English

Research Progress on the Photocatalytic Conversion of Methane and Methanol

• ZHANG Shuyi ^1,2, ,
• BAO Jingxian ^1,3, ,
• WU Bo ^1,2, ,
• ZHONG Liangshu ^{1,4, ,} ,
• SUN Yuhan ^{1,4, ,}

• 1.

  CAS Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute

• 2.

  Chinese Academy of Sciences, Shanghai 201203, P. R. China

• 3.

  University of the Chinese Academy of Sciences, Beijing 100049, P. R. China

• 4.

  College of Sciences, Shanghai University, Shanghai 200444, P. R. China

Corresponding author: Emails: zhongls@sari.ac.cn (Z.L.); Tel.: + 86-21-20608002 (Z.L.); sunyh@sari.ac.cn (S.Y.). +86-21-20325009 (S.Y.)

• Received Date: 08 October 2018
  Revised Date: 21 November 2018
  Available Online: 01 September 2019
• Fund Project:

  This work was supported by the National Key R & D Program of China (2017YFB0602202, 2018YFB0604700), National Natural Science Foundation of China (21573271, 91545112, 21703278), Key Research Program of Frontier Sciences, CAS (QYZDB-SSW-SLH035), the "Transformational Technologies for Clean Energy and Demonstration" and Strategic Priority Research Program of the Chinese Academy of Sciences (XDA21020600)

Abstract: With the increasing energy demands and the limited petroleum reserves, it is highly desirable to produce fuels and chemicals from non-petroleum feedstocks, such as coal, natural gas and biomass. Catalytic conversion of C₁ resources (CO, CO₂, CH₃OH, CH₄, etc.) affords various products and attracts increasing attention from both academia and industries. Methane and methanol are important C₁ feedstocks in the production of fuels and chemicals. In order to obtain high selectivity for the target product, it is necessary to control the activation of C―H bonds in methane and methanol. However, this remains a great challenge. Although the traditional thermal catalytic conversion of methane and methanol has been developed over decades, there are still some disadvantages associated with the catalytic process, such as harsh reaction conditions, high energy consumption, and low selectivity. Photocatalysis, which is driven by photoenergy, can compensate for the Gibbs free energy. In the photocatalytic reactions, semiconductor photocatalysts absorb photons and generate electrons and holes in their conduction and valence bands, respectively, to accelerate the reaction rate. The position of the conduction band determines the oxidation capacity, and the bandgap determines the light absorption property. Normally, the oxidation capacity of photocatalysts is regulated by choosing semiconductors with a suitable bandgap or anions/cations doping. Fabrication of heterojunction and loading metalsare recognized as effective methods to promote the separation of electron-hole pairs and improve the photocatalytic efficiency. In contrast to thermal catalysis, photocatalysis can be carried out under mild reaction conditions with low energy consumption. Recently, photocatalysis has been considered an attractive route for the efficient conversion of methane and methanol to fuels and chemicals. Partial oxidation of methane, which is necessary to avoid the formation of byproducts, can be achieved by adjusting the wavelength and intensity of the light and the oxidation capacity of the photocatalysts. In addition, light-induced plasmon resonance improves the efficiency of methane conversion by forming an intrinsic high-energy magnetic field that can polarize methane. In methanol conversion, the C―H bond can be selectively activated, instead of the O―H bond, by light irradiation. Therefore, C―C coupling can be realized for the production of various value-added chemicals from methanol. This review summarizes the recent advances in the photocatalytic conversion of methane and methanol including the reactions of reforming, oxidation, and coupling. Perspectives and challenges for further research on the photocatalytic conversion of methane and methanol are also discussed.

