锆/铪基催化剂催化转移加氢反应的研究进展

doi:10.3969/j.issn.1673-5854.2021.04.009

摘要/Abstract

摘要：

催化转化是可再生生物质资源利用的重要途径，高效催化剂的构建是生物质及其衍生物催化转化的关键环节。生物质衍生羰基类化合物加氢转化为醇或酯类化合物是生物质催化转化利用过程中重要的反应步骤。由于氢转移加氢反应过程具有反应条件温和的优点，因此非均相氢转移加氢催化剂在羰基类生物质平台分子转化中得到广泛应用。过渡金属锆、铪是常用的氢转移加氢反应活性金属。围绕不同锆/铪基氢转移催化剂的制备及其在生物质平台分子加氢转化反应中的应用进行综述。简要介绍了锆、铪氢转移催化剂的制备方法，详细介绍锆氧化物或氢氧化物、不同配体（羟基、羧酸、膦酸、磺酸、钨酸、胺类、有机金属骨架、沸石分子筛）配位锆/铪基催化剂、双金属催化剂，并对比分析它们的催化性能、循环稳定性和结构机理，最后对生物质氢转移加氢催化转化及其催化剂构建发展趋势进行了展望。

关键词: 生物质催化转化, 过渡金属铪、锆催化剂, 生物质平台分子, 催化转移加氢反应

Abstract:

Catalytic conversion is an important route for the utilization of the renewable biomass resources, and the construction of highly efficient catalysts is a crucial step for the catalytic conversion of biomass and its derivatives. The hydrogenation conversion of biomass derived carbonyl derivatives into alcohols or ester compounds is an important step during the catalytic conversion processes of biomass. Due to the mild reaction conditions of the transfer hydrogenation process, the heterogeneous transfer hydrogenation catalysts have broad applications in the conversion of biomass derived carbonyl compound platforms. The transition metal zirconium and hafnium are commonly used as active metals for the transfer hydrogenation reaction. This review summarized the preparation of the zirconium and hafnium based transfer hydrogenation catalysts and their applications in the hydrogenation conversion of biomass derived platforms. Firstly, the preparation of the zirconium and hafnium based transfer hydrogenation catalysts were briefly introduced. Then, zirconium oxide or hydroxide, zirconium/hafnium based catalyst with different ligand (hydroxyl, carboxylic acid, phosphonic acid, sulfonic acid, tungsten acid, amine, organic metal skeleton, zeolite molecular sieve) ligand, the double metal catalyst and the comparative analysis of their catalytic performance, cycle stability and structural mechanism were reviewed in detail, and the performances of these catalysts were compared. Finally, the future perspectives of the catalytic transfer hydrogenation of biomass and the construction of the catalysts were prospected.

Key words: catalytic conversion of biomass, transition metal hafnium/zirconium catalysts, biomass platform, catalytic hydrogen transfer reaction

中图分类号:

王晓璐, 姚雪峰, 陈宇新, 周华从, 刘全生. 锆/铪基催化剂催化转移加氢反应的研究进展[J]. 生物质化学工程, 2021, 55(4): 66-76.

Xiaolu WANG, Xuefeng YAO, Yuxin CHEN, Huacong ZHOU, Quansheng LIU. Research Progress on Zirconium/Hafnium Based Hydrogen Transfer Catalyst[J]. Biomass Chemical Engineering, 2021, 55(4): 66-76.

