Citation: Yanggang Wang, Xiaofeng Yang, Linhua Hu, Yadong Li, Jun Li. Theoretical study of the crystal plane effect and ion-pair active center for C-H bond activation by Co₃O₄ nanocrystals[J]. Chinese Journal of Catalysis, ;2014, 35(4): 462-467. doi: 10.1016/S1872-2067(14)60043-7 shu

Theoretical study of the crystal plane effect and ion-pair active center for C-H bond activation by Co₃O₄ nanocrystals

Yanggang Wang ^a ,
Xiaofeng Yang ^a,b ,
Linhua Hu ^a ,
Yadong Li ^a ,
Jun Li ^a,,

1.
a Department of Chemistry, Tsinghua University, Beijing 100084, China;

Corresponding author: Jun Li,
Received Date: 29 December 2013
Available Online: 20 January 2014
Fund Project: 国家纳米科技基础研究重大项目(2011CB932401) (2011CB932401)国家自然科学基金(21221062, 10979031). (21221062, 10979031)

Methane has attracted extensive interest in recent years due to its potential application as a replacement of oil and a feedstock for valuable chemicals. Due to the large C-H bond energy, the conversion of methane into useful products has been a challenge. In the present study, density functional theory (DFT) calculations were performed to study the activation of the C-H bond of methane on the (001) and (011) planes of Co₃O₄, which showed that CH₄ activation on Co₃O₄ nanocrystals was fairly easy with only small energy barriers (less than 1.1 eV). Surface Co-O ion pairs are the active site for C-H bond activation, where the two ions provide a synergistic effect for the activation of the strong C-H bond and yield surface Co-CH₃ and O-H species. The Co₃O₄(011) surface is shown to be more reactive for C-H bond activation than the Co₃O₄(001) surface, which is consistent with previous experimental results. Our results suggest that methane oxidation on Co₃O₄ nanocrystals has strong crystal plane effect and structure sensitivity and the ion-pair active center plays a significant role in activating the strong C-H bond.
- C-H bond activation,
- Methane conversion,
- Crystal plane effect,
- Microkinetic analysis,
- Ion-pair active center
1. [1]
  [1] Crabtree R H. Chem Rev, 1995, 95: 987
2. [2]
  [2] Copéret C. Chem Rev, 2010, 110: 656
3. [3]
  [3] Enger B C, Lödeng R, Holmen A. Appl Catal A, 2008, 346: 1
4. [4]
  [4] Wang X, Zhuang J, Peng Q, Li Y D. Nature, 2005, 437: 121
5. [5]
  [5] Somorjai G A, Tao F, Park J Y. Top Catal, 2008, 47: 1
6. [6]
  [6] Tian N, Zhou Z Y, Sun S G, Ding Y, Wang Z L. Science, 2007, 316: 732
7. [7]
  [7] Van Santen R A. Acc Chem Res, 2009, 42: 57
8. [8]
  [8] Xie X W, Li Y, Liu Z Q, Haruta M, Shen W J. Nature, 2009, 458: 746
9. [9]
  [9] Liu X W, Zhou K B, Wang L, Wang B Y, Li Y D. J Am Chem Soc, 2009, 131: 3140
10. [10]
  [10] Wang Y G, Yoon Y, Glezakou V A, Li J, Rousseau R. J Am Chem Soc, 2013, 135: 10673
11. [11]
  [11] Wang Y G, Mei D H, Li J, Rousseau R. J Phys Chem C, 2013, 117: 23082
12. [12]
  [12] Liotta L F, Carlo G D, Pantaleo G, Deganello G. Catal Commun, 2005, 6: 329
13. [13]
  [13] Liotta L F, Carlo G D, Pantaleo G, Veneziaa A M, Deganello G, Merlone Borla E, Pidriac M F. Top Catal, 2007, 42-43: 425
14. [14]
  [14] Liotta L F, Carlo G D, Pantaleo G, Deganello G. Appl Catal B, 2007, 70: 314
15. [15]
  [15] Hu L H, Peng Q, Li Y D. J Am Chem Soc, 2008, 130: 16136
16. [16]
  [16] Hu L H, Sun K Q, Peng Q, Xu B Q, Li Y D. Nano Res, 2010, 3: 363
17. [17]
  [17] Beaufils J P, Barbaux Y. J Appl Cryst, 1982, 15: 301
18. [18]
  [18] Ziólkowski J, Barbaux, Y. J Mol Catal, 1991, 67: 199
19. [19]
  [19] Jansson J. J Catal, 2000, 194: 55
20. [20]
  [20] Broqvist P, Panas I, Persson H. J Catal, 2002, 210: 198
21. [21]
  [21] Grillo F, Natil M M, Glisenti A. Appl Catal B, 2004, 48: 267
22. [22]
  [22] Petitto S C, Marsh E M, Carson G A, Langell M A. J Mol Catal A, 2008, 281: 49
23. [23]
  [23] Delley B. J Chem Phys 1990, 92: 508
24. [24]
  [24] Delley B. J Phys Chem, 1996, 100: 6107
25. [25]
  [25] Delley B. J Chem Phys, 2000, 113: 7756
26. [26]
  [26] Perdew J P, Burke K, Ernzerhof M. Phys Rev Lett, 1996, 77: 3865
27. [27]
  [27] Govind N, Petersen M, Fitzgerald G, King-Smith D, Andzelm J. Comput Mater Sci, 2003, 28: 250
28. [28]
  [28] Xu X L, Chen Z H, Li Y, Chen W K, Li J Q. Surf Sci, 2009, 603: 653
29. [29]
  [29] Zasada F, Stelmachowski P, Maniak G, Paul J F, Kotarba A, Sojka Z. Catal Lett, 2009, 127: 126
30. [30]
  [30] Walsh A, Wei S H, Yan Y, Al-Jassim M M, Turner J A, Woodhouse M, Parkinson B A. Phys Rev B, 2007, 76: 165119
31. [31]
  [31] Jiang D, Dai S. Phys Chem Chem Phys, 2011, 13: 978
32. [32]
  [32] Dutta P, Seehra M S, Thota S, Kumar J. J Phys-Condens Mat, 2008, 20: 015218
33. [33]
  [33] Roth W L. J Phys Chem Solids, 1964, 25: 1
34. [34]
  [34] Patil P S, Kadam L D, Lokhande C D. Thin Solid Films, 1996, 272: 29
35. [35]
  [35] Cheng C S, Serizawa M, Sakata H, Hirayama T. Mater Chem Phys, 1998, 53: 225
36. [36]
  [36] Barreca D, Massignan C, Daolio S, Fabrizio M, Piccirillo C, Armelao L, Tondello E. Chem Mater, 2001, 13: 588
37. [37]
  [37] Gulino A, Fragala I. Inorg Chim Acta, 2005, 358: 4466
38. [38]
  [38] Psofogiannakis G, St-Amant A, Ternan M. J Phys Chem B, 2006, 110: 24593
39. [39]
  [39] Wang C C, Wu J Y, Jiang J C. J Phys Chem C, 2013, 117, 6136
40. [40]
  [40] Molinari M, Parker S C, Sayle D C, Islam M S. J Phys Chem C, 2012, 116: 7073
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Theoretical study of the crystal plane effect and ion-pair active center for C-H bond activation by Co₃O₄ nanocrystals