Citation: Zhang Xiang, Guo Caihong, Wu Haishun. Recent Developments of Homogeneous Transition-Metal Catalysts for Low Temperature Dehydrogenation of Methanol[J]. Chinese Journal of Organic Chemistry, ;2019, 39(9): 2458-2466. doi: 10.6023/cjoc201902032 shu

Recent Developments of Homogeneous Transition-Metal Catalysts for Low Temperature Dehydrogenation of Methanol

  • Corresponding author: Guo Caihong, sxgch2006@163.com
  • Received Date: 26 February 2019
    Revised Date: 27 March 2019
    Available Online: 11 September 2019

    Fund Project: the National Natural Science Foundation of China 21373131Project supported by the National Natural Science Foundation of China (No. 21373131)

Figures(9)

  • It is extremely urgent to develop green energy and find alternatives to fossil fuels since the energy shortage and environmental pollution become the worldwide concern. Methanol has emerged as a promising carrier for hydrogen storage owing to its high hydrogen density, simple structure and environmental friendly substance. The methanol reforming has triggered great efforts on the development of homogeneous catalysts, and the aim is to decrease methanol dehydrogenation reaction temperature and improve the selectivity. This review summarizes the recent research progresses in the homogeneously transition-metal catalyzed thermal dehydrogenation of methanol and aqueous methanol reforming. It mainly focuses on the structural characteristics of Ru, Rh, Ir, Fe and Mn-based complexes, catalytic reaction conditions, the reaction yield, and the catalytic reaction mechanism. The differences in the reactivities of these catalysts are analyzed and compared. Not only a summary is given, but also some perspectives and inspiration for improving the performance of aqueous methanol reforming catalysts for future research are discussed.
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    1. [1]

      Armaroli, N.; Balzani, V. Chem. Asian J. 2011, 6, 768.  doi: 10.1002/asia.201000797

    2. [2]

      Behrendt, F.; Schüth, F. Chem. Ing. Tech. 2011, 83, 1984.  doi: 10.1002/cite.201100147

    3. [3]

      Cook, T. R.; Dogutan, D. K.; Reece, S. Y.; Surendranath, Y.; Teets, T. S.; Nocera, D. G. Chem. Rev. 2010, 110, 6474.  doi: 10.1021/cr100246c

    4. [4]

      Armaroli, N.; Balzani, V. ChemSusChem 2011, 4, 21.  doi: 10.1002/cssc.201000182

    5. [5]

      Zheng, J. Y.; Liu, X. X.; Xu, P.; Liu, P. F.; Zhao, Y. Z.; Yang, J. Int. J. Hydrogen Energy 2012, 37, 1048.  doi: 10.1016/j.ijhydene.2011.02.125

    6. [6]

      Xu, Y.; Tao, Z. -L.; Chen, J. Prog. Chem. 2006, 18, 200(in Chinese).  doi: 10.3321/j.issn:1005-281X.2006.02.008

    7. [7]

      Dalebrook, A. F.; Gan, W.; Grasemann, M.; Moret, S.; Laurenczy, G. Chem. Commun. 2013, 49, 8735.  doi: 10.1039/c3cc43836h

    8. [8]

      Chen, J.; Chen, Q. -X.; Chen, Y. -W.; Fan, S. -S.; Wang, Y. -H.; Yang, L.; Lang, X. -M.; Zhang, W. -X.; Huang, Y.; Xiong, W. -T. Energy Storage Sci. Tech. 2015, 4, 131(in Chinese).  doi: 10.3969/j.issn.2095-4239.2015.02.002

    9. [9]

      Chen, Z.; Yang, Y. -Q.; Bao, J. -G.; Wang, W. -Y.; Jiang, X. -M.; Chem. Ind. Eng. Prog. 2010, 29, 484(in Chinese).
       

    10. [10]

      Li, L. -L.; Fan, S. -S.; Chen, Q. -X.; Yang, G.; Wen, Y. -G. Energy Storage Sci. Tech. 2018, 7, 586(in Chinese).
       