Key words:
• Activation of C―H bond
•  /  C₁ chemistry
•  /  Methane
•  /  Methanol
•  /  Photocatalysis

• 1. [1]

     Herrerias, C. I.; Yao, X.; Li, Z.; Li, C. -J. Chem. Rev. 2007, 107, 2546. doi: 10.1021/cr050980b

  2. [2]

     Singh, M. K.; Akula, H. K.; Satishkumar, S.; Stahl, L.; Lakshman, M. K. ACS Catal. 2016, 6, 1921. doi: 10.1021/acscatal.5b02603

  3. [3]

     Yu, J. -T.; Pan, C. Chem. Commun. 2016, 52, 2220. doi: 10.1039/c5cc08872k

  4. [4]

     Cook, A. K.; Schimler, S. D.; Matzger, A. J.; Sanford, M. S. Science 2016, 351, 1421. doi: 10.1126/science.aad9289

  5. [5]

     Smith, K. T.; Berritt, S.; Gonzalez-Moreiras, M.; Ahn, S.; Smith, M. R., III; Baik, M. -H.; Mindiola, D. J. Science 2016, 351, 1424. doi: 10.1126/science.aad9730

  6. [6]

     Takamatsu, K.; Hirano, K.; Satoh, T.; Miura, M. J. Org. Chem. 2015, 80, 3242. doi: 10.1021/acs.joc.5b00307

  7. [7]

     Warratz, S.; Burns, D. J.; Zhu, C.; Korvorapun, K.; Rogge, T.; Scholz, J.; Jooss, C.; Gelman, D.; Ackermann, L. Angew. Chem. Int. Ed. 2017, 56, 1557. doi: 10.1002/anie.201609014

  8. [8]

     Zhang, F. -L.; Hong, K.; Li, T. -J.; Park, H.; Yu, J. -Q. Science 2016, 351, 252. doi: 10.1126/science.aad7893

  9. [9]

     Liao, K.; Negretti, S.; Musaev, D. G.; Bacsa, J.; Davies, H. M. L. Nature 2016, 533, 230. doi: 10.1038/nature17651

  10. [10]

      Liao, K. B.; Pickel, T. C.; Oyarskikh, V. B.; Acsa, J. B.; Usaev, D. G. M.; Davies, H. M. L. Nature 2017, 551, 609. doi: 10.1038/nature24641

  11. [11]

      Liao, K.; Yang, Y.-F.; Li, Y.; Sanders, J. N.; Houk, K. N.; Musaev, D. G.; Davies, H. M. L. Nat. Chem. 2018, 551, 609. doi: 10.1038/s41557-018-0087-7

  12. [12]

      Tzirakis, M. D.; Lykakis, I. N.; Orfanopoulos, M. Chem. Soc. Rev. 2009, 38, 2609. doi: 10.1039/B812100C

  13. [13]

      Zhang, X.; MacMillan, D. W. C. J. Am. Chem. Soc. 2017, 139, 11353. doi: 10.1021/jacs.7b07078

  14. [14]

      Capacci, A. G.; Malinowski, J. T.; McAlpine, N. J.; Kuhne, J.; MacMillan, D. W. C. Nat. Chem. 2017, 9, 1073. doi: 10.1038/nchem.2797

  15. [15]

      Maeda, H.; Takayama, H.; Segi, M. Photochem. Photobiol. Sci 2018, 17, 1118. doi: 10.1039/c8pp00239h

  16. [16]

      Jeffrey, J. L.; Terrett, J. A.; MacMillan, D. W. C. Science 2015, 349, 1532. doi: 10.1126/science.aac8555

  17. [17]

      Nicewicz, D. A.; MacMillan, D. W. C. Science 2008, 322, 77. doi: 10.1126/science.1161976

  18. [18]

      Shaw, M. H.; Shurtleff, V. W.; Terrett, J. A.; Cuthbertson, J. D.; MacMillan, D. W. C. Science 2016, 352, 1304. doi: 10.1126/science.aaf6635

  19. [19]

      Zuo, Z.; Ahneman, D. T.; Chu, L.; Terrett, J. A.; Doyle, A. G.; MacMillan, D. W. C. Science 2014, 345, 437. doi: 10.1126/science.1255525

  20. [20]

      Xie, S.; Shen, Z.; Deng, J.; Guo, P.; Zhang, Q.; Zhang, H.; Ma, C.; Jiang, Z.; Cheng, J.; Deng, D.; et al. Nat.Commun. 2018, 9, 1181. doi: 10.1038/s41467-018-03543-y

  21. [21]

