Research progress of the heterogeneous catalysts for 2,5-dimethylfuran synthesis via hydrogenolysis of 5-hydroxymethylfufural

doi:10.16085/j.issn.1000-6613.2020-0710

Abstract

Abstract:

With the increasing shortage of fossil energy, the utilization of clean and renewable biomass resources, especially the preparation of high-quality biofuels has become a research hotspot. 2,5-Dimethylfuran (DMF) is regarded as one of the most promising liquid biofuels due to its excellent physical and chemical properties. DMF can be synthesized by selective hydrogenolysis of 5-hydroxymethylfurfural (HMF). However, HMF is chemically active and can be converted into various downstream products, so it is critical to develop catalysts with high selectivity for DMF production. In this review, recent advances of noble and non-noble metal-based catalysts are reviewed in detail for the hydrogenolysis of HMF to DMF. The limitations and problems in current researches, potential research trends of the catalysts and reaction systems were proposed. In addition, it is pointed out that the direct preparation of DMF from biomass and the establishment of effective separation technology are important for realizing the industrial production of DMF.

Key words: biomass, 5-hydroxymethylfurfural, catalysis, hydrogenolysis, biofuel, 2,5-dimethylfuran

摘要：

随着化石能源的日益短缺，清洁可再生生物质资源的利用，尤其是制备高品质生物燃料逐渐成为研究热点。2,5-二甲基呋喃（DMF）具有优良的物理化学性质，被认为是最有前途的液体生物燃料之一，可通过生物质平台分子5-羟甲基糠醛（HMF）选择性氢解制备。HMF化学性质非常活泼，可以转化成多种下游产品，因此设计制备高选择性催化剂对于靶向合成DMF至关重要。本文依据贵金属和非贵金属对催化剂进行分类，详细综述了非均相催化剂在HMF氢解制备DMF反应中的研究新进展；针对目前研究中存在的局限性和问题，提出了催化剂和反应体系的研究方向。此外，指出以生物质为原料直接制备DMF及建立有效的分离技术是实现DMF工业化生产的重要途径。

关键词: 生物质, 5-羟甲基糠醛, 催化, 氢解, 生物燃料, 2,5-二甲基呋喃

CLC Number:

Tong WANG, Hualiang AN, Fang LI, Wei XUE, Yanji WANG. Research progress of the heterogeneous catalysts for 2,5-dimethylfuran synthesis via hydrogenolysis of 5-hydroxymethylfufural[J]. Chemical Industry and Engineering Progress, 2021, 40(2): 824-834.

王彤, 安华良, 李芳, 薛伟, 王延吉. 非均相催化剂催化5-羟甲基糠醛氢解制备2,5-二甲基呋喃研究进展[J]. 化工进展, 2021, 40(2): 824-834.

