Molecular Modeling of Heterogeneous Catalytic Reactivity
R. A. van Santen,
M. Neurock,
R. A. van Santen
Eindhoven University of Technology, Eindhoven, The Netherlands
Search for more papers by this authorR. A. van Santen,
M. Neurock,
R. A. van Santen
Eindhoven University of Technology, Eindhoven, The Netherlands
Search for more papers by this authorFirst published: 13 December 2002
Abstract
The approach to model heterogeneous catalysis based on mechanistic molecular insights derived from quantum chemical methods is explained by addressing key fundamental issues that control catalysis and using many examples. The Sabatier principle is used as the leading concept to understood and predict catalyst activity—catalyst composition relationships. The reaction energy diagram approach is used to help assess rate-limiting steps and selectivity principles for catalytic reaction. In order to predict catalytic kinetics, quantum chemical mechanistic information has to be complemented with information on the effects of reaction environment on the elementary steps. This includes changes due to interactions between adsorbed species as well as adsorbate-induced surface reconstruction.
QM results can subsequently be used along with transition state reaction theory to predict elementary rate constants for elementary steps that make up the overall catalytic cycle. This information along with data on the effects of the reaction environment provide the input for dynamic Monte Carlo methods that can ultimately simulate overall catalytic kinetics. This approach can be used to follow both catalytic activity as well as selectivity. Periodic trends in surface reactivity are discussed for transition metal oxide, reducible oxide, hydrodesulfurization, and zeolite catalysis.
Bibliography
- 1 P. Sabatier, La Catalyse en Chime Organique, Librairie Polytechnique, Paris, 1913.
- 2 T. Wolkenstein, Adv. Catal. 12, 189 (1962); G. M. Schwab, Discuss. Far. Soc. 8, 166 (1950); M. Boudart, J. Am. Chem. Soc. 72, 1040 (1950); A. Couper and D. D. Eley, Discuss. Far. Soc. 8, 172 (1952).
- 3
M. Boudart and
G. Djéga-Mariadassou,
Kinetics of Heterogeneous Catalytic Reactions,
Princeton University Press,
Princeton, N.J.,
1984.
10.1515/9781400853335 Google Scholar
- 4 B. Hammer and J. Norskov, Adv. Catal. 45, 71–129 (2000).
- 5 R. A. van Santen and M. Neurock, Catal. Rev. Sci. Eng. 37, 557 (1995).
- 6
R. A. van Santen,
Theoretical Heterogeneous Catalysis,
World Scientific,
Singapore,
1991.
10.1142/1210 Google Scholar
- 7 D. G. Truhlar and R. Morokuma, Transition State Modeling in Catalysis (ACS Symposium Series 721), American Chemical Society, Washington, D.C., 1999.
- 8
J. R. Whitter and
H. Yang,
Surf. Sci. Rep.
24,
55
(1996).
10.1016/0167-5729(96)80004-5 Google Scholar
- 9 P. E. M. Siegbahn, Adv. Chem. Phys. 93, 333 (1996).
- 10 M. Scheffler, C. Stompt, in K. Horn and M. Scheffler, eds., Handbook of Surface Science, Vol. 2: Electronic Structure, Elsevier, Amsterdam, 1999.
- 11 A. Eichler and G. Hafner, Phys. Rev. B 59, 5960 (1999).
- 12 M. C. Payne, M. P. Teter, D. C. Alan, T. A. Arias, and J. D. Joannopoulos, Rev. Mod. Phys. 64, 1045 (1992).
- 13 S. Glasstone, K. J. Laidler, and H. Eyring, The Theory of Rate Processes, McGraw-Hill, New York, 1941.
- 14
R. A. van Santen and
W. M. H. Sachtler,
Adv. Catal.
26,
69
(1977).
10.1016/S0360-0564(08)60070-X Google Scholar
- 15 G. A. Somorjai, Introduction to Surface Chemistry and Catalysis, John Wiley & Sons, Inc., New York, 1994.
- 16 C. T. Au and M. W. Roberts, Nature 319, 206 (1986); M. W. Roberts, Surf. Sci. 299/300, 769 (1994).
- 17
R. A. van Santen and
J. W. Niemantsverdriet,
Chemical Kinetics and Catalysis,
Plenum Press,
New York,
1995.
10.1007/978-1-4757-9643-8 Google Scholar
- 18 S. J. Lombardo and A. T. Bell, Surf. Sci. Rep. 13, 1 (1991).