      Villa, K.; Murcia-López, S.; Morante, J. R.; Andreu, T. Appl. Catal. B 2016, 187, 30. doi: 10.1016/j.apcatb.2016.01.032

  22. [22]

      Nomikos, G. N.; Panagiotopoulou, P.; Kondarides, D. I.; Verykios, X. E. Appl. Catal. B 2014, 146, 249. doi: 10.1016/j.apcatb.2013.03.018

  23. [23]

      Chen, F.; Yang, Q.; Li, X.; Zeng, G.; Wang, D.; Niu, C.; Zhao, J.; An, H.; Xie, T.; Deng, Y. Appl. Catal. B 2017, 200, 330. doi: 10.1016/j.apcatb.2016.07.021

  24. [24]

      Hammond, C.; Forde, M. M.; Ab Rahim, M. H.; Thetford, A.; He, Q.; Jenkins, R. L.; Dimitratos, N.; Lopez-Sanchez, J. A.; Dummer, N. F.; Murphy, D. M.; et al. Angew. Chem. Int. Ed. 2012, 51, 5129. doi: 10.1002/anie.201108706

  25. [25]

      Ab Rahim, M. H.; Forde, M. M.; Jenkins, R. L.; Hammond, C.; He, Q.; Dimitratos, N.; Lopez-Sanchez, J. A.; Carley, A. F.; Taylor, S. H.; Willock, D. J.; et al. Angew. Chem. Int. Ed. 2013, 52, 1280. doi: 10.1002/anie.201207717

  26. [26]

      Forde, M. M.; Armstrong, R. D.; Hammond, C.; He, Q.; Jenkins, R. L.; Kondrat, S. A.; Dimitratos, N.; Lopez-Sanchez, J. A.; Taylor, S. H.; Willock, D.; et al. J. Am. Chem. Soc. 2013, 135, 11087. doi: 10.1021/ja403060n

  27. [27]

      Agarwal, N.; Freakley, S. J.; McVicker, R. U.; Althahban, S. M.; Dimitratos, N.; He, Q.; Morgan, D. J.; Jenkins, R. L.; Willock, D. J.; Taylor, S. H.; et al. Science 2017, 358, 223. doi: 10.1126/science.aan6515

  28. [28]

      Liu, H.; Meng, X.; Dao, T. D.; Zhang, H.; Li, P.; Chang, K.; Wang, T.; Li, M.; Nagao, T.; Ye, J. Angew. Chem. Int. Ed. 2015, 54, 11545. doi: 10.1002/anie.201504933

  29. [29]

      Han, B.; Wei, W.; Chang, L.; Cheng, P.; Hu, Y. H. ACS Catal. 2015, 6, 494. doi: 10.1021/acscatal.5b02653

  30. [30]

      Liu, H.; Meng, X.; Dao, T. D.; Liu, L.; Li, P.; Zhao, G.; Nagao, T.; Yang, L.; Ye, J. J. Mater. Chem. A 2017, 5, 10567. doi: 10.1039/c7ta00704c

  31. [31]

      Pan, F.; Xiang, X.; Deng, W.; Zhao, H.; Feng, X.; Li, Y. ChemCatChem 2018, 10, 940. doi: 10.1002/cctc.201701565

  32. [32]

      Liu, H.; Dao, T. D.; Liu, L.; Meng, X.; Nagao, T.; Ye, J. Appl. Catal. B 2017, 209, 183. doi: 10.1016/j.apcatb.2017.02.080

  33. [33]

      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

  34. [34]

      Sastre, F.; Fornes, V.; Corma, A.; Garcia, H. Chemistry 2012, 18, 1820. doi: 10.1002/chem.201102273

  35. [35]

      Hu, Y.; Anpo, M.; Wei, C. J. Photochem. Photobiol. A 2013, 264, 48. doi: 10.1016/j.jphotochem.2013.05.005

  36. [36]

      Li, L.; Fan, S.; Mu, X.; Mi, Z.; Li, C. J. J. Am. Chem. Soc. 2014, 136, 7793. doi: 10.1021/ja5004119

  37. [37]

