利用空间位阻和氢溢流协同作用促进5-羟甲基糠醛选择性加氢制备5-甲基糠醛

doi:10.3866/PKU.WHXB202206019

Acta Phys. -Chim. Sin. ›› 2022, Vol. 38 ›› Issue (10): 2206019.doi: 10.3866/PKU.WHXB202206019

Special Issue: Catalytic Conversion of Biomass

• ARTICLE • Previous Articles Next Articles

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

Shaopeng Li¹^,²^,³, Jing Du³, Bin Zhang¹, Yanzhen Liu¹, Qingqing Mei¹, Qinglei Meng¹^,³, Minghua Dong¹^,², Juan Du¹, Zhijuan Zhao¹, Lirong Zheng⁴, Buxing Han¹^,²^,⁵, Meiting Zhao³^,*(), Huizhen Liu¹^,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

Received:2022-06-14 Accepted:2022-07-21 Published:2022-07-29
Contact: Meiting Zhao,Huizhen Liu E-mail:mtzhao@tju.edu.cn;liuhz@iccas.ac.cn
About author:Huizhen Liu, E-mail: liuhz@iccas.ac.cn
Meiting Zhao, E-mail: mtzhao@tju.edu.cn
Supported by:
the National Key Research and Development Program of China(2017YFA0403003);the National Key Research and Development Program of China(2017YFA0403101);National Natural Science Foundation of China(21871277);National Natural Science Foundation of China(21603235);National Natural Science Foundation of China(21403248);National Natural Science Foundation of China(21905195);China Postdoctoral Science Foundation(2021M702435);Beijing Municipal Science & Technology Commission(Z191100007219009)

Abstract

Abstract:

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.

Key words: Biomass, 5-Hydroxymethylfurfural, Selective hydrodeoxygenation, Steric hindrance, Hydrogen spillover

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 Phys. -Chim. Sin. 2022, 38(10), 2206019. doi: 10.3866/PKU.WHXB202206019

Figures/Tables 8

References 33

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
2	Román-Leshkov, Y.; Barrett, C. J.; Liu, Z. Y.; Dumesic, J. A. Nature 2007, 447, 982. doi: 10.1038/nature05923
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
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
5	Fang, R. Q.; Luque, R.; Li, Y. W. Green Chem. 2017, 19, 647. doi: 10.1039/c6gc02018f
6	Besson, M.; Gallezot, P.; Pinel, C. Chem. Rev. 2014, 114, 1827. doi: 10.1021/cr4002269
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
8	Thananatthanachon, T.; Rauchfuss, T. B. Angew. Chem. Int. Edit. 2010, 49, 6616. doi: 10.1002/anie.201002267
9	Nilges, P.; Schroder, U. Energ. Environ. Sci. 2013, 6, 2925. doi: 10.1039/c3ee41857j
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
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
12	Alamillo, R.; Tucker, M.; Chia, M.; Pagan-Torres, Y.; Dumesic, J. Green Chem. 2012, 14, 1413. doi: 10.1039/c2gc35039d
13	Nakagawa, Y.; Tomishige, K. Catal. Commun. 2010, 12, 154. doi: 10.1016/j.catcom.2010.09.003
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
15	Jung, M. E.; Im, G-Y. J. Org. Chem. 2009, 74, 8739. doi: 10.1021/jo902029x
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
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
18	Tradtrantip, L.; Sonawane, N. D.; Namkung, W.; Verkman, A. S. J. Med. Chem. 2009, 52, 6447. doi: 10.1021/jm9009873
19	Huber, G. W.; Iborra, S.; Corma, A. Chem. Rev. 2006, 106, 4044. doi: 10.1021/cr068360d
20	Corma, A.; de la Torre, O.; Renz, M.; Villandier, N. Angew. Chem. Int. Edit. 2011, 50, 2375. doi: 10.1002/anie.201007508
21	Mascal, M.; Nikitin, E. B. Angew. Chem. Int. Edit. 2008, 47, 7924. doi: 10.1002/anie.200801594
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
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
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
25	Tamura, M.; Tomishige, K. Angew. Chem. Int. Edit. 2015, 54, 864. doi: 10.1002/anie.201409601
26	Badri, A.; Binet, C.; Lavalley, J. C. J. Chem. Soc. Faraday T. 1997, 93, 1159. doi: 10.1039/a606628c
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
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
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
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
31	Sodesawa, T.; Sato, S.; Nozaki, F. Stud. Surf. Sci. Catal. 1993, 77, 401. doi: 10.1016/S0167-2991(08)63221-8
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
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


Entry	Catalyst	Time/h	Conv./%	Sel./%
Entry	Catalyst	Time/h	Conv./%	1	2	3	4
1	Pt@PVP/Nb₂O₅	24	> 99	92	–	–	–
2	Nb₂O₅	12	7	63	–	–	–
3	Pt/Nb₂O₅	3.0	80	12	60	17	0
4	Pt@PVP	12	16	37	45	-	–
5 ^b	Pt/C-com.	0.5	23	–	–	–	90
6	Pt@PVP/C	12	56	32	–	–	57
7	Pt@PVP/TiO₂	12	48	25	64	9	–


Entry	Cat./mg		Time/h	Conv./%	Sel./%
Entry	1	2	Time/h	Conv./%	1	2	3	4
1	40	–	1.5	0.6	61	–	–	–
2	–	10	1.5	65	trace	10	–	83
3	40	10	1.5	32	20	–	–	67
4	40	5	1.0	28	24	–	–	56
5	40	3	0.5	8	43	–	–	51
6	–	3	0.5	23	–	90	–	–