Figures/Tables 7

References 70

1	BICKER M, HIRTH J, VOGEL H. Dehydration of fructose to 5-hydroxymethylfurfural in sub-and supercritical acetone[J]. Green Chemistry, 2003, 5(2): 280-284.
2	RINALDI R, SCHÜTH F. Acid hydrolysis of cellulose as the entry point into biorefinery schemes[J]. ChemSusChem, 2009, 2: 1096-1107.
3	方向晨. 生物质在能源资源替代中的途径及前景展望[J]. 化工进展, 2011, 30(11): 2333-2339.
	FANG X C. Routes and prospects in the energy resources replacing by biomasses[J]. Chemical Industry and Engineering Progress, 2011, 30(11): 2333-2339.
4	王泽, 林伟刚, 宋文立, 等. 生物质热化学转化制备生物燃料及化学品[J]. 化学进展, 2007, 19(7): 1190-1197.
	WANG Z, LIN W G, SONG W L, et al. Bio-fuel and chemicals by thermochemical treating of biomass[J]. Progress in Chemistry, 2007, 19(7): 1190-1197.
5	林鹿, 何北海, 孙润仓, 等. 木质生物质转化高附加值化学品[J]. 化学进展, 2007, 19(7): 1206-1216.
	LIN L, HE B H, SUN R C, et al. High-value chemicals from lignocellulosic biomass[J]. Progress in Chemistry, 2007, 19(7): 1206-1216.
6	SERRANO-RUIZ J C, DUMESIC J A. Catalytic routes for the conversion of biomass into liquid hydrocarbon transportation fuels[J]. Energy & Environmental Science, 2011, 4(1): 83-99.
7	ZHANG X H, ZHANG Q, WANG T J, et al. Hydrodeoxygenation of lignin-derived phenolic compounds to hydrocarbons over Ni/SiO₂-ZrO₂ catalysts[J]. Bioresource Technology, 2013, 134: 73-80.
8	NORONHA F B, SCHMAL M, MORAWECK B, et al. Characterization of niobia-supported palladium-cobalt catalysts[J]. The Journal of Physical Chemistry B, 2000, 104(23): 5478-5485.
9	SAHA B, ABU-OMAR M M. Current technologies, economics, and perspectives for 2,5-dimethylfuran production from biomass-derived intermediates[J]. ChemSusChem, 2015, 8(7): 1133-1142.
10	GALKIN K I, ANANIKOV V P. When will 5-hydroxymethylfurfural, the “sleeping giant” of sustainable chemistry, awaken?[J]. ChemSusChem, 2019, 12: 2976-2982.
11	WANG X F, LIANG X H, LI J M, et al. Catalytic hydrogenolysis of biomass-derived 5-hydroxymethylfurfural to biofuel 2,5-dimethylfuran[J]. Applied Catalysis A: General, 2019, 576: 85-95.
12	TAN J, LIU Q, CHEN L, et al. Efficient production of ethyl levulinate from cassava over Al₂(SO₄)₃ catalyst in ethanol-water system[J]. Journal of Energy Chemistry, 2017, 26(1):115-120.
13	ANTONYRAJ C A, JEONG J, KIM B, et al. Selective oxidation of HMF to DFF using Ru/γ-alumina catalyst in moderate boiling solvents toward industrial production[J]. Industrial and Engineering Chemistry Research, 2013, 19(3): 1056-1059.
14	SHUAI X, ZHOU P, ZHANG Z, et al. Selective oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid using O₂ and a photocatalyst of Co-thioporphyrazine bonded to g-C₃N₄[J]. Journal of the American Chemical Society, 2017, 139(41): 14775-14782.
15	KUBOTA S R, CHOI K S. Electrochemical oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid (FDCA) in acidic media enabling spontaneous FDCA separation[J]. ChemSusChem, 2018, 11(13): 2138-2145.
