Citation: MU Xiaoyue, LI Lu. Photo-Induced Activation of Methane at Room Temperature[J]. Acta Physico-Chimica Sinica, ;2019, 35(9): 968-976. doi: 10.3866/PKU.WHXB201810007 shu

Photo-Induced Activation of Methane at Room Temperature

MU Xiaoyue ¹ ,
LI Lu ^1,2,,

1.
College of Chemistry, Jilin University, Changchun 130012, P. R. China
2.
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012, P. R. China

Corresponding author: LI Lu, luli@jlu.edu.cn
Received Date: 8 October 2018
Revised Date: 30 November 2018
Accepted Date: 30 November 2018
Available Online: 7 September 2018
Fund Project: the National Natural Science Foundation of China 21621001the 111 Project B17020the National Natural Science Foundation of China 21875090The project was supported by the National Natural Science Foundation of China (21875090, 21621001) and the 111 Project (B17020)

Methane, the most abundant constituent of natural gas, is a potential substitute for the dwindling petroleum resources for the chemical industry as a carbon-based feedstock. Over the last two decades, global research endeavors have focused on the development of more efficient and selective catalysts for the conversion of ubiquitous but inert methane. In addition, the transportation of gaseous methane in pipelines is unavoidably accompanied by leakage, and methane is recognized as a potent greenhouse gas (20 times more powerful than carbon dioxide per molecule). Thus, the conversion of methane into heavier derivatives is also of crucial environmental concern. Unfortunately, there is still a lack of economical and practical routes for methane conversion. Currently, the major route for methane conversion is the steam reforming of methane into synthetic gases, which is a multistep and energy-consuming route. Another option is to use photoenergy to drive the conversion of methane, which has significant advantages such as the capacity to minimize coking by running at room temperature. A promising approach to photocatalytic methane conversion is the photo-powered direct coupling or oxidation of methane to form ethane, methanol and hydrogen. The ethane or methanol produced can, in turn, be converted into ethene or liquid fuels through metathesis or dehydrogenation, respectively. Furthermore, the direct dehydrogenation of methane is the best way to produce clean H₂ energy from fossil fuels since methane has the highest H/C ratio among hydrocarbons. However, the methane conversion efficiency of previously reported photocatalysts is low. Furthermore, the wavelength of light used in previously reported photocatalytic systems usually needs to be less than 270 nm, which is beyond the range of the solar spectrum (wavelength λ > 290 nm) reaching the Earth's surface. To achieve substantial yield and selectivity, and to exploit solar energy effectively, the development of photocatalytic systems with distinctly higher activity, higher selectivity, and lower photon energy threshold is desired. Over the past decades, many efforts have been made to activate the strong C―H bond in methane by light at room temperature. Based on the current state of research on photocatalytic methane conversion, we have focused our review on the following aspects: non-oxidative coupling of methane, dehydroaromatization of methane, and total and partial oxidation of methane. Finally, we summarize the difference between photocatalysis and thermal catalysis in the methane conversion reaction.