      Meng, L.; Chen, Z.; Ma, Z.; He, S.; Hou, Y.; Li, H.-H.; Yuan, R.; Huang, X.-H.; Wang, X.; Wang, X.; et al. Energ. Environ. Sci. 2018, 11, 294. doi: 10.1039/c7ee02951a

  38. [38]

      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

  39. [39]

      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

  40. [40]

      Li, Z.; Mo, L.; Kathiraser, Y.; Kawi, S. ACS Catal. 2014, 4, 1526. doi: 10.1021/cs401027p

  41. [41]

      Zhao, Y.; Kang, Y. Q.; Li, H.; Li, H. X. Green Chem. 2018, 20, 2781. doi: 10.1039/c8gc00743h

  42. [42]

      Margossian, T.; Larmier, K.; Kim, S. M.; Krumeich, F.; Fedorov, A.; Chen, P.; Muller, C. R.; Coperet, C. J. Am. Chem. Soc. 2017, 139, 6919. doi: 10.1021/jacs.7b01625

  43. [43]

      Zhang, Y. X.; Dragan, A.; Geddes, C. D. J. Phys.Chem. C 2009, 113, 15811. doi: 10.1021/jp900958n

  44. [44]

      Xiong, Z.; Chen, X.; Wang, X.; Peng, L.; Yan, D.; Lei, H.; Fu, Y.; Wu, J.; Li, Z.; An, X.; et al. Appl. Surf. Sci. 2013, 268, 524. doi: 10.1016/j.apsusc.2012.12.161

  45. [45]

      Nagli, L.; Gaft, M.; Gornushkin, I.; Glaus, R. Opt. Commun. 2016, 378, 41. doi: 10.1016/j.optcom.2016.05.071

  46. [46]

      Kondratenko, V. A.; Berger-Karin, C.; Kondratenko, E. V. ACS Catal. 2014, 4, 3136. doi: 10.1021/cs5002465

  47. [47]

      Park, J. H.; Kwon, Y.-i.; Nam, G. D.; Joo, J. H. J. Mater. Chem. A 2018, 6, 14246. doi: 10.1039/c8ta03021a

  48. [48]

      Zhu, S.; Lian, X.; Fan, T.; Chen, Z.; Dong, Y.; Weng, W.; Yi, X.; Fang, W. Nanoscale 2018, 10, 14031. doi: 10.1039/c8nr02588f

  49. [49]

      Sushkevich, V. L.; Palagin, D.; Ranocchiari, M.; van Bokhoven, J. A. Science 2017, 356, 523. doi: 10.1126/science.aam9035

  50. [50]

      Khan, N. A.; Kennedy, E. M.; Dlugogorski, B. Z.; Adesina, A. A.; Stockenhuber, M. Catal. Commun. 2014, 53, 42. doi: 10.1016/j.catcom.2014.04.012

  51. [51]

      Aslam, M.; Ismail, I. M.; Chandrasekaran, S.; Hameed, A. J. Hazard. Mater. 2014, 276, 120. doi: 10.1016/j.jhazmat.2014.05.022

  52. [52]

      Tanaka, A.; Hashimoto, K.; Kominami, H. J. Am. Chem. Soc. 2014, 136, 586. doi: 10.1021/ja410230u

  53. [53]

      Hameed, A.; Ismail, I. M. I.; Aslam, M.; Gondal, M. A. Appl. Catal. A 2014, 470, 327. doi: 10.1016/j.apcata.2013.10.045

  54. [54]

      Li, R.; Han, H.; Zhang, F.; Wang, D.; Li, C. Energy Environ. Sci. 2014, 7, 1369. doi: 10.1039/c3ee43304h

  55. [55]

      Ohkubo, K.; Hirose, K. Angew. Chem. Int. Ed. 2018, 57, 2126. doi: 10.1002/anie.201710945

  56. [56]

      Keller, G. E.; Bhasin, M. M. J. Catal. 1982, 73, 9. doi: 10.1016/0021-9517[82] 90075-6

  57. [57]

      Brady, C.; Murphy, B.; Xu, B. ACS Catal. 2017, 7, 3924. doi: 10.1021/acscatal.7b00879

  58. [58]

