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
1. [1]
  Qinhui Guan , Yuhao Guo , Na Li , Jing Li , Tingjiang Yan . Molecular sieve-mediated indium oxide catalysts for enhancing photocatalytic CO₂ hydrogenation. Acta Physico-Chimica Sinica, 2025, 41(11): 100133-0. doi: 10.1016/j.actphy.2025.100133
2. [2]
  Pei Li , Yuenan Zheng , Zhankai Liu , An-Hui Lu . Boron-Containing MFI Zeolite: Microstructure Control and Its Performance of Propane Oxidative Dehydrogenation. Acta Physico-Chimica Sinica, 2025, 41(4): 2406012-0. doi: 10.3866/PKU.WHXB202406012
3. [3]
  Huan LI , Shengyan WANG , Long Zhang , Yue CAO , Xiaohan YANG , Ziliang WANG , Wenjuan ZHU , Wenlei ZHU , Yang ZHOU . Growth mechanisms and application potentials of magic-size clusters of groups Ⅱ-Ⅵ semiconductors. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1425-1441. doi: 10.11862/CJIC.20240088
4. [4]
  Hui Wang , Abdelkader Labidi , Menghan Ren , Feroz Shaik , Chuanyi Wang . Recent Progress of Microstructure-Regulated g-C₃N₄ in Photocatalytic NO Conversion: The Pivotal Roles of Adsorption/Activation Sites. Acta Physico-Chimica Sinica, 2025, 41(5): 100039-0. doi: 10.1016/j.actphy.2024.100039
5. [5]
  Yadan Luo , Hao Zheng , Xin Li , Fengmin Li , Hua Tang , Xilin She . Modulating reactive oxygen species in O, S co-doped C₃N₄ to enhance photocatalytic degradation of microplastics. Acta Physico-Chimica Sinica, 2025, 41(6): 100052-0. doi: 10.1016/j.actphy.2025.100052
6. [6]
  Jiayao Wang , Guixu Pan , Ning Wang , Shihan Wang , Yaolin Zhu , Yunfeng Li . Preparation of donor-π-acceptor type graphitic carbon nitride photocatalytic systems via molecular level regulation for high-efficient H₂O₂ production. Acta Physico-Chimica Sinica, 2025, 41(12): 100168-0. doi: 10.1016/j.actphy.2025.100168
7. [7]
  Meng Lin , Hanrui Chen , Congcong Xu . Preparation and Study of Photo-Enhanced Electrocatalytic Oxygen Evolution Performance of ZIF-67/Copper(I) Oxide Composite: A Recommended Comprehensive Physical Chemistry Experiment. University Chemistry, 2024, 39(4): 163-168. doi: 10.3866/PKU.DXHX202308117
8. [8]
  Deyun Ma , Fenglan Liang , Qingquan Xue , Yanping Liu , Chunqiang Zhuang , Shijie Li . Interfacial engineering of Cd_0.5Zn_0.5S/BiOBr S-scheme heterojunction with oxygen vacancies for effective photocatalytic antibiotic removal. Acta Physico-Chimica Sinica, 2025, 41(12): 100190-0. doi: 10.1016/j.actphy.2025.100190
9. [9]
  Haitao Wang , Lianglang Yu , Jizhou Jiang , Arramel , Jing Zou . S-Doping of the N-Sites of g-C₃N₄ to Enhance Photocatalytic H₂ Evolution Activity. Acta Physico-Chimica Sinica, 2024, 40(5): 2305047-0. doi: 10.3866/PKU.WHXB202305047
10. [10]
  Xuejiao Wang , Suiying Dong , Kezhen Qi , Vadim Popkov , Xianglin Xiang . Photocatalytic CO₂ Reduction by Modified g-C₃N₄. Acta Physico-Chimica Sinica, 2024, 40(12): 2408005-0. doi: 10.3866/PKU.WHXB202408005
11. [11]