16	ZHANG X Y, ZONG M H, LI N. Whole-cell biocatalytic selective oxidation of 5-hydroxymethylfurfural to 5-hydroxymethyl-2-furancarboxylic acid[J]. Green Chemistry, 2017, 19(19): 4544-4551.
17	JAE J, ZHENG W, KARIM A M, et al. The role of Ru and RuO₂ in the catalytic transfer hydrogenation of 5-hydroxymethylfurfural for the production of 2,5-dimethylfuran[J]. ChemCatChem, 2014, 6(3): 848-856.
18	TZENG T W, LIN C Y, PAO C W, et al. Understanding catalytic hydrogenolysis of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) using carbon supported Ru catalysts[J]. Fuel Processing Technology, 2020, 199: 106225.
19	RAUT A B, NANDA B, PARIDA K M, et al. Hydrogenolysis of biomass-derived 5-hydroxymethylfurfural to produce 2,5-dimethylfuran over Ru-ZrO₂-MCM-41 catalyst[J]. Chemistry Select, 2019, 4(20): 6080-6089.
20	NAGPURE A S, VENUGOPAL A K, LUCAS N, et al. Renewable fuels from biomass-derived compounds: Ru-containing hydrotalcites as catalysts for conversion of HMF to 2,5-dimethylfuran[J]. Catalysis Science & Technology, 2015, 5(3): 1463-1472.
21	YANG Y, LIU Q Y, LI D, et al. Selective hydrodeoxygenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran on Ru-MoO_x/C catalysts[J]. RSC Advances, 2017, 7(27): 16311-16318.
22	GAO Z, FAN G, LIU M, et al. Dandelion-like cobalt oxide microsphere-supported RuCo bimetallic catalyst for highly efficient hydrogenolysis of 5-hydroxymethylfurfural[J]. Applied Catalysis B: Environmental, 2018, 237(5): 649-659.
23	WANG X, LIU Y, LIANG X. Hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran over supported Pt-Co bimetallic catalysts under mild conditions[J]. Green Chemistry, 2018, 20(12): 2894-2902.
24	LUO J, YUN H, MIRONENKO A V, et al. Mechanisms for high selectivity in the hydrodeoxygenation of 5-hydroxymethylfurfural over PtCo nanocrystals[J]. ACS Catalysis, 2016, 6(7): 4095-4104.
25	LUO J, LEE J D, YUN H, et al. Base metal-Pt alloys: a general route to high selectivity and stability in the production of biofuels from HMF[J]. Applied Catalysis B: Environmental, 2016, 199(15): 439-446.
26	WANG G H, HILGERT J, RICHTER F H, et al. Platinum-cobalt bimetallic nanoparticles in hollow carbon nanospheres for hydrogenolysis of 5-hydroxymethylfurfural[J]. Nature Materials, 2014, 13(3): 293-300.
27	SCHOLZ D, AELLIG C, HERMANS I. Catalytic transfer hydrogenation/hydrogenolysis for reductive upgrading of furfural and 5-(hydroxymethyl)furfural[J]. ChemSusChem, 2014, 7(1): 268-275.
28	CHATTERJEE M, ISHIZAKA T, KAWANAMI H. Hydrogenation of 5-hydroxymethylfurfural in supercritical carbon dioxide-water: a tunable approach to dimethylfuran selectivity[J]. Green Chemistry, 2014, 16(3): 1543-1551.
29	MITRA J, ZHOU X, RAUCHFUSS T. Pd/C-catalyzed reactions of HMF: decarbonylation, hydrogenation, and hydrogenolysis[J]. Green Chemistry, 2015, 17(1): 307-313.
30	LIAO W P, ZHU Z G, CHEN N M, et al. Highly active bifunctional Pd-Co₉S₈/S-CNT catalysts for selective hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran[J]. Molecular Catalysis, 2020, 482: 110756.