      Liu, Y.; Li, D.; Wang, T.; Liu, Y.; Xu, T.; Zhang, Y. ACS Catal. 2016, 6, 5366. doi: 10.1021/acscatal.6b01362

  59. [59]

      Okolie, C.; Lyu, Y.; Kovarik, L.; Stavitski, E.; Sievers, C. ChemCatChem 2018, 10, 2700. doi: 10.1002/cctc.201701892

  60. [60]

      Guo, J. J.; Hu, A.; Chen, Y.; Sun, J.; Tang, H.; Zuo, Z. Angew. Chem. Int. Ed. 2016, 55, 15319. doi: 10.1002/anie.201609035

  61. [61]

      Hu, A.; Guo, J. J.; Pan, H.; Tang, H.; Gao, Z.; Zuo, Z. J. Am. Chem. Soc. 2018, 140, 1612. doi: 10.1021/jacs.7b13131

  62. [62]

      Hu, A.; Guo, J. -J.; Pan, H.; Zuo, Z. Science 2018, 361, 668. doi: 10.1126/science.aat9750

  63. [63]

      Su, L. -W.; Li, X. -R.; Sun, Z. -Y. Energ. Policy 2013, 63, 130. doi: 10.1016/j.enpol.2013.08.031

  64. [64]

      Chiarello, G. L.; Aguirre, M. H.; Selli, E. J. Catal. 2010, 273, 182. doi: 10.1016/j.jcat.2010.05.012

  65. [65]

      Liu, Z.; Yin, Z.; Cox, C.; Bosman, M.; Qian, X.; Li, N.; Zhao, H.; Du, Y.; Li, J.; Nocera, D. G. Sci. Adv. 2016, 2, e1501425. doi: 10.1126/sciadv.1501425

  66. [66]

      Liu, Y.; Yang, S.; Yin, S.-N.; Feng, L.; Zang, Y.; Xue, H. Chem. Eng. J. 2018, 334, 2401. doi: 10.1016/j.cej.2017.12.016

  67. [67]

      DePuccio, D. P.; Landry, C. C. Catal. Sci.Technol. 2016, 6, 7512. doi: 10.1039/c6cy01449f

  68. [68]

      Liu, J.; Han, C.; Yang, X.; Gao, G.; Shi, Q.; Tong, M.; Liang, X.; Li, C. J. Catal. 2016, 333, 162. doi: 10.1016/j.jcat.2015.11.005

  69. [69]

      Liang, X.; Yang, X.; Gao, G.; Li, C.; Li, Y.; Zhang, W.; Chen, X.; Zhang, Y.; Zhang, B.; Lei, Y.; et al. J. Catal. 2016, 339, 68. doi: 10.1016/j.jcat.2016.03.033

  70. [70]

      Yang, X.; Zhang, A.; Gao, G.; Han, D.; Han, C.; Wang, J.; Lu, H.; Liu, J.; Tong, M. Catal. Commun. 2014, 43, 192. doi: 10.1016/j.catcom.2013.10.010

  71. [71]

      Han, C. H.; Yang, X. Z.; Gao, G. J.; Wang, J.; Lu, H. L.; Liu, J.; Tong, M.; Liang, X. Y. Green Chem. 2014, 16, 3603. doi: 10.1039/c4gc00367e

  72. [72]

      Fan, Y. H.; Bao, J. X.; Shi, L.; Li, S. G.; Lu, Y. W.; Liu, H. J.; Wang, H.; Zhong, L. S.; Sun, Y. H. Catal. Lett. 2018, 148, 2274. doi: 10.1007/s10562-018-2465-6

  73. [73]

      Fan, Y.; Li, S.; Bao, J.; Shi, L.; Yang, Y.; Yu, F.; Gao, P.; Wang, H.; Zhong, L.; Sun, Y. Green Chem. 2018, 20, 3450. doi: 10.1039/c8gc00971f

  74. [74]

      Chiarello, G. L.; Ferri, D.; Selli, E. J. Catal. 2011, 280, 168. doi: 10.1016/j.jcat.2011.03.013

  75. [75]

      Highfield, J. G.; Chen, M. H.; Nguyen, P. T.; Chen, Z. Energ. Environ. Sci. 2009, 2. doi: 10.1039/b907781m