- Methane conversion,
- C―H bond activation,
- Photocatalysis,
- Non-oxidative dehydrogenation,
- Zeolites,
- Semiconductors
1. [1]
  Choudhary, V. R.; Kinage, A. K.; Choudhary, T. V. Science 1997, 275, 1286. doi: 10.1126/science.275.5304.1286 doi: 10.1126/science.275.5304.1286
2. [2]
  Lunsford, J. H. Catal. Today 2000, 63, 165. doi: 10.1016/S0920-5861(00)00456-9 doi: 10.1016/S0920-5861(00)00456-9
3. [3]
  Holmen, A. Catal. Today 2009, 142, 2. doi: 10.1016/j.cattod.2009.01.004 doi: 10.1016/j.cattod.2009.01.004
4. [4]
  Schwach, P.; Pan, X. L.; Bao, X. H. Chem. Rev. 2017, 117, 8497. doi: 10.1021/acs.chemrev.6b00715 doi: 10.1021/acs.chemrev.6b00715
5. [5]
  Gunsalus, N. J.; Koppaka, A.; Park, S. H.; Bischof, S. M.; Hashiguchi, B. G.; Periana, R. A. Chem. Rev. 2017, 117, 8521. doi: 10.1021/acs.chemrev.6b00739 doi: 10.1021/acs.chemrev.6b00739
6. [6]
  Tang, P.; Zhu, Q. J.; Wu, Z. X.; Ma, D. Energy Environ. Sci. 2014, 7, 2580. doi: 10.1039/C4EE00604F doi: 10.1039/C4EE00604F
7. [7]
  Richard, A. K. Science 2010, 328, 1624. doi: 10.1126/science.328.5986.1624 doi: 10.1126/science.328.5986.1624
8. [8]
  Schwarz, H. Angew. Chem. Int. Ed. 2011, 50, 10096. doi: 10.1002/anie.201006424 doi: 10.1002/anie.201006424
9. [9]
  Lelieveld, J.; Lechtenböhmer, S.; Assonov, S. S.; Brenninkmeijer, C. A. M.; Dienst, C.; Fischedick, M.; Hanke, T. Nature 2005, 434, 841. doi: 10.1038/434841a doi: 10.1038/434841a
10. [10]
  Bergman, R. G. Nature 2007, 446, 391. doi: 10.1038/446391a doi: 10.1038/446391a
11. [11]
  Arora, S.; Prasad, R. RSC Adv. 2016, 6, 108668. doi: 10.1039/C6RA20450C doi: 10.1039/C6RA20450C
12. [12]
  Pakhare, D.; Spivey, J. Chem. Soc. Rev. 2014, 43, 7813. doi: 10.1039/C3CS60395D doi: 10.1039/C3CS60395D
13. [13]
  Jones, G.; Jakobsen, J. G.; Shim, S. S.; Kleis, J.; Andersson, M. P.; Rossmeisl, J.; Abild-Pedersen, F.; Bligaard, T.; Helveg, S.; Hinnemann, B. et al. J. Catal. 2008, 259, 147. doi: 10.1016/j.jcat.2008.08.003 doi: 10.1016/j.jcat.2008.08.003
14. [14]
  Hook, J. P. V. Catal. Rev. -Sci. Eng. 1980, 21, 1. doi:10.1080/03602458008068059 doi: 10.1080/03602458008068059
15. [15]
  Latimer, A. A.; Kulkarni, A. R.; Aljama, H, ; Montoya, J. H.; Yoo, J. S.; Tsai, C.; Abild-Pedersen, F.; Studt, F.; N rskov, J. K. Nat. Mater. 2017, 16, 225. doi:10.1038/nmat4760 doi: 10.1038/nmat4760
16. [16]
  Liang, Z.; Li, T.; Kim, M.; Asthagiri, A.; Weaver, J. F. Science 2017, 356, 299. doi: 10.1126/science.aam9147 doi: 10.1126/science.aam9147
17. [17]
  Labinger, J. A.; Bercaw, J. E. Nature 2002, 417, 507. doi: 10.1038/417507a doi: 10.1038/417507a
18. [18]
  Sushkevich, V. L.; Palagin, D.; Ranocchiari, M.; van Bokhoven, J. A. Science 2017, 356, 523. doi: 10.1126/science.aam9035 doi: 10.1126/science.aam9035
19. [19]