31	NISHIMURA S, IKEDA N, EBITANI K. Selective hydrogenation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) under atmospheric hydrogen pressure over carbon supported PdAu bimetallic catalyst[J]. Catalysis Today, 2014, 232(1): 89-98.
32	ZHANG F, LIU Y, YUAN F, et al. Efficient production of the liquid fuel 2,5-dimethylfuran from 5-hydroxymethylfurfural in the absence of acid additive over bimetallic PdAu supported on graphitized carbon[J]. Energy and Fuels, 2017, 31(6): 6364-6373.
33	GAWADE A B, TIWARI M S, YADAV G D. Biobased green process: selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethyl furan under mild conditions using Pd-Cs_2.5H_0.5PW₁₂O₄₀/K-10 clay[J]. ACS Sustainable Chemistry and Engineering, 2016, 4(8): 4113-4123.
34	SAHA B, BOHN C M, ABU-OMAR M M. Zinc-assisted hydrodeoxygenation of biomass-derived 5-hydroxymethylfurfural to 2, 5-dimethylfuran[J]. ChemSusChem, 2014, 7(11): 3095-3101.
35	SARKAR C, KOLEY P, SHOWN I, et al. Integration of interfacial and alloy effects to modulate catalytic performance of metal-organic-framework-derived Cu-Pd nanocrystals toward hydrogenolysis of 5-hydroxymethylfurfural[J]. ACS Sustainable Chemistry and Engineering, 2019, 7: 10349-10362.
36	SHANG Y N, LIU C W, ZHANG Z N, et al. Insights into the synergistic effect in Pd immobilized to MOF-derived Co-CoO_x@ N-doped carbon for efficient selective hydrogenolysis of 5-hydroxylmethylfurfural[J]. Industrial and Engineering Chemistry Research, 2020, 59: 6532-6542.
37	KONG X, ZHU Y, ZHENG H, et al. Switchable synthesis of 2,5-dimethylfuran and 2,5-dihydroxymethyltetrahydrofuran from 5-hydroxymethylfurfural over Raney Ni catalyst[J]. RSC Advances, 2014, 4(105): 60467-60472.
38	KONG X, ZHENG R, ZHU Y, et al. Rational design of Ni-based catalysts derived from hydrotalcite for selective hydrogenation of 5-hydroxymethylfurfural[J]. Green Chemistry, 2015, 17(4): 2504-2514.
39	KONG X, ZHU Y, ZHENG H, et al. Ni nanoparticles inlaid nickel phyllosilicate as a metal-acid bifunctional catalyst for low-temperature hydrogenolysis reactions[J]. ACS Catalysis, 2015, 5(10): 5914-5920.
40	HUANG Y B, CHEN M Y, YAN L, et al. Nickel-tungsten carbide catalysts for the production of 2,5-dimethylfuran from biomass-derived molecules[J]. ChemSusChem, 2014, 7(4): 1068-1072.
41	YANG P, XIA Q, LIU X, et al. High-yield production of 2,5-dimethylfuran from 5-hydroxymethylfurfural over carbon supported Ni-Co bimetallic catalyst[J]. Journal of Energy Chemistry, 2016, 25(6): 1015-1020.
42	GOYAL R, SARKAR B, BAG A, et al. Studies of synergy between metal-support interfaces and selective hydrogenation of HMF to DMF in water[J]. Journal of Catalysis, 2016, 340: 248-260.
43	ZHU C, LIU Q, LI D, et al. Selective hydrodeoxygenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran over Ni supported on zirconium phosphate catalysts[J]. ACS Omega, 2018, 3(7): 7407-7417.