    11. [11]

      Niaz, S.; Manzoor, T.; Pandith, A. H. Renew. Sust. Energ. Rev. 2015, 50, 457.  doi: 10.1016/j.rser.2015.05.011

    12. [12]

      Ares, J. R. Int. J. Hydrogen Energy 2014, 39, 9824.  doi: 10.1016/j.ijhydene.2014.05.096

    13. [13]

      Sordakis, K.; Tang, C.; Vogt, L. K.; Junge, H.; Dyson, P. J.; Beller, M.; Laurenczy, G. Chem. Rev. 2018, 118, 372.  doi: 10.1021/acs.chemrev.7b00182

    14. [14]

      Alberico, E.; Nielsen, M. Chem. Commun. (Camb.) 2015, 51, 6714.  doi: 10.1039/C4CC09471A

    15. [15]

      He, T.; Pachfule, P.; Wu, H.; Xu, Q.; Chen, P. Nat. Rev. Mater. 2016, 1, 16059.  doi: 10.1038/natrevmats.2016.59

    16. [16]

      Li, H. -W.; Yan, Y.; Orimo, S. -I.; Züttel, A.; Jensen, C. M. Energies 2011, 4, 185.  doi: 10.3390/en4010185

    17. [17]

      Peng, B.; Chen, J. Energ. Environ. Sci. 2008, 1, 479.  doi: 10.1039/B809243P

    18. [18]

      Zhu, Q. -L.; Xu, Q. Energ. Environ. Sci. 2015, 8, 478.  doi: 10.1039/C4EE03690E

    19. [19]

      Klerke, A.; Christensen, C. H.; N rskov, J. K.; Vegge, T. J. Mater. Chem. 2008, 18, 2304.  doi: 10.1039/b720020j

    20. [20]

      Moury, R.; Moussa, G.; Demirci, U. B.; Hannauer, J.; Bernard, S.; Petit, E.; van der Lee, A.; Miele, P. Phys. Chem. Chem. Phys. 2012, 14, 1768.  doi: 10.1039/C2CP23403C

    21. [21]

      Zhao, H. Y.; Oyama, S. T.; Naeemi, E. D. Catal. Today 2010, 149, 172.  doi: 10.1016/j.cattod.2009.02.039

    22. [22]

    23. [23]

      Johnson, T. C.; Morris, D. J.; Wills, M. Chem. Soc. Rev. 2010, 39, 81.  doi: 10.1039/B904495G

    24. [24]

    25. [25]

      Smith, T. A.; Maitlis, P. M. J. Organomet. Chem. 1984, 269, c7.  doi: 10.1016/0022-328X(84)80283-1

    26. [26]

      Wang, W. -H.; Himeda, Y.; Muckerman, J. T.; Manbeck, G. F.; Fujita, E. Chem. Rev. 2015, 115, 12936.  doi: 10.1021/acs.chemrev.5b00197

    27. [27]

      Sá, S.; Silva, H.; Brand o, L.; Sousa, J. M.; Mendes, A. Appl. Catal. B-Environ. 2010, 99, 43.  doi: 10.1016/j.apcatb.2010.06.015

    28. [28]

      Iulianelli, A.; Ribeirinha, P.; Mendes, A.; Basile, A. Renew. Sust. Energ. Rev. 2014, 29, 355.  doi: 10.1016/j.rser.2013.08.032

    29. [29]

      Cortright, R. D.; Davda, R. R.; Dumesic, J. A. Nature 2002, 418, 964.  doi: 10.1038/nature01009

    30. [30]

      Lin, L.; Zhou, W.; Gao, R.; Yao, S.; Zhang, X.; Xu, W.; Zheng, S.; Jiang, Z.; Yu, Q.; Li, Y. -W.; Shi, C.; Wen, X. -D.; Ma, D. Nature 2017, 544, 80.  doi: 10.1038/nature21672

    31. [31]

      Palo, D. R.; Dagle, R. A.; Holladay, J. D. Chem. Rev. 2007, 107, 3992.  doi: 10.1021/cr050198b

    32. [32]

      Navarro, R. M.; Pe a, M. A.; Fierro, J. L. G. Chem. Rev. 2007, 107, 3952.  doi: 10.1021/cr0501994

    33. [33]

      Wu, S.; Xiong. X. -D.; Wang, S. -G. Rare Metals 2007, 31, 237(in Chinese).  doi: 10.3969/j.issn.0258-7076.2007.02.022

    34. [34]

      Smith, T. A.; Aplin, R. P.; Maitlis, P. M. J. Organomet. Chem. 1985, 291, c13.  doi: 10.1016/0022-328X(85)80213-8

    35. [35]

      Shinoda, S.; Itagaki, H.; Saito, Y. J. Chem. Soc.; Chem. Commun. 1985, 13, 860.  doi: 10.1039/C39850000860

    36. [36]