- 19 V. P. Zhdanov, Surf. Sci. Rep. 12, 183 (1991).
- 20
V. P. Zhdanov,
Elementary Physics Chemical Processes on Solid Surfaces,
Plenum Press,
New York,
1991.
10.1007/978-1-4899-2373-8 Google Scholar
- 21 R. J. Gelten, R. A. van Santen, and A. P. J. Jansen, in P. B. Balbuna and J. M. Seminario, eds., From Classical to Quantum Methods, Molecular Dynamics, Elsevier, Amsterdam, 1999, Chapt. 18.
- 22 D. Frenkel and B. Smit, Understanding Molecular Simulations, Academic Press, New York, 1996.
- 23 H. A. Kramers, Physica 7, 284 (1940).
- 24
F. Keil,
Diffusion und Chemische Reaktionen in der Gas/Feststoff Katalyse,
Springer-Verlag,
New York,
1999.
10.1007/978-3-642-60224-5 Google Scholar
- 25 F. J. Keil, Chem.-Ing.-Tech. 68, 639 (1996).
- 26 J. A. Dumesic, A. A. Trenino, B. A. Mulligan, L. A. Greppi, V. R. Balse, K. T. Sarunoski, C. E. Beall, T. Katoaka, and D. F. Rudd, Ind. Eng. Chem. Rev. 26, 1399 (1987).
- 27 J. A. Dumesic, D. F. Rudd, C. M. Apiricio, J. E. Rekoska, and A. A. Trenino, The Microkinetics of Heterogeneous Catalysis, American Chemical Society, Washington, D.C., 1993.
- 28 P. Stolze, Physica Scripta 36, 824 (1987).
- 29 E. W. Hansen and M. Neurock, Chem. Eng. Sci. 54, 3411 (1999).
- 30 F. Ercolessi, M. Parinello, and E. Tosatti, Surf. Sci. 177, 314 (1986); F. Ercolessi, M. Parinello, and E. Tosatti, Philos. Mag. A 58, 213 (1988).
- 31 B. Smit and T. L. M. Maesen, Nature 374, 42 (1995).
- 32 H. van Koningsveld, J. C. Jansen, and H. van Bekkum, Zeolites 10, 235–242 (1990).
- 33 M. Iwamoto, M. Misono, Y. Morooka, and S. Kimura, Stud. Surf. Sci. Catal. 54, (1992).
- 34 J. M. Thomas and W. J. Thomas, Principles and Practice of Heterogeneous Catalysis, VCH, Weinheim, 1997.
- 35 J. Fahrenfort, L. L. van Reynen, and W. M. H. Sachtler, in J. H. de Boer, ed., The Mechanism of Heterogeneous Catalysis, Elsevier, Amsterdam, 1960.
- 36 R. R. Chianelli and T. A. Pecoraro, J. Catal. 86, 226 (1984).
- 37
J. M. Sinfelt,
Prog. Solid State Chem.
10,
55
(1975);
10.1016/0079-6786(75)90006-0 Google ScholarCatal. Lett. 9, 159 (1991).
- 38 G. Ertl, Catalysis 4, 210 (1983).
- 39 T. Engel and G. Ertl, Adv. Catal. 28, 1 (1979).
- 40 P. van Ragué Schleyer, ed., Encyclopedia of Computational Chemistry, John Wiley & Sons, Inc., New York, 1998.
- 41 R. A. van Santen, P. W. N. M. van Leuven, J. A. Moulijn, and B. A. Averill, Catalysis: An Integrated Approach (Studies in Surface Science and Catalysis 123), Elsevier, Amsterdam, 1999.
- 42 M. Neurock and R. A. van Santen, J. Am. Chem. Soc. 116, 4427 (1994).
- 43 M. Neurock, Appl. Catal., A 160, 169 (1997).
- 44 R. A. van Santen, P. W. N. M. van Leeuwen, J. A. Moulijn, and B. A. Averill, Catalysis: An Integrated Approach (Studies in Surface Science and Catalysis 150), Elsevier, Amsterdam, 1999.
- 45 A. Yakovlev and R. A. van Santen, manuscript in preparation.
- 46 I. M. Ciobica, F. Fréchard, R. A. van Santen, A. W. Kleyn, and J. Hafner, Chem. Phys. Lett. 311, 185 (1999).