44	SUN Y, XIONG C X, LIU Q C, et al. Catalytic transfer hydrogenolysis/hydrogenation of biomass-derived 5-formyloxymethylfurfural to 2,5-dimethylfuran over Ni-Cu bimetallic catalyst with formic acid as a hydrogen donor[J]. Industrial & Engineering Chemistry Research, 2019, 58(14): 5414-5422.
45	GUO D W, LIU X X, CHENG F, et al. Selective hydrogenolysis of 5-hydroxymethylfurfural to produce biofuel 2,5-dimethylfuran over Ni/ZSM-5 catalysts[J]. Fuel, 2020, 274: 117853.
46	PRZYDACZ M, JEDRZEJCZYK M, BRZEZINSKA M, et al. Solvothermal hydrodeoxygenation of hydroxymethylfurfural derived from biomass towards added value chemicals on Ni/TiO₂ catalysts[J]. The Journal of Supercritical Fluids, 2020, 163: 104827.
47	GYNGAZOVA M S, NEGAHDAR L, BLUMENTHAL L C, et al. Experimental and kinetic analysis of the liquid phase hydrodeoxygenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran over carbon-supported nickel catalysts[J]. Chemical Engineering Science, 2017, 173: 455-464.
48	MANI C M, BRAUN M, MOLINARI V, et al. A high-throughput composite catalyst based on nickel carbon cubes for the hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran[J]. ChemCatChem, 2017, 9(17): 3388-3394.
49	LUO J, MONAI M, WANG C, et al. Unraveling the surface state and composition of highly selective nanocrystalline Ni-Cu alloy catalysts for hydrodeoxygenation of HMF[J]. Catalysis Science and Technology, 2017, 7(8): 1735-1743.
50	YU L, HE L, CHEN J, et al. Robust and recyclable nonprecious bimetallic nanoparticles on carbon nanotubes for the hydrogenation and hydrogenolysis of 5-hydroxymethylfurfural[J]. ChemCatChem, 2015, 7(11): 1701-1707.
51	ROMÁN-LESHKOV Y, BARRETT C J, LIU Z Y, et al. Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates[J]. Nature, 2007, 447(7147): 982-985.
52	HANSEN T S, BARTA K, ANASTAS P T, et al. One-pot reduction of 5-hydroxymethylfurfural via hydrogen transfer from supercritical methanol[J]. Green Chemistry, 2012, 14(9): 2457-2461.
53	KUMALAPUTRI A J, BOTTARI G, ERNE P M, et al. Tunable and selective conversion of 5-HMF to 2,5-furandimethanol and 2,5-dimethylfuran over copper-doped porous metal oxides[J]. ChemSusChem, 2014, 7(8): 2266-2275.
54	ZHANG Z H, WANG C X, GOU X, et al. Catalytic in-situ hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran over Cu-based catalysts with methanol as a hydrogen donor[J]. Applied Catalysis A, General, 2019, 570: 245-250.
55	GAO Z, LI C, FAN G, et al. Nitrogen-doped carbon-decorated copper catalyst for highly efficient transfer hydrogenolysis of 5-hydroxymethylfurfural to convertibly produce 2,5-dimethylfuran or 2,5-dimethyltetrahydrofuran[J]. Applied Catalysis B: Environmental, 2018, 226: 523-533.
56	WANG Q, FENG J T, ZHENG L R, et al. Interfacial structure-determined reaction pathway and selectivity for 5-(hydroxymethyl)furfural hydrogenation over Cu-based catalysts[J]. ACS Catalysis, 2019, 10(2): 1353-1365.
57	BOTTARI G, KUMALAPUTRI A J, KRAWCZYK K K, et al. Copper-zinc alloy nanopowder: a robust precious-metal-free catalyst for the conversion of 5-hydroxymethylfurfural[J]. ChemSusChem, 2015, 8(8): 1323-1327.