      Itagaki, H.; Shinoda, S.; Saito, Y.; Bull. Chem. Soc. Jpn. 1988, 61, 2291.  doi: 10.1246/bcsj.61.2291

    37. [37]

      Morton, D.; Cole-Hamilton, D. J. J. Chem. Soc. Chem. Commun.; 1988, 1154.  doi: 10.1002/chin.198904276

    38. [38]

      Fujii, T.; Saito, Y. J. Mol. Catal. 1991, 67, 185.  doi: 10.1016/0304-5102(91)85045-4

    39. [39]

      Sieffert, N.; Bühl, M. J. Am. Chem. Soc. 2010, 132, 8056.  doi: 10.1021/ja101044c

    40. [40]

      Rodríguezlugo, R. E.; Trincado, M.; Vogt, M.; Tewes, F.; Santisoquinones, G.; Grützmacher, H. Nat. Chem. 2013, 5, 342.  doi: 10.1038/nchem.1595

    41. [41]

      Nielsen, M.; Alberico, E.; Baumann, W.; Drexler, H. -J.; Junge, H.; Gladiali, S.; Beller, M. Nature 2013, 495, 85.  doi: 10.1038/nature11891

    42. [42]

      Li, H.; Hall, M. B. J. Am. Chem. Soc. 2015, 137, 12330.  doi: 10.1021/jacs.5b07444

    43. [43]

      Jing, Y.; Chen, X.; Yang, X. J. Organomet. Chem. 2016, 820, 55.  doi: 10.1016/j.jorganchem.2016.07.020

    44. [44]

      Sinha, V.; Trincado, M.; Grützmacher, H.; de Bruin, B.; J. Am. Chem. Soc. 2018, 140, 13103.  doi: 10.1021/jacs.8b09011

    45. [45]

      Kuriyama, W.; Matsumoto, T.; Ogata, O.; Ino, Y.; Aoki, K.; Tanaka, S.; Ishida, K.; Kobayashi, T.; Sayo, N.; Saito, T. Org. Process. Res. Dev. 2012, 16, 166.  doi: 10.1021/op200234j

    46. [46]

      (a) Bertoli, M.; Choualeb, A.; Lough, A. J.; Moore, B.; Spasyuk, D.; Gusev, D. G. Organometallics 2011, 30, 3479.
      (b) Nielsen, M.; Kammer, A.; Cozzula, D.; Junge, H.; Gladiali, S.; Beller, M. Angew. Chem.; Int. Ed. Engl. 2011, 50, 9593.

    47. [47]

      Lei, M.; Pan, Y.; Ma, X. Eur. J. Inorg. Chem. 2015, 2015, 794.  doi: 10.1002/ejic.201403027

    48. [48]

      Alberico, E.; Lennox, A. J.; Vogt, L. K.; Jiao, H.; Baumann, W.; Drexler, H. J.; Nielsen, M.; Spannenberg, A.; Checinski, M. P.; Junge, H.; Beller, M. J. Am. Chem. Soc. 2016, 138, 14890.  doi: 10.1021/jacs.6b05692

    49. [49]

      Yang, X. ACS Catal. 2014, 4, 1129.  doi: 10.1021/cs500061u

    50. [50]

      Monney, A.; Barsch, E.; Sponholz, P.; Junge, H.; Ludwig, R.; Beller, M. Chem. Commun. 2014, 50, 707.  doi: 10.1039/C3CC47306F

    51. [51]

      Hu, P.; Diskin-Posner, Y.; Ben-David, Y.; Milstein, D. ACS Catal. 2014, 4, 2649.  doi: 10.1021/cs500937f

    52. [52]

      Heim, L. E.; Schl rer, N. E.; Choi, J. H.; Prechtl, M. H. Nat. Commun. 2014, 5, 3621.  doi: 10.1038/ncomms4621

    53. [53]

      Crabtree, R. H. New J. Chem. 2011, 35, 18.  doi: 10.1039/C0NJ00776E

    54. [54]

      (a) Crabtree, R. H. Chem. Rev. 2017, 117, 9228.
      (b) Grützmacher, H.; Angew. Chem.; Int. Ed. 2008, 47, 1814.