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参考文献 93

1	BOZELL J J , PETERSEN G R . Technology development for the production of biobased products from biorefinery carbohydrates: The US Department of Energy's "Top 10" revisited[J]. Green Chemistry, 2010, 12 (4): 525- 728. doi: 10.1039/c004584p
2	FANG R , DHAKSHINAMOORTHY A , LI Y , et al. Metal organic frameworks for biomass conversion[J]. Chemical Society Reviews, 2020, 49 (11): 3638- 3687. doi: 10.1039/D0CS00070A
3	NAKAGAWA Y , TAMURA M , TOMISHIGE K . Catalytic reduction of biomass-derived furanic compounds with hydrogen[J]. ACS Catalysis, 2013, 3 (12): 2655- 2668. doi: 10.1021/cs400616p
4	RUPPERT A M , JEDRZEJCZYK M , SNEKA-PŁATEK O , et al. Ru catalysts for levulinic acid hydrogenation with formic acid as a hydrogen source[J]. Green Chemistry, 2016, 18 (7): 2014- 2028. doi: 10.1039/C5GC02200B
5	YI Y , LIU H , XIAO L P , et al. Highly efficient hydrogenation of levulinic acid into γ-valerolactone using an iron pincer complex[J]. ChemSusChem, 2018, 11 (9): 1474- 1478. doi: 10.1002/cssc.201800435
6	CAO Y , NOEL T . Efficient electrocatalytic reduction of furfural to furfuryl alcohol in a microchannel flow reactor[J]. Organic Process Research & Development, 2019, 23 (3): 403- 408.
7	LUO H Y , CONSOLI D F , GUNTHER W R , et al. Investigation of the reaction kinetics of isolated Lewis acid sites in Beta zeolites for the Meerwein-Ponndorf-Verley reduction of methyl levulinate to γ-valerolactone[J]. Journal of Catalysis, 2014, 320, 198- 207. doi: 10.1016/j.jcat.2014.10.010
8	WRIGHT W R , PALKOVITS R . Development of heterogeneous catalysts for the conversion of levulinic acid to gamma-valerolactone[J]. ChemSusChem, 2012, 5 (9): 1657- 1667. doi: 10.1002/cssc.201200111
9	PASINI T , LOLLI A , ALBONETTI S , et al. Methanol as a clean and efficient H-transfer reactant for carbonyl reduction: Scope, limitations, and reaction mechanism[J]. Journal of Catalysis, 2014, 317, 206- 219. doi: 10.1016/j.jcat.2014.06.023
10	PANAGIOTOPOULOU P , MARTIN N , VLACHOS D G . Liquid-phase catalytic transfer hydrogenation of furfural over homogeneous Lewis acid-Ru/C catalysts[J]. ChemSusChem, 2015, 8 (12): 2046- 2054. doi: 10.1002/cssc.201500212
11	LI X , DU Z , WU Y , et al. A novel hafnium-graphite oxide catalyst for the Meerwein-Ponndorf-Verley reaction and the activation effect of the solvent[J]. RSC Advances, 2020, 10 (17): 9985- 9995. doi: 10.1039/C9RA10795A
12	YANG Z , HUANG Y B , GUO Q X , et al. RANEY(R) Ni catalyzed transfer hydrogenation of levulinate esters to gamma-valerolactone at room temperature[J]. Chemical Communications, 2013, 49 (46): 5328- 5330. doi: 10.1039/c3cc40980e
13	TANG X , LI Z , ZENG X , et al. In situ catalytic hydrogenation of biomass-derived methyl levulinate to gamma-valerolactone in methanol[J]. ChemSusChem, 2015, 8 (9): 1601- 1607. doi: 10.1002/cssc.201403392
14	ZHOU H , SONG J , FAN H , et al. Cobalt catalysts: Very efficient for hydrogenation of biomass-derived ethyl levulinate to gamma-valerolactone under mild conditions[J]. Green chemistry, 2014, 16 (8): 3870- 3875. doi: 10.1039/C4GC00482E
15	LI F , LI Z , FRANCE L J , et al. Highly efficient transfer hydrogenation of levulinate esters to γ-valerolactone over basic zirconium carbonate[J]. Industrial & Engineering Chemistry Research, 2018, 57 (31): 10126- 10136.