58	ZHU Y, KONG X, ZHENG H, et al. Efficient synthesis of 2,5-dihydroxymethylfuran and 2,5-dimethylfuran from 5-hydroxymethylfurfural using mineral-derived Cu catalysts as versatile catalysts[J]. Catalysis Science and Technology, 2015, 5(8): 4208-4217.
59	BRZEZIŃSKA M, KELLER N, RUPPERT A M. Self-tuned properties of CuZnO catalysts for hydroxymethylfurfural hydrodeoxygenation towards dimethylfuran production[J]. Catalysis Science & Technology, 2020, 10(3): 658-670.
60	GUO W W, LIU H Y, ZHANG S Q, et al. Efficient hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran over a cobalt and copper bimetallic catalyst on N-graphene-modified Al₂O₃[J]. Green Chemistry, 2016, 18(23): 6222-6228.
61	CHEN B F, LI F B, HUANG Z J, et al. Carbon-coated Cu-Co bimetallic nanoparticles as selective and recyclable catalysts for production of biofuel 2,5-dimethylfuran[J]. Applied Catalysis B: Environmental, 2017, 200: 192-199.
62	ZHANG Z H, YAO S Y, WANG C X, et al. CuZnCoO_x multifunctional catalyst for in situ hydrogenation of 5-hydroxymethylfurfural with ethanol as hydrogen carrier[J]. Journal of Catalysis, 2019, 373: 314-321.
63	LI J, LIU J L, LIU H Y, et al. Selective hydrodeoxygenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran over heterogeneous iron catalysts[J]. ChemSusChem, 2017, 10(7): 1436-1447.
64	LI J, ZHANG J J, LIU H Y, et al. Graphitic carbon nitride (g-C₃N₄)-derived Fe-N-C catalysts for selective hydrodeoxygenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran[J]. ChemistrySelect, 2017, 2(34): 11062-11070.
65	CHEN N M, ZHU Z G, SU T, et al. Catalytic hydrogenolysis of hydroxymethylfurfural to highly selective 2,5-dimethylfuran over FeCoNi/h-BN catalyst[J]. Chemical Engineering Journal, 2020, 381: 122755.
66	LI D, LIU Q Y, ZHU C H, et al. Selective hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran over Co₃O₄ catalyst by controlled reduction[J]. Journal of Energy Chemistry, 2019, 30: 34-41.
67	WANG J S, WEI Q H, MA Q X, et al. Constructing Co@N-doped graphene shell catalyst via Mott-Schottky effect for selective hydrogenation of 5-hydroxylmethylfurfural[J]. Applied Catalysis B: Environmental, 2020, 263: 118339-118349.
68	CHEN N M, ZHU Z G, MA H K, et al. Catalytic upgrading of biomass-derived 5-hydroxymethylfurfural to biofuel 2,5-dimethylfuran over Beta zeolite supported non-noble Co catalyst[J]. Molecular Catalysis, 2020, 486: 110882.
69	AN Z, WANG W L, DONG S H, et al. Well-distributed cobalt-based catalysts derived from layered double hydroxides for efficient selective hydrogenation of 5-hydroxymethyfurfural to 2,5-methylfuran[J]. Catalysis Today, 2019, 319: 128-138.
70	刘迎新,曾茂,楼炯涛,等. 5-羟甲基糠醛选择性加氢制备2,5-二甲基呋喃研究进展[J]. 高校化学工程学报, 2018, 32(2): 255-265.
	LIU Y X, ZENG M, LOU J T, et al. Review on 2,5-dimethylfuran synthesis via selectivity hydrogenation of 5-hydroxymethylfufural[J]. Journal of Chemical Engineering of Chinese Universities, 2018, 32(2): 255-265.