- 47 I. M. Ciobica, F. Fréchard, and R. A. van Santen, in manuscript preparation.
- 48 J.-F. Paul and P. Sautet, J. Phys. Chem. B. 102, 1578–1585 (1998).
- 49 I. M. Ciobica, F. Fréchard, R. A. van Santen, A. Kleyn, and J. Hafner, J. Phys. Chem. B 104, 3364 (2000).
- 50 A. Gotti and R. Prins, J. Catal. 175, 302–311 (1998); A. F. Gusovius, T. C. Watling, and R. Prins, Appl. Catal., A. 188(1/2), 187–199 (1999); A. Gotti and R. Prins, Catal. Lett. 37(3/4), 143–151 (1996).
- 51 M. Neurock, Top. Catal. 9, 135 (1999).
- 52 P. J. Berlowitz and D. W. Goodman, J. Catal. 108, 364–368 (1987).
- 53 A. B. Anderson, R. W. Grimes, and S. Y. Hong, J. Phys. Chem. 91, 4245 (1987); A. B. Anderson, J. Chem. Phys. 62, 1187 (1975).
- 54 A. de Koster, A. P. J. Jansen, R. A. van Santen, and J. J. C. Geerlings, Faraday Discuss. Chem. Soc. 87, 263 (1989); A. D. van Langeveld, A. de Koster, and R. A. van Santen, Surf. Sci. 225, 143 (1990).
- 55 T. Zambelli, J. Winterlin, J. Trost, and G. Ertl, Science 273, 1688 (1996).
- 56 S. Dahl, A. Logadottir, R. C. Egeberg, J. H. Larsen, I. Chorkendorf, E. Törnvist, and J. K. Norskov, Phys. Rev. Lett. 83, 1814 (1999).
- 57 B. Hammer, Phys. Rev. Lett. 83, 3681–3684 (1999).
- 58 M. Mavrikakis, L. B. Hansen, B. Hammer, and J. K. Norskov, Phys. Rev. Lett. 81, 2819–2822 (1998); M. Mavrikakis, L. B. Hansen, J. J. Mortensen, B. Hammer, and J. K. Norskov, ACS Symposium Series 721, 245 (1999).
- 59 C. G. M. van de Moesdijk, in J. R. Rosak, ed., Catalysis of Organic Reactions in Chemical Industries, Vol. 18, Marcel Dekker, Inc., New York, 1984, p. 379.
- 60 S. Sagai, T. Takeuchi, T. Bon, H. Miki, R. Kawasaki, and T. Kioka, Surf. Sci. 282, 67 (1993).
- 61 M. Neurock and R. A. van Santen, J. Am. Chem. Soc. 116, 6860 (1994).
- 62 Lu. Gang, J. van Grondelle, B. G. Anderson, and R. A. van Santen, J. Catal. 186, 100 (1999).
- 63 J. K. Norskov, Surf. Sci. 299/300, 690–706 (1994).
- 64 F. Fréchard and R. A. van Santen, Surf. Sci. 407, 200 (1998).
- 65 M. A. van Hove and G. A. Somorjai, Surf. Sci. 299/300, 487–501 (1994).
- 66 M. Bowker, Top. Catal. 3, 461–468 (1996); M. Bowker and F. M. Leibsle, Catal. Lett. 38(1/2), 123–126 (1996); S. Pulston, A. H. Jones, R. A. Bennett, and M. Bowker, J. Phys: Condens. Matter 8, L765–L771 (1996); M. Bowker, S. Pulston, R. A. Bennett, and P. Stone, J. Phys.: Condens. Matter 10, 7713–7722 (1998); S. Silva, R. M. Lemor, and F. M. Leibsle, Surf. Sci. 421(1/2), 135–145, 146–156 (1999).
- 67 R. A. van Santen and C. P. M. de Groot, J. Catal. 98, 530 (1986).
- 68 C. Song, J. N. Garces, and Y. Sugi, eds., Shape Selective Catalysis (ACS Symposium Series 738), American Chemical Society, Washington, D.C., 2000.
- 69 S. R. Blaszkowski, M. A. C. Nascimento, and R. A. van Santen, J. Phys. Chem. 100, 3463 (1996).
- 70 M. A. van Daelen, K. S. Li, J. M. Newsam, and R. A. van Santen, Chem. Phys. Lett. 226, 100 (1994).
