Citation: Shaopeng Li, Jing Du, Bin Zhang, Yanzhen Liu, Qingqing Mei, Qinglei Meng, Minghua Dong, Juan Du, Zhijuan Zhao, Lirong Zheng, Buxing Han, Meiting Zhao, Huizhen Liu. Selective Hydrogenation of 5-(Hydroxymethyl)furfural to 5-Methylfurfural by Exploiting the Synergy between Steric Hindrance and Hydrogen Spillover[J]. Acta Physico-Chimica Sinica, ;2022, 38(10): 220601. doi: 10.3866/PKU.WHXB202206019 shu

Selective Hydrogenation of 5-(Hydroxymethyl)furfural to 5-Methylfurfural by Exploiting the Synergy between Steric Hindrance and Hydrogen Spillover

Shaopeng Li ^{1, 2, 3} ,
Jing Du ³ ,
Bin Zhang ¹ ,
Yanzhen Liu ¹ ,
Qingqing Mei ¹ ,
Qinglei Meng ^{1, 3} ,
Minghua Dong ^{1, 2} ,
Juan Du ¹ ,
Zhijuan Zhao ¹ ,
Lirong Zheng ⁴ ,
Buxing Han ^{1, 2, 5} ,
Meiting Zhao ^3,, ,
Huizhen Liu ^{1, 2, 5,,}

1.
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid and Interface and Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
2.
School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China
3.
Institute of Molecular Aggregation Science, Tianjin University, Tianjin 300072, China
4.
Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
5.
Physical Science Laboratory, Huairou National Comprehensive Science Center, Beijing 101407, China

Corresponding author: Meiting Zhao, mtzhao@tju.edu.cn Huizhen Liu, liuhz@iccas.ac.cn
Received Date: 14 June 2022
Revised Date: 7 July 2022
Accepted Date: 21 July 2022
Available Online: 29 July 2022
Fund Project: the National Key Research and Development Program of China 2017YFA0403003the National Key Research and Development Program of China 2017YFA0403101National Natural Science Foundation of China 21871277National Natural Science Foundation of China 21603235National Natural Science Foundation of China 21403248National Natural Science Foundation of China 21905195China Postdoctoral Science Foundation 2021M702435Beijing Municipal Science & Technology Commission Z191100007219009

