2002, 106, 7868.
- 25 Karlsen, E. J; Pettersson, L. G. M., J. Phys. Chem. B 2002, 106, 5719.
- 26 Snis, A; Stromberg, D; Panas, I., Surf. Sci. 1993, 292, 317.
- 27 Snis, A; Pana, I., Surf. Sci. 1998, 412/413, 477.
- 28 Wyckoff, R. W. G., Crystal Structures, Wiley, New York, 1963, p. 126.
- 29 Sauer, J; Ugliengo, P; Garrone, E; Saunders, V. R., Chem. Rev. 1994, 94, 2095.
- 30 Pacchioni, G; Clotet, A; Ricart, J. M., Surf. Sci. 1994, 315, 337.
- 31 Pacchioni, G; Minerva, T; Bagus, P. S., Surf. Sci. 1992, 275, 450.
- 32 Pacchioni, G; Cogliandro, G; Bagus, P. S., Surf. Sci. 1991, 255, 344.
- 33 Lu, X; Xu, X; Wang, N; Zhang, Q; Ehara, M; Nakatsuji, H., Chem. Phys. Lett. 1998, 291, 457.
- 34 Ferrari, A. M; Pacchioni, G., J. Phys. Chem. 1996, 100, 9032.
- 35 Ferrari, A. M; Pacchioni, G., J. Chem. Phys. 1997, 107, 2066.
- 36 Xu, Y. J; Li, J. Q; Zhang, Y. F; Chen, W. K., Surf. Sci. 2003, 525, 13.
- 37 Pacchioni, G; Cogliandro, C; Bagus, P. S., Int. J. Quantum Chem. 1992, 42, 1115.
- 38 Stevens, W. J; Basch, H; Krauss, M., J. Chem. Phys. 1984, 81, 6026.
- 39 Boys, S; Bernardi, F., Mol. Phys. 1970, 19, 553.
- 40 Becke, A. D., J. Chem. Phys. 1993, 98, 5648.
- 41 Lee, C; Yang, W; Parr, R. G., Phys. Rev. B 1997, 37, 785.
- 42 Frisch, M. J; Trucks, G. W; Schlegel, H. B; Scuseria, G. E; Robb, M. A; Cheeseman, J. R; Zakrzewski, V. G; Montgomery, J. A; Stratmann, Jr. R. E; Burant, J. C; Dapprich, S; Millam, J. M; Daniels, A. D; Kudin, K. N; Strain, M. C; Farkas, O; Tomasi, J; Barone, V; Cossi, M; Cammi, R; Mennucci, B; Pomelli, C; Adamo, C; Clifford, S; Ochterski, J; Petersson, G. A; Ayala, P. Y; Cui, Q; Morokuma, K; Malick, D. K; Rabuck, A. D; Raghavachari, K; Foresman, J. B; Cioslowski, J; Ortiz, J. V; Stefanov, B. B; Liu, G; Liashenko, A; Piskorz, P; Komaromi, I; Gomperts, R; Martin, R. L; Fox, D. J; Keith, T; Al-Laham, M. A; Peng, C. Y; Nanayakkara, A; Gonzalez, C; Challacombe, M; Gill, P. M. W; Johnson, B; Chen, W; Wong, M. W; Andres, J. L; Gonzalez, C; Head-Gordon, M; Replogle, E. S; Pople, J. A., Gaussian 98, Revision A. 3, Gaussian, Inc., Pittsburgh PA, 1998.
- 43 Ziegler, T., Chem. Rev. 1991, 91, 651.
- 44 Weast, R. C., Handbook of Chemistry and Physics, CRC Press, Cleveland, 1979, p. 224.
- 45 Damin, A; Dovesi, R; Zecchina, A; Ugliengo, P., Surf. Sci. 2001. 479, 255.
- 46 Valentin, C. D; Pacchioni, G; Chiesa, M; Giamello, E; Abbet, S; Heiz, U., J. Phys. Chem. B 2002, 106, 1637.
- 47 Kantorovich, L. N., Surf. Sci. 1995, 343, 221.
- 48 Clluccia, S; Barton, A., J. Chem. Soc., Faraday Trans. I 1981, 77, 2203.
- 49 Sushko, P. V; Shluger, A. L; Catlow, C. R. A., Surf. Sci. 2000, 450, 153.
- 50 Nada, R; Hess, A. C., Surf. Sci. 1995, 336, 353.
- 51 Winter, E. S. R., J. Catal. 1974, 34, 431.
- 52 Winter, E. S. R., J. Catal. 1974, 34, 440.
- 53 Winter, E. S. R., J. Catal. 1970, 19, 32.
- 54 Valentin, C. D; Pacchioni, G., J. Phys. Chem. B 2002, 106, 7666.
- 55 Marchese, L; Coluccia, S; Martra, C; Giamello, E; Zecchina, A., Mater. Chem. Phys. 1991, 29, 437.
- 56 Giamello, E; Murphy, D; Marchese, L; Martra, G; Zecchina, A., J. Chem. Soc., Faraday Trans. 1993, 89, 3715.
- 57 Che, M; Tench, A. J., Adv. Catal. 1983, 32, 1.
- 58 Giamello, E; Murphy, D; Garrone, E; Zecchina, A., Spectrochim. Acta A 1993, 49, 1323.