  Berndt, H.; Martin, A.; Brückner, A.; Schreier, E.; Müller, D.; Kosslick, H.; Wolf, G. -U.; Lücke, B. J. Catal. 2000, 191, 384. doi: 10.1006/jcat.1999.2786 doi: 10.1006/jcat.1999.2786
20. [20]
  R. A. Periana, O. Mironov, D. Taube, G. Bhalla, C. J. J. Science 2003, 301, 814. doi: 10.1126/science.1086466 doi: 10.1126/science.1086466
21. [21]
  Lunsford, J. H. Angew. Chem. Int. Ed. 1995, 34, 970. doi: 10.1002/anie.199509701 doi: 10.1002/anie.199509701
22. [22]
  Spivey, J. J.; Hutchings, G. Chem. Soc. Rev. 2014, 43, 792. doi: 10.1039/C3CS60259A doi: 10.1039/C3CS60259A
23. [23]
  Zheng, H.; Ma, D.; Bao, X. H.; Hu, J. Z.; Kwak, J. H.; Wang, Y.; Peden, C. H. F. J. Am. Chem. Soc. 2008, 130, 3722. doi: 10.1021/ja7110916 doi: 10.1021/ja7110916
24. [24]
  Wang, L.; Tao, L.; Xie, M.; Xu, G. Catal. Lett. 1993, 21, 35. doi: 10.1007/BF00767368 doi: 10.1007/BF00767368
25. [25]
  Guo, X. G.; Fang, G. Z.; Li, G.; Ma, H.; Fan, H. J.; Yu, L.; Ma, C.; Wu, X.; Deng, D. H.; Wei, M. M. et al. Science 2014, 344, 616. doi: 10.1126/science.1253150 doi: 10.1126/science.1253150
26. [26]
  Cui, X. J.; Li, H. B.; Wang, Y.; Hu, Y. L.; Hua, L.; Li, H. Y.; Han, X. W.; Liu, Q. F.; Yang, F.; He, L. M. et al. Chem 2018, 4, 1902. doi: 10.1016/j.chempr.2018.05.006 doi: 10.1016/j.chempr.2018.05.006
27. [27]
  Xu, Y. D.; Bao, X. H.; Lin, L. W. J. Catal. 2003, 216, 386. doi: 10.1016/S0021-9517(02)00124-0 doi: 10.1016/S0021-9517(02)00124-0
28. [28]
  Kato, Y.; Yoshida, H.; Hattori, T. Chem. Commun. 1998, 21, 2389. doi: 10.1039/A806825I doi: 10.1039/A806825I
29. [29]
  Yuliati, L.; Yoshida, H. Chem. Soc. Rev. 2008, 37, 1592. doi: 10.1039/B710575B doi: 10.1039/B710575B
30. [30]
  Yoshida, H.; Matsushita, N.; Kato, Y.; Hattori, T. J. Phys. Chem. B 2003, 107, 8355. doi: 10.1021/jp034458+
31. [31]
  Li, L.; Li, G. -D.; Yan, C.; Mu, X. -Y.; Pan, X. -L.; Zou, X. -X.; Wang, K. -X.; Chen, J. -S. Angew. Chem. Int. Ed. 2011, 50, 8299. doi: 10.1002/anie.201102320 doi: 10.1002/anie.201102320
32. [32]
  Dietl, N.; Engeser, M.; Schwarz, H. Angew. Chem. Int. Ed. 2009, 48, 4861. doi: 10.1002/anie.200901596 doi: 10.1002/anie.200901596
33. [33]
  Copéret, C. Chem. Rev. 2010, 110, 656. doi: 10.1021/cr900122p doi: 10.1021/cr900122p
34. [34]
  Yuliati, L.; Hamajima, T.; Hattori, T.; Yoshida, H. J. Phys. Chem. C 2008, 112, 7223. doi: 10.1021/jp712029w doi: 10.1021/jp712029w
35. [35]
  Anderson, M. W.; Terasaki, O.; Ohsuna, T.; Philippou, A.; Mackay, S. P.; Ferreira, A.; Rocha, J.; Lidin, S. Nature 1994, 367, 347. doi: 10.1038/367347a0 doi: 10.1038/367347a0
36. [36]
  Li, L.; Cai, Y. -Y.; Li, G. -D.; Mu, X. -Y.; Wang, K. -X.; Chen, J. -S.; Angew. Chem. Int. Ed. 2012, 51, 4702. doi: 10.1002/anie.201200045 doi: 10.1002/anie.201200045
37. [37]
  Li, L.; Fan, S.; Mu, X.; Mi, Z.; Li, C. -J. J. Am. Chem. Soc. 2014, 136, 7793. doi: 10.1021/ja5004119 doi: 10.1021/ja5004119