Selective hydrogenation is a vital class of reaction. Various unsaturated functional groups in organic compounds, such as aromatic rings, alkynyl (C≡C), carbonyl (C＝O), nitro (-NO₂), and alkenyl (C＝C) groups, are typical targets in selective hydrogenation. Therefore, selectivity is a key indicator of the efficiency of a designed hydrogenation reaction. 5-(Hydroxymethyl)furfural (HMF) is an important platform compound in the context of biomass conversion, and recently, the hydrogenation of HMF to produce fuels and other valuable chemicals has received significant attention. Controlling the selectivity of HMF hydrogenation is paramount because of the different reducible functional groups (C＝O, C-OH, and C＝C) in HMF. Moreover, the exploration of new routes for hydrogenating HMF to valuable chemicals is becoming attractive. 5-Methylfurfural (MF) is also an important organic compound; thus, the selective hydrogenation of HMF to MF is an essential synthetic route. However, this reaction has challenging thermodynamic and kinetic aspects, making it difficult to realize. Herein, we propose a strategy to design a highly efficient catalytic system for selective hydrogenation by exploiting the synergy between steric hindrance and hydrogen spillover. The design and preparation of the Pt@PVP/Nb₂O₅ catalyst (PVP = polyvinyl pyrrolidone; Nb₂O₅ = niobium(V) oxide) were also conducted. Surprisingly, HMF could be converted to MF with 92% selectivity at 100% HMF conversion. The reaction pathway was revealed through the combination of control experiments and density functional theory calculations. Although PVP blocked HMF from accessing the surface of Pt, hydrogen (H₂) could be activated on the surface of Pt due to its small molecular size, and the activated H₂ could migrate to the surface of Nb₂O₅ through a phenomenon called H₂ spillover. The Lewis acidic surface of Nb₂O₅ could not adsorb the C＝O group but could adsorb and activate the C-OH group of HMF; therefore, when HMF was adsorbed on Nb₂O₅, the C-OH groups were hydrogenated by the spilled over H₂ to form MF. The high selectivity of this reaction was realized because of the unique combination of steric effects, hydrogen spillover, and tuning of the electronic states of the Pt and Nb₂O₅ surfaces. This new route for producing MF has great potential for practical application owing to its discovered advantages. We believe that this novel strategy can be used to design catalysts for other selective hydrogenation reactions. Furthermore, this study demonstrates a significant breakthrough in selective hydrogenation, which will be of interest to researchers working on the utilization of biomass, organic synthesis, catalysis, and other related fields.
- Biomass,
- 5-Hydroxymethylfurfural,
- Selective hydrodeoxygenation,
- Steric hindrance,
- Hydrogen spillover
1. [1]
  Ragauskas, A. J.; Williams, C. K.; Davison, B. H.; Britovsek, G.; Cairney, J.; Eckert, C. A.; Frederick, W. J., Jr.; Hallett, J. P.; Leak, D. J.; Liotta, C. L.; et al. Science 2006, 311, 484. doi: 10.1126/science.1114736 doi: 10.1126/science.1114736
2. [2]
  Román-Leshkov, Y.; Barrett, C. J.; Liu, Z. Y.; Dumesic, J. A. Nature 2007, 447, 982. doi: 10.1038/nature05923 doi: 10.1038/nature05923
3. [3]
  Putten, R. J.; Waal, J. C.; Jong, E.; Rasrendra, C. B.; Heeres, H. J.; Vries, J. G. Chem. Rev. 2013, 113, 1499. doi: 10.1021/cr300182k doi: 10.1021/cr300182k
4. [4]
  Vriamont, C.; Haynes, T.; Cague-Murphy, E. M.; Pennetreau, F.; Riant, O.; Hermans, S. J. Catal. 2015, 329, 389. doi: 10.1016/j.jcat.2015.06.003 doi: 10.1016/j.jcat.2015.06.003
5. [5]
  Fang, R. Q.; Luque, R.; Li, Y. W. Green Chem. 2017, 19, 647. doi: 10.1039/c6gc02018f doi: 10.1039/c6gc02018f
6. [6]
  Besson, M.; Gallezot, P.; Pinel, C. Chem. Rev. 2014, 114, 1827. doi: 10.1021/cr4002269 doi: 10.1021/cr4002269
7. [7]
  Luo, J.; Yun, H.; Mironenko, A. V.; Goulas, K.; Lee, J. D.; Monai, M.; Wang, C.; Vorotnikov, V.; Murray, C. B.; Vlachos, D. G.; et al. ACS Catal. 2016, 6, 4095. doi: 10.1021/acscatal.6b00750 doi: 10.1021/acscatal.6b00750
8. [8]
  Thananatthanachon, T.; Rauchfuss, T. B. Angew. Chem. Int. Edit. 2010, 49, 6616. doi: 10.1002/anie.201002267 doi: 10.1002/anie.201002267
9. [9]