- 71 H. Burghgraef, A. P. J. Jansen, and R. A. van Santen, J. Chem. Phys. 98, 8810 (1993).
- 72 H. Jónsson, G. Mills, and W. Jacobsen, Enrico Fermi Summer School (Lenco '97) Proceedings, Italy, 1997.
- 73 P. van Beurden and G. J. Kramer, submitted.
- 74 M. S. Daw, S. M. Foiles, and M. I. Baskes, Mat. Sci. Rep. 9, 251–310 (1993); M. I. Baskes, Phys. Rev. B 46, 2727–2742 (1992).
- 75 M. Neurock and A. T. Bell, NSF Workshop Report: Theory and Modeling of Catalytic Reaction Systems, National Science Foundation, Washington, D.C., 1996.
- 76 F. Keil, J. Hinderer, and A. R. Garayhi, Catal. Today 50, 637–650 (1999).
- 77 R. I. Masel, Principles of Adsorption and Reaction on Solid Surfaces, John Wiley & Sons, Inc., New York, 1996.
- 78 G. Froment and K. B. Bischoff, Chemical Reactor Analysis and Design, 2nd ed., John Wiley & Sons, Inc., New York, 1990.
- 79 J. A. Dumesic, D. F. Rudd, L. M. Aparicio, J. E. Rekoske, and A. A. Trevino, The Microkinetics of Heterogeneous Catalysis, American Chemical Society, Washington, D.C., 1993.
- 80
M. Boudart and
G. Djega-Mariadassou,
Kinetics of Heterogeneous Catalytic Reactions, Princeton University Press,
Princeton,
N.J.,
1984.
10.1515/9781400853335 Google Scholar
- 81 J. A. Dumesic and A. A. Trevino, J. Catal. 116, 119–129 (1989).
- 82 P. Stoltze and J. K. Norskov, J. Catal. 110, 1–10 (1988).
- 83 J. B. McDermott, C. Libanati, C. Lamarca, and M. T. Klein, Ind. Eng. Chem. Res. 29, 22–29 (1990).
- 84 C. Libanati, C. LaMarca, and M. T. Klein, Abstr. Am. Chem. Soc. 37(Part 1), 201 (1991).
- 85 M. Neurock, C. Libanati, A. Nigam, and M. T. Klein, Chem. Eng. Sci. 45, 2083–2088 (1990).
- 86 M. Neurock, S. Stark, and M. T. Klein, Molecular Simulation of Kinetic Interactions in Complex Mixtures, Computer-Aided Design of Catalysts, Vol. 55: Marcel Dekker, Inc., New York, 1993.
- 87 C. Libanati, Thermal Degradation of Poly(arylether Sulfones), University of Delaware, 1991.
- 88 P. V. Joshi, A. Kumar, T. I. Mizan, and M. T. Klein, Energy Fuel 13, 1135 (1999).
- 89 S. C. Korre and M. T. Klein, Catal. Today 31, 79–91 (1996).
- 90 W. D. Provine and M. T. Klein, Chem. Eng. Sci. 49, 4223–4248 (1994).
- 91 W. Feng, E. Vynckier, and G. F. Froment, Ind. Eng. Chem. Res. 32, 2997–3005 (1993).
- 92 M. A. Baltanas, K. K. Vanraemdonck, G. F. Froment, and S. R. Mohedas, Ind. Eng. Res. Chem. 8, 899–910 (1989).
- 93 G. F. Froment, Chem. Eng. Sci. 47, 2163–2177 (1992).
- 94 K. Binder, ed., in Monte Carlo Methods in Statistical Physics ( Topics in Current Physics, Vol. 7), Springer-Verlag, New York, 1979.
- 95 P. Dufour, M. Dumont, V. Chabart, and J. Lion, Comp. Chem. 13, 25–32 (1989).
- 96 S. M. Dunn and J. B. Anderson, J. Chem. Phys. 102, 2812–2815 (1995).
- 97 K. A. Fichthorn, E. Gulari, and R. M. Ziff, Surf. Sci. 243, 273–294 (1991).
- 98 A. P. J. Jansen, Comp. Phys. Comm. 86, 1–12 (1994).
- 99 H. C. Kang and W. H. Weinberg, Chem. Rev. 95, 667–676 (1995).
- 100 B. Meng and W. H. Weinberg, J. Chem. Phys. 100, 5280 (1994).
- 101 B. Meng and W. H. Weinberg, J. Chem. Phys. 102, 9435 (1995).
