Water reactivity with tungsten oxides: H 2 production and kinetic traps

Journal of Chemical Physics

Volumn 131, Issue 14, 2009, Pages

  Mayhall, Nicholas J ^a   Rothgeb, David W ^a   Hossain, Ekram ^a   Jarrold, Caroline Chick ^a   Raghavachari, Krishnan ^a  

^a INDIANA UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYTIC APPLICATIONS; CLUSTER IONS; ELECTRONIC STRUCTURE CALCULATIONS; HIGH POTENTIAL; KINETIC TRAPS; METAL-OXIDE CLUSTERS; MULTIPLE MODES; REACTION PROFILE; SINGLE PEAK; SMALL MOLECULES; TUNGSTEN OXIDE;

ELECTRONIC STRUCTURE; HYDROGEN; METALLIC COMPOUNDS; TUNGSTEN; TUNGSTEN COMPOUNDS; ULTRATHIN FILMS;

OXIDES;

HYDROGEN; OXIDE; TUNGSTEN; TUNGSTEN OXIDE; WATER;

ARTICLE; CHEMICAL MODEL; CHEMICAL STRUCTURE; CHEMISTRY; CONFORMATION; KINETICS; THERMODYNAMICS;

HYDROGEN; KINETICS; MODELS, CHEMICAL; MODELS, MOLECULAR; MOLECULAR CONFORMATION; OXIDES; THERMODYNAMICS; TUNGSTEN; WATER;

EID: 70350441758     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.3242294     Document Type: Article

References (41)