  Nilges, P.; Schroder, U. Energ. Environ. Sci. 2013, 6, 2925. doi: 10.1039/c3ee41857j doi: 10.1039/c3ee41857j
10. [10]
  Yang, P. P.; Cui, Q. Q.; Zu, Y. H.; Liu, X. H.; Lu, G. Z.; Wang, Y. Q. Catal. Commun. 2015, 66, 55. doi: 10.1016/j.catcom.2015.02.014 doi: 10.1016/j.catcom.2015.02.014
11. [11]
  Wang, G. H.; Hilgert, J.; Richter, F. H.; Wang, F.; Bongard, H. J.; Spliethoff, B.; Weidenthaler, C.; Schüth, F. Nat. Mater. 2014, 13, 294. doi: 10.1038/nmat3872 doi: 10.1038/nmat3872
12. [12]
  Alamillo, R.; Tucker, M.; Chia, M.; Pagan-Torres, Y.; Dumesic, J. Green Chem. 2012, 14, 1413. doi: 10.1039/c2gc35039d doi: 10.1039/c2gc35039d
13. [13]
  Nakagawa, Y.; Tomishige, K. Catal. Commun. 2010, 12, 154. doi: 10.1016/j.catcom.2010.09.003 doi: 10.1016/j.catcom.2010.09.003
14. [14]
  Liu, F.; Audemar, M.; Vigier, K. D.; Clacens, J. M.; De, C. F.; Jerome, F. Green Chem. 2014, 16, 4110. doi: 10.1039/c4gc01158a doi: 10.1039/c4gc01158a
15. [15]
  Jung, M. E.; Im, G-Y. J. Org. Chem. 2009, 74, 8739. doi: 10.1021/jo902029x doi: 10.1021/jo902029x
16. [16]
  Wang, W.; Zhao, X. M.; Wang, J. L.; Geng, X.; Gong, J. F.; Hao, X. Q.; Song, M. P. Tetrahedron Lett. 2014, 55, 3192. doi: 10.1016/j.tetlet.2014.04.020 doi: 10.1016/j.tetlet.2014.04.020
17. [17]
  Michail, K.; Matzi, V.; Maier, A.; Herwig, R.; Greilberger, J.; Juan, H.; Kunert, O.; Wintersteiger, R. Anal. Bioanal. Chem. 2007, 387, 2801. doi: 10.1007/s00216-007-1121-6 doi: 10.1007/s00216-007-1121-6
18. [18]
  Tradtrantip, L.; Sonawane, N. D.; Namkung, W.; Verkman, A. S. J. Med. Chem. 2009, 52, 6447. doi: 10.1021/jm9009873 doi: 10.1021/jm9009873
19. [19]
  Huber, G. W.; Iborra, S.; Corma, A. Chem. Rev. 2006, 106, 4044. doi: 10.1021/cr068360d doi: 10.1021/cr068360d
20. [20]
  Corma, A.; de la Torre, O.; Renz, M.; Villandier, N. Angew. Chem. Int. Edit. 2011, 50, 2375. doi: 10.1002/anie.201007508 doi: 10.1002/anie.201007508
21. [21]
  Mascal, M.; Nikitin, E. B. Angew. Chem. Int. Edit. 2008, 47, 7924. doi: 10.1002/anie.200801594 doi: 10.1002/anie.200801594
22. [22]
  Li, S.; Dong, M.; Yang, J.; Cheng, X.; Shen, X.; Liu, S.; Wang, Z. -Q.; Gong, X. -Q.; Liu, H.; Han, B. Nat. Commun. 2021, 12, 584. doi: 10.1038/s41467-020-20878-7 doi: 10.1038/s41467-020-20878-7
23. [23]
  Shao, Y.; Xia, Q. N.; Dong, L.; Liu, X. H.; Han, X.; Parker, S. F.; Cheng, Y. Q.; Daemen, L. L.; Ramirez-Cuesta, A. J.; Yang, S. H.; et al. Nat. Commun. 2017, 8, 16104. doi: 10.1038/ncomms16104 doi: 10.1038/ncomms16104
24. [24]
  Chen, G. X.; Xu, C. F.; Huang, X. Q.; Ye, J. Y.; Gu, L.; Li, G.; Tang, Z. C.; Wu, B. H.; Yang, H. Y.; Zhao, Z. P.; et al. Nat. Mater. 2016, 15, 564. doi: 10.1038/NMAT4555 doi: 10.1038/NMAT4555
25. [25]
  Tamura, M.; Tomishige, K. Angew. Chem. Int. Edit. 2015, 54, 864. doi: 10.1002/anie.201409601 doi: 10.1002/anie.201409601
26. [26]
  Badri, A.; Binet, C.; Lavalley, J. C. J. Chem. Soc. Faraday T. 1997, 93, 1159. doi: 10.1039/a606628c doi: 10.1039/a606628c
27. [27]
  Xia, Q. N.; Chen, Z. J.; Shao, Y.; Gong, X. Q.; Wang, H. F.; Liu, X. H.; Parker, S. F.; Han, X.; Yang, S. H.; Wang, Y. Q. Nat. Commun. 2016, 7, 11162. doi: 10.1038/ncomms11162 doi: 10.1038/ncomms11162
28. [28]
  Xia, Q. N.; Cuan, Q.; Liu, X. H.; Gong, X. Q.; Lu, G. Z.; Wang, Y. Q. Angew. Chem. Int. Edit. 2014, 53, 9755. doi: 10.1002/anie.201403440 doi: 10.1002/anie.201403440
29. [29]
  Chen, H. L.; Yang, H.; Briker, Y.; Fairbridge, C.; Omotoso, O.; Ding, L. H.; Zheng, Y.; Ring, Z. Catal. Today 2007, 125, 256. doi: 10.1016/j.cattod.2007.01.024 doi: 10.1016/j.cattod.2007.01.024
30. [30]
  Karim, W.; Spreafico, C.; Kleibert, A.; Gobrecht, J.; VandeVondele, J.; Ekinci, Y.; van Bokhoven, J. A. Nature 2017, 541, 68. doi: 10.1038/nature20782 doi: 10.1038/nature20782
31. [31]
  Sodesawa, T.; Sato, S.; Nozaki, F. Stud. Surf. Sci. Catal. 1993, 77, 401. doi: 10.1016/S0167-2991(08)63221-8 doi: 10.1016/S0167-2991(08)63221-8
32. [32]
  Liu, R. X.; Yu, Y. C.; Yoshida, K.; Li, G. M.; Jiang, H. X.; Zhang, M. H.; Zhao, F. Y.; Fujita, S.; Arai, M. J. Catal. 2010, 269, 191. doi: 10.1016/j.jcat.2009.11.007 doi: 10.1016/j.jcat.2009.11.007
33. [33]
  Ma, D.; Lu, S.; Liu, X.; Guo, Y.; Wang, Y. Chin. J. Catal. 2019, 40, 609. doi: 10.1016/S1872-2067(19)63317-6 doi: 10.1016/S1872-2067(19)63317-6
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