38. [38]
  Li, L.; Mu, X.; Liu, W.; Kong, X.; Fan, S.; Mi, Z.; Li, C. J. Angew. Chem. Int. Ed. 2014, 53, 14106. doi: 10.1002/anie.201408754 doi: 10.1002/anie.201408754
39. [39]
  Goldberger, J.; He, R. R.; Zhang, Y. F.; Lee, S.; Yan, H. Q.; Choi, H. J.; Yang, P. D. Nature 2003, 422, 599. doi: 10.1038/nature01551 doi: 10.1038/nature01551
40. [40]
  Ibbetson, J. P.; Fini, P. T.; Ness, K. D.; DenBaars, S. P.; Speck, J. S.; Mishra, U. K. Appl. Phys. Lett. 2000, 77, 250. doi: 10.1063/1.126940 doi: 10.1063/1.126940
41. [41]
  Eller, B. S.; Yang, J. L.; Nemanich, R. J. J. Electron. Mat. 2014, 43, 4560. doi: 10.1007/s11664-014-3383-z doi: 10.1007/s11664-014-3383-z
42. [42]
  Meng, L.; Chen, Z.; Ma, Z.; He, S.; Hou, Y.; Li, H.; Yuan, R.; Huang, X.; Wang, X.; Wang X.; et al. Energy Environ. Sci. 2018, 11, 294. doi: 10.1056/NEJMoa1304459 doi: 10.1056/NEJMoa1304459
43. [43]
  Yu, L. H.; Shao, Y.; Li, D. Z. Appl. Catal. B-Environ. 2017, 204, 216. doi: 10.1016/j.apcatb.2016.11.039 doi: 10.1016/j.apcatb.2016.11.039
44. [44]
  Kaliaguine, S. L.; Shelimov B. N.; Kazansky, V. B. J. Catal. 1978, 55, 384. doi: 10.1016/0021-9517(78)90225-7 doi: 10.1016/0021-9517(78)90225-7
45. [45]
  Chen, X.; Li, Y.; Pan, X.; Cortie, D.; Huang, X.; Yi, Z. Nat. Commun. 2016, 7, 12273. doi: 10.1038/ncomms12273 doi: 10.1038/ncomms12273
46. [46]
  Wada, K.; Yamada, H.; Watanabe Y.; Mitsudo, T. J. Chem. Soc. Faraday Trans. 1998, 94, 1771. doi: 10.1007/s10562-008-9491-8 doi: 10.1007/s10562-008-9491-8
47. [47]
  López, H. H.; Martínez, A. Catal. Lett. 2002, 83, 37. doi: 10.1023/A:1020649313699 doi: 10.1023/A:1020649313699
48. [48]
  Thampi, K. R.; Kiwi, J.; Grätzel, M. Catal. Lett. 1988, 1, 109. doi: 10.1007/BF00765891 doi: 10.1007/BF00765891
49. [49]
  Ward, M. D.; Brazdil, J. F.; Mehandru, S. P.; Anderson, A. B. J. Phys. Chem. 1987, 91, 6515. doi: 10.1021/j100310a019
50. [50]
  Wada, K.; Yoshida, K.; Watanabe, Y. J. Chem. Soc. Faraday Trans. 1995, 91, 1647. doi: 10.1039/FT9959101647 doi: 10.1039/FT9959101647
51. [51]
  Noceti, R. P.; Taylor, C. E.; D'Este, J. R. Catal. Today 1997, 33, 199. doi: 10.1016/S0920-5861(96)00155-1 doi: 10.1016/S0920-5861(96)00155-1
52. [52]
  Villa, K.; Murcia-López, M.; Andreu, T.; Morante, J. R. Appl. Catal. B: Environ. 2015, 163, 150. doi: 10.1016/j.apcatb.2014.07.055 doi: 10.1016/j.apcatb.2014.07.055
53. [53]
  Murcia-López, S.; Bacariza, M. C.; Villa, K.; Lopes, J. M.; Henriques, C.; Morante, J. R.; Andreu, T. ACS Catal. 2017, 7, 2878. doi: 10.1021/acscatal.6b03535 doi: 10.1021/acscatal.6b03535
54. [54]
  Hu, A. H.; Guo, J. J.; Pan, H.; Zuo, Z. W. Science 2018, doi: 10.1126/science.aat9750 doi: 10.1126/science.aat9750
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