- 102 B. Meng and W. H. Weinberg, Surf. Sci. 364, 151–163 (1996).
- 103 B. Meng and W. H. Weinberg, Surf. Sci. 374, 17 (1997).
- 104 A. Milchev and K. Binder, Surf. Sci. 164, 1–18 (1985).
- 105 R. M. Nieminen and A. P. J. Jansen, Appl. Catal., A: Gen. 160, 99–123 (1997).
- 106 M. Silverberg and A. Ben-Shaul, J. Chem. Phys. 87, 3178 (1987).
- 107 M. Silverberg and A. Ben-Shaul, J. Stat. Phys. 52, 1179 (1988).
- 108 M. Silverberg and A. Ben-Shaul, Surf. Sci. 214 (1989).
- 109 V. P. Zhdanov and P. R. Norton, Surf. Sci. 350, 271–276 (1996).
- 110 V. P. Zhdanov, J. L. Sales, and R. O. Unac, Surf. Sci. 381, L599–L604 (1997).
- 111 V. P. Zhdanov and B. Kasemo, Surf. Sci. 412/413, 527–543 (1998).
- 112 R. M. Ziff, E. Gulari, and Y. Barshad, Phys. Rev. Lett. 56, 2553 (1986).
- 113 L. K. Doraiswamy and B. D. Kulkarni, The Analysis of Chemically Reacting Systems: A Stochastic Approach, Gordon and Breach Science, New York, 1987.
- 114 V. P. Zhdanov, Surf. Sci. 133, 469–483 (1983).
- 115 V. P. Zhdanov, Surf. Sci. Rep. 12, 183–242 (1991).
- 116 V. P. Zhdanov and B. Kasemo, Physica D 70, 383 (1994).
- 117 V. P. Zhdanov and P. R. Norton, Surf. Sci. 312, 441–449 (1994).
- 118 V. P. Zhdanov, Surf. Rev. Lett. 3, 1555–1559 (1996).
- 119 V. P. Zhdanov and B. Kasemo, Surf. Sci. 405, 27–37 (1998).
- 120 V. P. Zhdanov, Surf. Sci. 426, 345–357 (1999).
- 121 H. J. Kreuzer, Surf. Sci. 238, 305–316 (1990).
- 122 H. J. Kreuzer, Appl. Phys. A 51, 491–497 (1990).
- 123 H. J. Kreuzer and J. Zhang, Appl. Phys. A 51, 183–190 (1990).
- 124 S. H. Payne and H. J. Kreuzer, Surf. Sci. 222, 404–429 (1989).
- 125 S. H. Payne and H. J. Kreuzer, Surf. Sci. 338, 261–278 (1995).
- 126 E. W. Hansen and M. Neurock, Surf. Sci. 441, 410–424 (1999).
- 127 E. W. Hansen and M. Neurock, Surf. Sci. 464(2/3), 91–107 (2000).
- 128 E. W. Hansen and M. Neurock, J. Catal. 196, 241–252 (2001).
- 129 E. W. Hansen and M. Neurock, unpublished work (2000).
- 130 M. Neurock and E. W. Hansen, Comp. Chem. Eng. 22, 1045 (1998).
- 131 D. T. Gillespie, J. Comp. Phys. 22, 403 (1976).
- 132 D. T. Gillespie, J. Phys. Chem. 81, 2340 (1977).
- 133 K. Fichthorn, E. Gulari, and R. Ziff, Chem. Eng. Sci. 44, 1403–1411 (1989).
- 134 D. Gupta and C. S. Hirtzel, Chem. Phys. Lett. 149, 527–533 (1988).
- 135 A. S. McLeod and L. F. Gladden, Catal. Lett. 43, 189–194 (1997).
- 136 J. S. Turner, J. Phys. Chem. 81, 2379–2406 (1977).
- 137 S. Titmuss, A. Wander, and D. A. King, Chem. Rev. 96, 1291–1305 (1996).
- 138 Q. Ge and D. King, Adv. Catal. 45, 207 (2000).
- 139 H. J. Kreuzer and S. H. Payne, Equilibria and Dynamics of Gas Adsorption on Heterogeneous Solid Surfaces, Vol. 104, Elsevier, Amsterdam, 1997.
- 140 C. Stampfl, H. J. Kreuzer, S. H. Payne, H. Pfnur, and M. Scheffler, Phys. Rev. Lett. 83, 2993 (1999).