1. A. Fujishima and K. Honda, Nature (London) 0028-0836 238, 37 (1972). 10.1038/238037a0
2. Q. Sun, B. K. Rao, P. Jena, D. Stolcic, Y. D. Kim, G. Gantefor, and A. W. Castleman, J. Chem. Phys. 0021-9606 121, 9417 (2004). 10.1063/1.1807374 (Pubitemid 40001705)
3. H. J. Zhai, X. Huang, L. F. Cui, X. Li, J. Li, and L. S. Wang, J. Phys. Chem. A 1089-5639 109, 6019 (2005). 10.1021/jp051496f (Pubitemid 41048758)
4. S. G. Li and D. A. Dixon, J. Phys. Chem. A 1089-5639 110, 6231 (2006). 10.1021/jp060735b (Pubitemid 43953083)
5. X. Huang, H. J. Zhai, T. Waters, J. Li, and L. S. Wang, Angew. Chem., Int. Ed. 1433-7851 45, 657 (2006). 10.1002/anie.200503652
6. X. Huang, H. J. Zhai, J. Li, and L. S. Wang, J. Phys. Chem. A 1089-5639 110, 85 (2006). 10.1021/jp055325m (Pubitemid 43133482)
7. H. Nair, M. J. Liszka, J. E. Gatt, and C. D. Baertsch, J. Phys. Chem. C 1932-7447 112, 1612 (2008). 10.1021/jp076300l (Pubitemid 351288275)
8. Q. Sun, B. K. Rao, P. Jena, D. Stolcic, G. Gantefor, and Y. Kawazoe, Chem. Phys. Lett. 0009-2614 387, 29 (2004). 10.1016/j.cplett.2004.01.080
9. E. I. Ross-Medgaarden, W. V. Knowles, T. Kim, M. S. Wong, W. Zhou, C. J. Kiely, and I. E. Wachs, J. Catal. 0021-9517 256, 108 (2008). 10.1016/j.jcat.2008.03.003
10. M. Gratzel, Nature (London) 0028-0836 414, 338 (2001). 10.1038/35104607 (Pubitemid 33097816)
11. E. L. Miller, B. Marsen, D. Paluselli, and R. Rocheleau, Electrochem. Solid-State Lett. 1099-0062 8, A247 (2005). 10.1149/1.1887196
12. M. A. Butler, J. Appl. Phys. 0021-8979 48, 1914 (1977). 10.1063/1.323948
13. B. Cole, B. Marsen, E. Miller, Y. F. Yan, B. To, K. Jones, and M. Al-Jassim, J. Phys. Chem. C 1932-7447 112, 5213 (2008). 10.1021/jp077624c
14. L. Weinhardt, M. Blum, M. Bar, C. Heske, B. Cole, B. Marsen, and E. L. Miller, J. Phys. Chem. C 1932-7447 112, 3078 (2008). 10.1021/jp7100286 (Pubitemid 351362340)
15. K. Raghavachari and M. Halls, Mol. Phys. 0026-8976 102, 381 (2004). 10.1080/00268970410001675590
16. N. J. Mayhall and K. Raghavachari, J. Phys. Chem. A 1089-5639 111, 8211 (2007). 10.1021/jp074894m (Pubitemid 47387838)
17. B. L. Yoder, J. T. Maze, K. Raghavachari, and C. C. Jarrold, J. Chem. Phys. 0021-9606 122, 094313 (2005). 10.1063/1.1853379 (Pubitemid 41042141)
18. N. J. Mayhall, D. W. Rothgeb, E. Hossain, K. Raghavachari, and C. C. Jarrold, J. Chem. Phys. 0021-9606 130, 124313 (2009). 10.1063/1.3100782
19. D. Rothgeb, E. Hossain, A. T. Kuo, J. L. Troyer, C. C. Jarrold, N. J. Mayhall, and K. Raghavachari, J. Chem. Phys. 0021-9606 130, 124314 (2009). 10.1063/1.3096414
20. A. D. Becke, J. Chem. Phys. 0021-9606 98, 5648 (1993). 10.1063/1.464913
21. C. T. Lee, W. T. Yang, and R. G. Parr, Phys. Rev. B 0163-1829 37, 785 (1988). 10.1103/PhysRevB.37.785
22. D. Andrae, U. Haussermann, M. Dolg, H. Stoll, and H. Preuss, Theor. Chim. Acta 0040-5744 77, 123 (1990). 10.1007/BF01114537
23. R. A. Kendall, T. H. Dunning, and R. J. Harrison, J. Chem. Phys. 0021-9606 96, 6796 (1992). 10.1063/1.462569
24. J. M. L. Martin and A. Sundermann, J. Chem. Phys. 0021-9606 114, 3408 (2001). 10.1063/1.1337864 (Pubitemid 32253352)
25. F. Jensen, Introduction to Computational Chemistry, 2nd ed. (Wiley, Chichester, England; Hoboken, NJ, 2007).
26. M. J. Frisch, G. W. Trucks, H. B. Schlegel, Gaussian Development Version, Revision G.01, Gaussian Inc., Pittsburgh, PA, 2007.
27. V. D. Moravec and C. C. Jarrold, J. Chem. Phys. 0021-9606 108, 1804 (1998). 10.1063/1.475557
28. R. B. Wyrwas, B. L. Yoder, J. T. Maze, and C. C. Jarrold, J. Phys. Chem. A 1089-5639 110, 2157 (2006). 10.1021/jp057195n (Pubitemid 43342967)
29. In addition to simple electron counting, these oxidation reactions also exhibit an increase in NBO atomic charges.
30. 6- however, the resulting bridged hydroxide is bound to the "left" tungsten center more strongly than the "right," with bond lengths of 2.1 and 2.3 Å, respectively.
31. We highlight the fact that the complexation free energies are, in many cases, positive. This is a result of the inclusion of translational entropy calculated at 298 K using the ideal gas approximation. We also note that employing the standard approach of neglecting imaginary frequency vibrational modes from our thermochemical analysis, the absolute free energy of a transition state may actually become smaller than that of the reactant. This is seen in Figs..
32. K. Raghavachari, G. W. Trucks, J. A. Pople, and M. Head-Gordon, Chem. Phys. Lett. 0009-2614 157, 479 (1989). 10.1016/S0009-2614(89)87395-6
33. N. C. Handy, J. A. Pople, M. Head-Gordon, K. Raghavachari, and G. W. Trucks, Chem. Phys. Lett. 0009-2614 164, 185 (1989). 10.1016/0009-2614(89)85013- 4
34. Harvey and co-workers (Refs.) explored spin-crossover phenomena for various transition metal reactions. They found that spin-crossover reactions for thermochemically favorable processes occur "fast or very fast" (Ref.). As the change in spin state (depicted as a star) in Fig. is exothermic by about 10 kcal/mol, we expect this to happen readily. However, spin-crossover mechanisms are complicated and we plan to explore these types of transitions with more accurate computational models employing spin-orbit corrections.
35. M. Besora, J. Carreon-Macedo, A. Cimas, and J. Harvey, Adv. Inorg. Chem. 0898-8838 61, 573 (2009). 10.1016/S0898-8838(09)00210-4
36. J. Carreon-Macedo and J. N. Harvey, J. Am. Chem. Soc. 0002-7863 126, 5789 (2004). 10.1021/ja049346q (Pubitemid 38621417)
37. A. E. Reed, L. Curtiss, and F. Weinhold, Chem. Rev. (Washington, D.C.) 0009-2665 88, 899 (1988). 10.1021/cr00088a005
38. A. E. Reed and F. Weinhold, J. Chem. Phys. 0021-9606 83, 1736 (1985). 10.1063/1.449360
39. A. E. Reed and F. Weinhold, J. Chem. Phys. 0021-9606 78, 4066 (1983). 10.1063/1.445134
40. A. E. Reed, R. B. Weinstock, and F. Weinhold, J. Chem. Phys. 0021-9606 83, 735 (1985). 10.1063/1.449486
41. See EPAPS supplementary material at http://dx.doi.org/10.1063/1.3242294 E-JCPSA6-131-013939 for a list of optimized molecular geometries used in this paper.