[1]	Yucui Hou, Zhuosen He, Shuhang Ren, Weize Wu. Catalytic Oxidation of Biomass to Formic Acid under O₂ with Homogeneous Catalysts [J]. Acta Phys. -Chim. Sin., 2023, 39(9): 2212065-0.
[2]	Huixian Han, Lan Chen, Jiancheng Zhao, Haitao Yu, Yang Wang, Helian Yan, Yingxiong Wang, Zhimin Xue, Tiancheng Mu. Biomass-based Acidic Deep Eutectic Solvents for Efficient Dissolution of Lignin: Towards Performance and Mechanism Elucidation [J]. Acta Phys. -Chim. Sin., 2023, 39(7): 2212043-0.
[3]	Shuyi Zheng, Jia Wu, Ke Wang, Mengchen Hu, Huan Wen, Shibin Yin. Electronic Modulation of Ni-Mo-O Porous Nanorods by Co Doping for Selective Oxidation of 5-Hydroxymethylfurfural Coupled with Hydrogen Evolution [J]. Acta Phys. -Chim. Sin., 2023, 39(12): 2301032-.
[4]	Yan Yang, Bowen He, Hualong Ma, Sen Yang, Zhouhong Ren, Tian Qin, Fagui Lu, Liwen Ren, Yixiao Zhang, Tianfu Wang, Xi Liu, Liwei Chen. PtRuAgCoNi High-Entropy Alloy Nanoparticles for High-Efficiency Electrocatalytic Oxidation of 5-Hydroxymethylfurfural [J]. Acta Phys. -Chim. Sin., 2022, 38(12): 2201050-.
[5]	Hao Zhou, Yaxuan Jing, Yanqin Wang. Activation/Cleavage of C―O/C―C Bonds during Biomass Conversion [J]. Acta Phys. -Chim. Sin., 2022, 38(10): 2203016-.
[6]	Jianan Teng, Guangyue Xu, Yao Fu. Aerobic Oxidation of 5-Hydroxymethylfurfural to Dimethyl Furan-2, 5-dicarboxylate over CoMn@NC Catalysts Using Atmospheric Oxygen [J]. Acta Phys. -Chim. Sin., 2022, 38(10): 2204031-.
[7]	Xueling Lang, Shutao Lei, Bolong Li, Xiaohong Li, Bing Ma, Chen Zhao. Approaches for the Synthesis of High-Melting Waxes: A Review [J]. Acta Phys. -Chim. Sin., 2022, 38(10): 2204045-.
[8]	Aiguo ZHONG,Rongrong LI,Qin HONG,Jie ZHANG,Dan CHEN. Understanding the Isomerization of Monosubstituted Alkanes from Energetic and Information-Theoretic Perspectives [J]. Acta Phys. -Chim. Sin., 2018, 34(3): 303-313.
[9]	Shan-Hui ZHU,Jian-Guo WANG,Wei-Bin FAN. Advances in Catalytic Hydrogenolysis of Glycerol to Fine Chemicals [J]. Acta Phys. -Chim. Sin., 2016, 32(1): 85-97.
[10]	ZHU Zhi-Wen, XU Guo-Hua, ANYue, HE Chao-Hong. Characterization of a Homogeneously Mixed Octyltriethoxyilane/Octadecyltrichlorosilane Self-Assembled Monolayer and Analysis of Its Formation Mechanism [J]. Acta Phys. -Chim. Sin., 2014, 30(8): 1509-1517.
[11]	HUANG Wen, ZHAO Jin, KANG Qi, XU Kaichen, YU Zhen, WANG Jian, MA Yan-Wen, HUANG Wei. Preparation of Three-Dimensional Carbon Microtube/Carbon Nanotube Composites and Their Application in Supercapacitor [J]. Acta Phys. -Chim. Sin., 2012, 28(10): 2269-2275.
[12]	GONG Yan-Yan, LIU Min, JIA Song-Yan, FENG Jian-Ping, SONG Chun-Shan, GUO Xin-Wen. Production of 5-Hydroxymethylfurfural from Inulin Catalyzed by Sulfonated Amorphous Carbon in an Ionic Liquid [J]. Acta Phys. -Chim. Sin., 2012, 28(03): 686-692.
[13]	XU Yong, YAN Shi-Zhi, YE Tong-Qi, ZHANG Zhao, LI Quan-Xin. Dimethyl Ether Production from Biomass Char and CO₂-Rich Bio-Syngas [J]. Acta Phys. -Chim. Sin., 2011, 27(08): 1926-1932.
[14]	YE Tong-Qi, ZHANG Zhao-Xia, XU Yong, YAN Shi-Zhi, ZHU Jiu-Fang, LIU Yong, LI Quan-Xin. Higher Alcohol Synthesis from Bio-Syngas over Na-Promoted CuCoMn Catalyst [J]. Acta Phys. -Chim. Sin., 2011, 27(06): 1493-1500.
[15]	XIE Ling-Hai, CHANG Yong-Zheng, GU Ju-Fen, SUN Rui-Juan, LI Jie-Wei, ZHAO Xiang-Hua, HUANG Wei. Design of Organic/Polymeric π-Semiconductors: the Four-Element Principle [J]. Acta Phys. -Chim. Sin., 2010, 26(07): 1784-1794.

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

RichHTML

PDF

Like

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 8

References 33

Related Articles 15

Metrics

Recommended 0