- 141 E. Shustorovich, Surf. Sci. 150, L115 (1985).
- 142 E. Shustorovich, Surf. Sci. 175, 561 (1986).
- 143 E. Shustorovich, Surf. Sci. Rep. 6, 1 (1986).
- 144 E. Shustorovich, Acc. Chem. Res. 21, 183 (1988).
- 145 E. Shustorovich, Surf. Sci. 205, 336 (1988).
- 146 E. Shustorovich, Adv. Catal. 37, 101 (1990).
- 147 E. Shustorovich and A. T. Bell, Surf. Sci. 253, 386 (1991).
- 148 E. Shustorovich and A. T. Bell, Surf. Sci. 248, 359 (1991).
- 149 E. Shustorovich and A. T. Bell, Surf. Sci. 289, 127 (1989).
- 150 E. Shustorovich, Surf. Sci. Rep. 31, 1–112 (1998).
- 151 A. T. Bell and E. Shustorovich, Sur. Sci. 235, 343–350 (1990).
- 152 H. L. Sellers, Surf. Sci. 294, 650 (1993).
- 153 H. L. Sellers, Surf. Sci. 310, 281 (1994).
- 154 H. L. Sellers and E. Shustorovich, Surf. Sci. 356, 209 (1996).
- 155 D. Duca, G. La Manna, and M. R. Russo, Phys. Chem. Chem. Phys. 1, 1375 (1999).
- 156 D. Duca, P. Baranyai, and T. Vidoczy, J. Comp. Chem. 19, 396–403 (1998).
- 157 D. Mei, E. W. Hansen, and M. Neurock, J. Phys. Chem. B, accepted.
- 158 J. Horiuti and M. Polanyi, Trans. Faraday Soc. 30, 1164 (1934); E. Stuve, R. J. Madix, J. Phys. Chem. 85, 105–112 (1985).
- 159 M. Neurock and R. A. van Santen, J. Phys. Chem. B, 104, 1127 (2000).
- 160 V. Ponec and G. C. Bond, Catalysis by Metals and Alloys, Vol. 95, Elsevier, Amsterdam, 1995.
- 161 J. A. Gates and L. L. Kesmodel, Surf. Sci. 120, L461 (1982).
- 162 V. Pallasana, M. Neurock, and G. Coulston, Catal. Today 50, 589 (1999).
- 163 S. Hub, L. Milaire, and R. Touronde, Appl. Catal. 63, 307 (1988).
- 164 M. Neurock and R. A. van Santen, J. Am. Chem. Soc. 116, 4427 (1994).
- 165 R. A. van Santen, M. C. Zonnevylle, and A. P. J. Jansen, Philos. Trans. R. Soc. London, A 341, 269 (1992).
- 166 F. Fréchard, R. A. van Santen, A. Siokou, J. W. Niemantsverdriet, and J. Hafner, J. Chem. Phys. 111, 8124 (1999).
- 167
R. Hoffmann,
Solids and Surfaces, a Chemist's View of Bonding in Extended Structures,
VCH,
Weinheim,
1988.
10.21236/ADA196638 Google Scholar
- 168
R. A. van Santen, and
E. J. Baerends,
Theoretical Models of Chemical Bonding,
Springer-Verlag,
New York,
1991.
10.1007/978-3-642-58177-9_9 Google Scholar
- 169 J. K. Norskov and N. P. Lang, Phys. Rev. B 21, 2136 (1980); J. K. Norskov, Phys. Rev. B 26, 2875 (1982); J. K. Norskov, Rep. Progr. Phys. 53, 1253 (1990).
- 170 R. A. van Santen, J. Chem. Soc., Faraday Trans. 1 83, 1915 (1987).
- 171 W. A. Harrison, The Electronic Structure and the Properties of Solids, Freeman, San Francisco, Calif., 1980.
- 172 D. F. Shriver, P. W. Atkins, and C. H. Langford, Inorganic Chemistry, Oxford, University, Oxford, 1994, p. 248.
- 173 C. J. Ballhausen, Introduction to Ligand Field Theory, McGraw-Hill, New York, 1962.
- 174 D. A. Dowden and D. Wells, Actes 2nd Congress Int. Catalysis, Paris, 1961, p. 1499.
- 175 D. A. Dowden, Endeavor 24, 69 (1965).