    55. [55]

      Kothandaraman, J.; Kar, S.; Goeppert, A.; Sen, R.; Prakash, G. K. S. Top. Catal. 2018, 61, 542.  doi: 10.1007/s11244-018-0963-9

    56. [56]

      Heim, L. E.; Thiel, D.; Gedig, C.; Deska, J.; Prechtl, M. H. G. Angew. Chem.; Int. Ed. 2015, 54, 10308.  doi: 10.1002/anie.201503737

    57. [57]

      Kothandaraman, J.; Goeppert, A.; Czaun, M.; Olah, G. A.; Prakash, G. K. S. J. Am. Chem. Soc. 2016, 138, 778.  doi: 10.1021/jacs.5b12354

    58. [58]

      Van de Watering, F. F.; Lutz, M.; Dzik, W. I.; de Bruin, B.; Reek, J. N. H. ChemCatChem 2016, 8, 2752.  doi: 10.1002/cctc.201600709

    59. [59]

      Shinoda, S.; Yamakawa, T. J. Chem. Soc.; Chem. Commun. 1990, 1511.  doi: 10.1002/chin.199115049

    60. [60]

      Shinoda, S.; Ohnishi, T.; Yamakawa, T. Catal. Sur. Asia 1997, 1, 25.  doi: 10.1023/A:1019060526478

    61. [61]

      Robles-Dutenhefnera, P. A.; Mourab, E. M.; Gamac, G. J. J. Mol. Catal. A Chem. 2000, 164, 39.  doi: 10.1016/S1381-1169(00)00202-8

    62. [62]

      Campos, J.; Sharninghausen, L. S.; Manas, M. G.; Crabtree, R. H. Inorg. Chem. 2015, 54, 5079.  doi: 10.1021/ic502521c

    63. [63]

      Manas, M. G.; Campos, J.; Sharninghausen, L. S.; Lin, E.; Crabtree, R. H. Green Chemistry 2015, 17, 594.  doi: 10.1039/C4GC01694G

    64. [64]

      Fujita, K.; Kawahara, R.; Aikawa, T.; Yamaguchi, R. Angew. Chem. 2015, 127, 9185.  doi: 10.1002/ange.201502194

    65. [65]

      Prichatz, C.; Alberico, E.; Baumann, W.; Junge, H.; Beller, M. ChemCatChem 2017, 9, 1891.  doi: 10.1002/cctc.201700015

    66. [66]

      Shen, Y.; Zhan, Y.; Li, S.; Ning, F.; Du, Y.; Huang, Y.; He, T.; Zhou, X. Chem. Sci. 2017, 8, 7498.  doi: 10.1039/C7SC01778B

    67. [67]

      Morton, D.; Cole-Hamilton, D. J. J. Chem. Soc. Chem. Commun. 1987, 0, 248.  doi: 10.1039/C39870000248

    68. [68]

      Zhan, Y. L.; Shen, Y. B.; Li, S. P.; Yue, B. H.; Zhou, X. C. Chin. Chem. Lett. 2017, 28, 1353.  doi: 10.1016/j.cclet.2017.03.038

    69. [69]

      Chai, H. -N.; Liu, B.; Liu, A. -Q.; Yu, K. J. Mol. Catal 2018, 32, 481(in Chinese).  doi: 10.16084/j.cnki.issn1001-3555.2018.05.008

    70. [70]

      Alberico, E.; Sponholz, P.; Cordes, C.; Nielsen, M.; Drexler, H. J.; Baumann, W.; Junge, H.; Beller, M. Angew. Chem.; Int. Ed. Engl. 2013, 52, 14162.  doi: 10.1002/anie.201307224

    71. [71]

      Bielinski, E. A.; F rster, M.; Zhang, Y.; Bernskoetter, W. H.; Hazari, N.; Holthausen, M. C. ACS Catal. 2015, 5, 2404.  doi: 10.1021/acscatal.5b00137

    72. [72]

      Wakizaka, M.; Matsumoto, T.; Tanaka, R.; Chang, H. -C. Nat. Commun. 2016, 7, 12333.  doi: 10.1038/ncomms12333

    73. [73]

      Eisenstein, O.; Crabtree, R. H. New J. Chem. 2013, 37, 21.  doi: 10.1039/C2NJ40659D

    74. [74]

      Andérez-Fernández. M; Vogt, L. K.; Fischer, S.; Zhou, W.; Jiao, H.; Garbe, M.; Elangovan, S.; Junge, K.; Junge, H.; Ludwig, R.; Beller, M. Angew. Chem.; Int. Ed. Engl. 2017, 56, 559.  doi: 10.1002/anie.201610182

    75. [75]

      Wei, Z.; de Aguirre, A.; Junge, K.; Beller, M.; Jiao, H. J. Catal. Sci. Technol. 2018, 8, 3649.  doi: 10.1039/C8CY00746B

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