  76. [76]

      Naldoni, A.; D'Arienzo, M.; Altomare, M.; Marelli, M.; Scotti, R.; Morazzoni, F.; Selli, E.; Dal Santo, V. Appl. Catal. B 2013, 130-131, 239. doi: 10.1016/j.apcatb.2012.11.006

  77. [77]

      Guo, Q.; Xu, C.; Ren, Z.; Yang, W.; Ma, Z.; Dai, D.; Fan, H.; Minton, T. K.; Yang, X. J. Am. Chem. Soc. 2012, 134, 13366. doi: 10.1021/ja304049x

  78. [78]

      Shen, M.; Henderson, M. A. J. Phys.Chem. C 2012, 116, 18788. doi: 10.1021/jp3046774

  79. [79]

      Zhang, J.; Peng, C.; Wang, H.; Hu, P. ACS Catal. 2017, 7, 2374. doi: 10.1021/acscatal.6b03348

  80. [80]

      Iwase, Y.; Kobayashi, T.; Inazu, K.; Miyaji, A.; Baba, T. Catal. Lett. 2007, 118, 146. doi: 10.1007/s10562-007-9171-0

  81. [81]

      Tang, X. C.; Zeng, Z. W.; Jiang, L. H.; Chen, L. A.; Wang, Z. M.; Jia, D. A. Z. Acta Chim. Sin. 2010, 68, 2013.

  82. [82]

      Jogunola, O.; Salmi, T.; Kangas, M.; Mikkola, J. P. Chem. Eng. J. 2012, 203, 469. doi: 10.1016/j.cej.2012.06.085

  83. [83]

      Lu, Z.; Gao, D.; Yin, H.; Wang, A.; Liu, S. J. Ind. Eng. Chem 2015, 31, 301. doi: 10.1016/j.jiec.2015.07.002

  84. [84]

      Phillips, K. R.; Jensen, S. C.; Baron, M.; Li, S. C.; Friend, C. M. J. Am. Chem. Soc. 2013, 135, 574. doi: 10.1021/ja3106797

  85. [85]

      Shen, Z. B.; Xie, S. J.; Fan, W. Q.; Zhang, Q. H.; Xie, Z. K.; Yang, W. M.; Wang, Y. D.; Lin, J. C.; Wu, X. J.; Wan, H. L.; et al. Catal. Sci.Technol. 2016, 6, 6485. doi: 10.1039/c6cy01468b

  86. [86]

      Xie, S. J.; Shen, Z. B.; Zhang, H. M.; Cheng, J.; Zhang, Q. H.; Wang, Y. Catal. Sci. Technol. 2017, 7, 923. doi: 10.1039/c6cy02510b

  87. [87]

      Pospech, J.; Fleischer, I.; Franke, R.; Buchholz, S.; Beller, M. Angew Chem. Int. Ed. 2013, 52, 2852. doi: 10.1002/anie.201208330

  88. [88]

      Chan, L. K. M.; Poole, D. L.; Shen, D.; Healy, M. P.; Donohoe, T. J. Angew. Chem. Int. Ed. 2014, 53, 761. doi: 10.1002/anie.201307950

  89. [89]

      Liu, Z. H.; Yang, Z. Z.; Yu, X. X.; Zhang, H. Y.; Yu, B.; Zhao, Y. F.; Liu, Z. M. Org. Lett. 2017, 19, 5228. doi: 10.1021/acs.orglett.7b02462

  90. [90]

      Zhu, C. J.; Zhang, Y. F.; Zhao, H. Q.; Huang, S. J.; Zhang, M.; Su, W. P. Adv. Synth. Catal. 2015, 357, 331. doi: 10.1002/adsc.201500006

  91. [91]

      Yang, J.; Xie, D.; Zhou, H.; Chen, S.; Duan, J.; Huo, C.; Li, Z. Adv. Synth. Catal. 2018, 360, 3471. doi: 10.1002/adsc.201800467

  92. [92]

      Griesbeck, A. G.; Reckenthaler, M. Beilstein J. Org. Chem. 2014, 10, 1143. doi: 10.3762/bjoc.10.114

•