- 176 J. C. Volta and J. L. Portefaix, Appl. Catal. 18, 1 (1985).
- 177
J. Haber, in
C. Morterra,
A. Zecchina, and
G. Costa, eds.,
Structure and Reactivity of Surfaces,
Elsevier,
Amsterdam,
1989,
p. 447.
10.1016/S0167-2991(08)60707-7 Google Scholar
- 178 H.-J. Freund, Angew Chem., Int. Ed. Engl. 36, 452 (1997).
- 179 L. Pauling, The Nature of the Chemical Bond, Oxford University Press, 1950, p. 384.
- 180
R. A. V. Santen,
Theoretical Heterogeneous Catalysis,
World Scientific,
Singapore,
1991,
pp. 289–293.
10.1142/1210 Google Scholar
- 181 K. Refson, R. A. Wogelius, D. G. Fraser, M. C. Payne, M. H. Lee, and V. Milman, Phys. Rev. B 52, 823 (1995).
- 182 W. Langel and M. Parinello, J. Chem. Phys. 103, 3240 (1995).
- 183 P. J. D. Lindan, N. M. Harrison, J. M. Holender, and M. J. Gillan, Chem. Phys. Lett. 261, 246 (1996).
- 184 J. Woning and R. A. van Santen, Chem. Phys. Lett. 101, 541 (1983).
- 185 G. Pacchioni, A. M. Ferrari, A. M. Marquez, and F. Illas, J. Comp. Chem. 18, 617 (1997); M. A. Nygren, L. G. M. Petterson, Z. Barandarion, and L. Seyo, J. Chem. Phys. 100, 2010 (1994).
- 186 A. Bielanski and J. Haber, Catal. Rev.—Sci. Eng. 19(1), 1 (1987).
- 187 K. Brückman, J.-M. Tatibouët, M. Che, E. Serwicka, and J. Haber, J. Catal. 139, 455 (1993).
- 188 J. N. Allison and W. A. Goddard, in R. K. Graselli and J. Z. Brazdil, eds., Solid State Chemistry in Catalysis (ACS Symposium Series 279), American Chemical Society, Washington, D.C., 1985, p. 23.
- 189 M. D. Nygren and L. G. M. Petterson, J. Chem. Phys. 105, 9339 (1996); H.-J. Freund, Surf. Sci. 423, 90 (1999).
- 190 B. C. Wiegand and C. M. Friend, Chem. Rev. 92, 491 (1992).
- 191 P. Raybaud, J. Hafner, G. Kresse, S. Kasztelan, and H. Toulhoat, J. Catal. 190, 128–143 (2000).
- 192 P. Raybaud, J. Hafner, G. Kresse, S. Kasztelan, and H. Toulhoat, J. Catal. 189, 129–146 (2000).
- 193 P. Raybaud, G. Kresse, J. Hafner, and H. Toulhoat, J. Phys.: Condens Matter 9, 11085 (1997).
- 194 P. Raybaud, J. Hafner, G. Kresse, and H. Toulhoat, J. Phys.: Condens Matter 9, 11107 (1997).
- 195 P. Raybaud, J. Hafner, G. Krenc, and H. Toulhoat, Phys. Rev. Lett. 80, 1481 (1998).
- 196 L. S. Byskov, B. Hammer, J. K. Norskov, B. S. Clausen, and H. Topsøe, Catal. Lett. 47, 177 (1997); L. S. Byskov, J. K. Norskov, B. S. Clausen, and H. Topsøe, J. Catal. 187, 109 (1999).
- 197 H. Nakamura, A. Travert, and R. A. van Santen, J. Am. Catal. Soc. 124, 7084 (2002).
- 198 S. M. A. M. Bouwens, D. C. Koningsberger, V. H. J. de Beer, S. P. A. Louwers, and R. Prins, Catal. Lett. 5, 273 (1990).
- 199 R. J. Angelici, in T. Weber, R. Prins, and R. A. van Santen, eds., Transition Metal Sulphides: Density and Catalysis, NATO-ASI, Kluwer, Academic Publishers, Boston, Mass., 1998, pp. 89–127.
- 200 M. C. Zonnevylle, R. Hoffmann, and S. Harris, Surf. Sci. 199, 320 (1998).
- 201 M. Neurock and R. A. van Santen, J. Am. Chem. Soc. 116, 4427 (1994).