催化剂	氢供体	温度/℃	反应时间/h	HMF转化率/%	DMF产率/%	参考文献
Ru/C+RuO₂	异丙醇	190	6	100	72	[17]
r-Ru₂@MSC-30	H₂(0.5MPa)	125	1	100	69.52	[18]
Ru-ZrO₂-MCM-41	H₂(1.5MPa)	160	1	100	90	[19]
Ru@Mg(Al)O	异丙醇	220	5	—	14	[20]
Ru-MoO_x/C	H₂(1.5MPa)	180	1	100	79.8	[21]
RuCo/CoO_x	H₂(0.5MPa)	200	2	100	96.5	[22]
Pt-Co/MWCNTs	H₂(1MPa)	160	8	100	92.3	[23]
Pt₃Co₂	H₂(3.3MPa)	160	—	100	98	[24]
Pt₃Ni/C	H₂(3.3MPa)	200	—	100	98	[25]
PtCu/C	H₂(3.3MPa)	200	—	100	96	[25]
Pt₂Zn/C	H₂(3.3MPa)	200	—	100	97	[25]
PtCo/HCS	H₂(1MPa)	180	2	100	98	[26]
Pd/Fe₂O₃	异丙醇	180	24	100	72	[27]
Pd/C	H₂(1MPa)	80	2	100	100	[28]
Pd/C	H₂(2MPa)	120	15	95	85	[29]
Pd-Co₉S₈/S-CNT	H₂(0.3MPa)	120	13	96	83.7	[30]
Pd₅₀Au₅₀/C	H₂(0.1MPa)	60	6	>99	>99	[31]
PdAu₄/GC800	H₂(1MPa)	150	4	86.8	81.9	[32]
Pd-Cs_2.5H_0.5PW₁₂O₄₀/K-10	H₂(1MPa)	90	2	98	79	[33]
Pd/C/Zn	H₂(0.8MPa)	150	8	>99	85	[34]
Cu-Pd@C	H₂(1.5MPa)	120	7	100	96	[35]
Pd/Co-CoO_x@NC	H₂(1.5MPa)	180	2	100	97.8	[36]
Raney Ni	H₂(1.5MPa)	180	15	100	88.5	[37]
Ni-Al₂O₃	H₂(1.2MPa)	180	4	100	91.5	[38]
NiSi-PS	H₂(1.5MPa)	130	3	100	72.9	[39]
7Ni-30W₂C/AC	H₂(4MPa)	180	3	100	96	[40]
2%Ni-20%Co/C	甲酸	210	24	99	90	[41]
Ni-OMD3	H₂(3MPa)	200	6	>99.9	98.7	[42]
Ni/ZrP	H₂(3MPa)	240	20	100	68.1	[43]
Ni/ZSM-5	H₂(0.25MPa)	180	7	91.2	96.2	[45]
Ni/TiO₂	H₂(3MPa)	220	2	100	85	[46]
Ni/C	H₂(4.5MPa)	180	2	100	75	[47]
Ni@SAZn-PC	H₂(0.6MPa)	150	1	56	50	[48]
NiCu₃/C	H₂(3.3MPa)	180	—	100	98.7	[49]
Ni₂-Fe₁/CNTs	H₂(3MPa)	200	3	100	91.3	[50]
Cu-PMO	甲醇	260	3	100	48	[52]
Cu20-Ru2-PMO	H₂(5MPa)	220	1	100	62.6	[53]
Cu/Al₂O₃	甲醇	240	6	>99.9	73.9	[54]
NC-Cu/MgAlO	环己醇	220	0.5	100	96.1	[55]
Co@Cu/3CoAlO_x	H₂(1.5MPa)	180	5	>99	98.5	[56]
CuZn	H₂(2MPa)	200	6	100	89	[57]
CnZn-2	H₂(1.5MPa)	220	5	100	91.8	[58]
CuZnO(P)	H₂(3MPa)	220		100	79	[59]
CuCo?/NGr/α-Al₂O₃	H₂(2MPa)	180	6	100	>99	[60]
Cu-Co@C(Cu∶Co=1∶3)	H₂(5MPa)	180	8	100	99.4	[61]
CuZnCo_x	乙醇	210	5	100	99	[62]
FeN_x/C	H₂(4MPa)	240	5	100	86.2	[63]
Fe-N-C	H₂(4MPa)	240	3	100	85.7	[64]
Fe-Co-Ni/h-BN	H₂(2MPa)	180	4.5	100	94	[65]
Co-CoO_x	H₂(1MPa)	170	12	100	83.3	[66]
Co@NGs	H₂(2MPa)	200	6	99.9	94.7	[67]
20Co/β-DAC723R	H₂(1.5MPa)	150	3	100	83.1	[68]
Co-(ZnO-ZnAl₂O₄)	H₂(0.7MPa)	130	6	100	74.2	[69]