  Zhiquan Zhang , Baker Rhimi , Zheyang Liu , Min Zhou , Guowei Deng , Wei Wei , Liang Mao , Huaming Li , Zhifeng Jiang . Insights into the Development of Copper-Based Photocatalysts for CO₂ Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2406029-0. doi: 10.3866/PKU.WHXB202406029
12. [12]
  Xinyu Xu , Jiale Lu , Bo Su , Jiayi Chen , Xiong Chen , Sibo Wang . Steering charge dynamics and surface reactivity for photocatalytic selective methane oxidation to ethane over Au/Ti-CeO₂. Acta Physico-Chimica Sinica, 2025, 41(11): 100153-0. doi: 10.1016/j.actphy.2025.100153
13. [13]
  Tong Zhou , Xue Liu , Liang Zhao , Mingtao Qiao , Wanying Lei . Efficient Photocatalytic H₂O₂ Production and Cr(Ⅵ) Reduction over a Hierarchical Ti₃C₂/In₄SnS₈ Schottky Junction. Acta Physico-Chimica Sinica, 2024, 40(10): 2309020-0. doi: 10.3866/PKU.WHXB202309020
14. [14]
  Guoqiang Chen , Zixuan Zheng , Wei Zhong , Guohong Wang , Xinhe Wu . Molten Intermediate Transportation-Oriented Synthesis of Amino-Rich g-C₃N₄ Nanosheets for Efficient Photocatalytic H₂O₂ Production. Acta Physico-Chimica Sinica, 2024, 40(11): 2406021-0. doi: 10.3866/PKU.WHXB202406021
15. [15]
  Bowen Liu , Jianjun Zhang , Han Li , Bei Cheng , Chuanbiao Bie . MOF-derived ZnO/PANI S-scheme heterojunction for efficient photocatalytic phenol mineralization coupled with H₂O₂ generation. Acta Physico-Chimica Sinica, 2025, 41(10): 100121-0. doi: 10.1016/j.actphy.2025.100121
16. [16]
  Xin Zhou , Zhi Zhang , Yun Yang , Shuijin Yang . A Study on the Enhancement of Photocatalytic Performance in C/Bi/Bi₂MoO₆ Composites by Ferroelectric Polarization: A Recommended Comprehensive Chemical Experiment. University Chemistry, 2024, 39(4): 296-304. doi: 10.3866/PKU.DXHX202310008
17. [17]
  Yingqi BAI , Hua ZHAO , Huipeng LI , Xinran REN , Jun LI . Perovskite LaCoO₃/g-C₃N₄ heterojunction: Construction and photocatalytic degradation properties. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 480-490. doi: 10.11862/CJIC.20240259
18. [18]
  Jiawei Hu , Kai Xia , Ao Yang , Zhihao Zhang , Wen Xiao , Chao Liu , Qinfang Zhang . Interfacial Engineering of Ultrathin 2D/2D NiPS₃/C₃N₅ Heterojunctions for Boosting Photocatalytic H₂ Evolution. Acta Physico-Chimica Sinica, 2024, 40(5): 2305043-0. doi: 10.3866/PKU.WHXB202305043
19. [19]
  Yu Wang , Haiyang Shi , Zihan Chen , Feng Chen , Ping Wang , Xuefei Wang . 具有富电子Pt^δ−壳层的空心AgPt@Pt核壳催化剂：提升光催化H₂O₂生成选择性与活性. Acta Physico-Chimica Sinica, 2025, 41(7): 100081-0. doi: 10.1016/j.actphy.2025.100081
20. [20]
  Heng Chen , Longhui Nie , Kai Xu , Yiqiong Yang , Caihong Fang . Remarkable Photocatalytic H₂O₂ Production Efficiency over Ultrathin g-C₃N₄ Nanosheet with Large Surface Area and Enhanced Crystallinity by Two-Step Calcination. Acta Physico-Chimica Sinica, 2024, 40(11): 2406019-0. doi: 10.3866/PKU.WHXB202406019

Get Citation

PDF

XML

Metrics

PDF Downloads(7)
Abstract views(1187)
HTML views(131)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142