- 202 H. Topsøe, B. S. Clausen, N.-I. Topsøe, J. K. Norskov, C. V. Ovesen, and G. J. C. Jacobsen, Bull. Soc. Chem. Belg. 104, 283 (1995).
- 203 T. A. Pecoraro and R. R. Chianelli, J. Catal. 67, 430 (1981).
- 204 V. Moruzzi, J. F. Janak, and A. R. Williams, Calculated Electronic Properties of Metals, Pergamm Press, New York, 1998.
- 205 E. J. M. Hensen, H. J. A. Brons, G. M. H. J. Lardinois, V. H. J. de Beer, J. A. R. van Veen, and R. A. van Santen, J. Catal. 187, 95 (1999).
- 206 N. Hermann, M. Brovson, and H. Topsøe, Catal. Lett. 65, 169 (2000).
- 207 J. K. Norskov, B. S. Clausen, and H. Topsøe, J. Catal. 13, 1 (1992).
- 208 S. Harris, Chem. Phys. 67, 229 (1982); S. Harris, Chem. Phys. Lett. 101, 603 (1983).
- 209 T. S. Smit and R. H. Johnson, Catal. Lett. 28, 361 (1994).
- 210 E. J. M. Hensen, M. J. Vissenberg, V. H. J. de Beer, J. A. R. van Veen, and R. A. van Santen, J. Catal. 163, 429 (1996).
- 211 E. J. M. Hensen, G. M. H. J. Lardinois, V. H. J. de Beer, J. A. R. van Veen, and R. A. van Santen, J. Catal. 187, 95 (1999).
- 212 L. Triguero, S. de Carolis, M. Baudin, M. Wojcik, K. Hermannson, M. A. Nygren, and L. G. M. Petterson, Faraday Disc. 114, 351 (1999).
- 213 C. R. A. Catlow and J. M. Thomas, Philos Trans. R. Soc. Chem. A 341, 255 (1992).
- 214 X. Rozanska and R. A. van Santen, Adv. Chem. Eng., in press; S. R. Blaszkowski and R. A. van Santen, Top. Catal. 4, 145 (1997); M. V. Frash and R. A. van Santen, Top. Catal. 9, 19 (1999).
- 215 F. J. M. M. de Gauw, and R. A. van Santen, Stud. Surf. Sci. Catal. 130A, 127–135 (2000).
- 216 S. P. Bates, W. J. M. van Well, R. A. van Santen, and B. Smit, J. Am. Chem. Soc. 118, 6753 (1996); J. Phys. Chem. 100, 17573 (1996); H. Koller, G. Engelhardt, and R. A. van Santen, Top. Catal. 9, 163 (1999).
- 217 A. M. Rigby, G. J. Kramer, and R. A. van Santen, J. Catal. 170, 1 (1997); S. P. Bates and R. A. van Santen, Adv. Catal. 42, 1 (1998); P. E. Sinclair and C. R. A. Catlow, J. Chem. Soc. Faraday Trans. 92, 2099 (1996); J. Phys. Chem. B 101, 295 (1997); M. Krossner and J. Sauer, J. Phys. Chem. 100, 6199 (1996); F. Haase, J. Sauer, and J. Hutter, Chem. Phys. Lett. 266, 397 (1997); H. Knözinger and S. J. Huber, Chem. Soc. Faraday. Trans. 94, 2047 (1998); F. Wakabayashi, J. Kondo, K. Domen, and C. Hirose, Stud. Surf. Sci. Catal. 90, 157 (1994); S. G. Hedge, P. Ratnasamy, L. M. Kustov, and V. B. Kazansky, Zeolites 8, 137 (1988).
- 218 E. L. Meijer, R. A. van Santen, and A. P. J. Jansen, J. Phys. Chem. 100, 9282 (1996); J. Phys. Chem. A 103, 2553 (1999).
- 219 X. Rozanska and R. A. van Santen, manuscript in preparation.
- 220 P. Sinclair, P. de Vries, P. Sherwood, C. R. A. Catlow, and R. A. van Santen, J. Chem. Soc. 94, 3401 (1998).
- 221 U. Eichler, M. Brändle, and J. Sauer, J. Phys. Chem. B 101, 10035 (1997).
- 222 P. B. Weisz, Adv. Catal. 13, 137 (1962); M. L. Conradt and W. E. Garwood, Ind. Eng. Chem. Prod. Res. Dev. 3, 38 (1964).