催化剂	氢供体	温度/℃	反应时间/h	HMF转化率/%	DMF产率/%	参考文献
Ru/C+RuO₂	异丙醇	190	6	100	72	[17]
r-Ru₂@MSC-30	H₂(0.5MPa)	125	1	100	69.52	[18]
Ru-ZrO₂-MCM-41	H₂(1.5MPa)	160	1	100	90	[19]
Ru@Mg(Al)O	异丙醇	220	5	—	14	[20]
Ru-MoO_x/C	H₂(1.5MPa)	180	1	100	79.8	[21]
RuCo/CoO_x	H₂(0.5MPa)	200	2	100	96.5	[22]
Pt-Co/MWCNTs	H₂(1MPa)	160	8	100	92.3	[23]
Pt₃Co₂	H₂(3.3MPa)	160	—	100	98	[24]
Pt₃Ni/C	H₂(3.3MPa)	200	—	100	98	[25]
PtCu/C	H₂(3.3MPa)	200	—	100	96	[25]
Pt₂Zn/C	H₂(3.3MPa)	200	—	100	97	[25]
PtCo/HCS	H₂(1MPa)	180	2	100	98	[26]
Pd/Fe₂O₃	异丙醇	180	24	100	72	[27]
Pd/C	H₂(1MPa)	80	2	100	100	[28]
Pd/C	H₂(2MPa)	120	15	95	85	[29]
Pd-Co₉S₈/S-CNT	H₂(0.3MPa)	120	13	96	83.7	[30]
Pd₅₀Au₅₀/C	H₂(0.1MPa)	60	6	>99	>99	[31]
PdAu₄/GC800	H₂(1MPa)	150	4	86.8	81.9	[32]
Pd-Cs_2.5H_0.5PW₁₂O₄₀/K-10	H₂(1MPa)	90	2	98	79	[33]
Pd/C/Zn	H₂(0.8MPa)	150	8	>99	85	[34]
Cu-Pd@C	H₂(1.5MPa)	120	7	100	96	[35]
Pd/Co-CoO_x@NC	H₂(1.5MPa)	180	2	100	97.8	[36]
Raney Ni	H₂(1.5MPa)	180	15	100	88.5	[37]
Ni-Al₂O₃	H₂(1.2MPa)	180	4	100	91.5	[38]
NiSi-PS	H₂(1.5MPa)	130	3	100	72.9	[39]
7Ni-30W₂C/AC	H₂(4MPa)	180	3	100	96	[40]
2%Ni-20%Co/C	甲酸	210	24	99	90	[41]
Ni-OMD3	H₂(3MPa)	200	6	>99.9	98.7	[42]
Ni/ZrP	H₂(3MPa)	240	20	100	68.1	[43]
Ni/ZSM-5	H₂(0.25MPa)	180	7	91.2	96.2	[45]
Ni/TiO₂	H₂(3MPa)	220	2	100	85	[46]
Ni/C	H₂(4.5MPa)	180	2	100	75	[47]
Ni@SAZn-PC	H₂(0.6MPa)	150	1	56	50	[48]
NiCu₃/C	H₂(3.3MPa)	180	—	100	98.7	[49]
Ni₂-Fe₁/CNTs	H₂(3MPa)	200	3	100	91.3	[50]
Cu-PMO	甲醇	260	3	100	48	[52]
Cu20-Ru2-PMO	H₂(5MPa)	220	1	100	62.6	[53]
Cu/Al₂O₃	甲醇	240	6	>99.9	73.9	[54]
NC-Cu/MgAlO	环己醇	220	0.5	100	96.1	[55]
Co@Cu/3CoAlO_x	H₂(1.5MPa)	180	5	>99	98.5	[56]
CuZn	H₂(2MPa)	200	6	100	89	[57]
CnZn-2	H₂(1.5MPa)	220	5	100	91.8	[58]
CuZnO(P)	H₂(3MPa)	220		100	79	[59]
CuCo?/NGr/α-Al₂O₃	H₂(2MPa)	180	6	100	>99	[60]
Cu-Co@C(Cu∶Co=1∶3)	H₂(5MPa)	180	8	100	99.4	[61]
CuZnCo_x	乙醇	210	5	100	99	[62]
FeN_x/C	H₂(4MPa)	240	5	100	86.2	[63]
Fe-N-C	H₂(4MPa)	240	3	100	85.7	[64]
Fe-Co-Ni/h-BN	H₂(2MPa)	180	4.5	100	94	[65]
Co-CoO_x	H₂(1MPa)	170	12	100	83.3	[66]
Co@NGs	H₂(2MPa)	200	6	99.9	94.7	[67]
20Co/β-DAC723R	H₂(1.5MPa)	150	3	100	83.1	[68]
Co-(ZnO-ZnAl₂O₄)	H₂(0.7MPa)	130	6	100	74.2	[69]

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