16	URBANO F J , ARAMENDÍA M A , MARINAS A , et al. An insight into the Meerwein-Ponndorf-Verley reduction of α, β-unsaturated carbonyl compounds: Tuning the acid-base properties of modified zirconia catalysts[J]. Journal of Catalysis, 2009, 268 (1): 79- 88. doi: 10.1016/j.jcat.2009.09.005
17	MA J , LIU Z , SONG J , et al. Au@h-Al₂O₃ analogic yolk-shell nanocatalyst for highly selective synthesis of biomass-derived D-xylonic acid via regulation of structure effects[J]. Green Chemistry, 2018, 20 (22): 5188- 5195. doi: 10.1039/C8GC02618A
18	BORONA T M , CORMA A , RENZ M . Mechanism of the Meerwein-Ponndorf-Verley-Oppenauer (MPVO) redox equilibrium on Sn- and Zr-beta zeolite catalysts[J]. The Journal of Physical Chemistry B, 2006, 110, 21168- 21174. doi: 10.1021/jp063249x
19	ANTUNES M , LIMA S , NEVES P , et al. One-pot conversion of furfural to useful bio-products in the presence of a Sn, Al-containing zeolite beta catalyst prepared via post-synthesis routes[J]. Journal of Catalysis, 2015, 329, 522- 537. doi: 10.1016/j.jcat.2015.05.022
20	BAKURU V R , CHURIPARD S R , MARADUR S P , et al. Exploring the Bronsted acidity of UiO-66(Zr, Ce, Hf) metal-organic frameworks for efficient solketal synthesis from glycerol acetalization[J]. Dalton Transactions, 2019, 48 (3): 843- 847. doi: 10.1039/C8DT03512A
21	LI H , FANG Z , HE J , et al. Orderly layered Zr-benzylphosphonate nanohybrids for efficient acid-base-mediated bifunctional/cascade catalysis[J]. ChemSusChem, 2017, 10 (4): 681- 586. doi: 10.1002/cssc.201601570
22	VALEKAR A H , CHO K H , CHITALE S K , et al. Catalytic transfer hydrogenation of ethyl levulinate to γ-valerolactone over zirconium-based metal-organic frameworks[J]. Green Chemistry, 2016, 18 (16): 4542- 4552. doi: 10.1039/C6GC00524A
23	VALEKAR A H , LEE M , YOON J W , et al. Catalytic transfer hydrogenation of furfural to furfuryl alcohol under mild conditions over Zr-MOFs: Exploring the role of metal node coordination and modification[J]. ACS Catalysis, 2020, 10 (6): 3720- 3372. doi: 10.1021/acscatal.9b05085
24	冉锐, 吴晓东, 樊俊, 等. 水热法合成Ce_0.67Zr_0.33O_0.2固溶体研究[J]. 中国稀土学报, 2004, 22, 26- 28. doi: 10.3321/j.issn:1000-4343.2004.z2.006
25	TANG X , CHEN H , HU L , et al. Conversion of biomass to γ-valerolactone by catalytic transfer hydrogenation of ethyl levulinate over metal hydroxides[J]. Applied Catalysis B: Environmental, 2014, 147, 827- 834. doi: 10.1016/j.apcatb.2013.10.021
26	ZAHN G , SCHULZE H A , LIPPKE J , et al. A water-born Zr-based porous coordination polymer: Modulated synthesis of Zr-fumarate MOF[J]. Microporous and Mesoporous Materials, 2015, 203, 186- 194. doi: 10.1016/j.micromeso.2014.10.034
27	YUN W C , YANG M T , LIN K A . Water-born zirconium-based metal organic frameworks as green and effective catalysts for catalytic transfer hydrogenation of levulinic acid to gamma-valerolactone: Critical roles of modulators[J]. Journal of Colloid and Interface Science, 2019, 543, 52- 63. doi: 10.1016/j.jcis.2019.02.036
28	HU L , LIU S , SONG J , et al. Zirconium-containing organic-inorganic nanohybrid as a highly efficient catalyst for the selective synthesis of biomass-derived 2, 5-dihydroxymethylfuran in isopropanol[J]. Waste and Biomass Valorization, 2019, 11 (7): 3485- 3499.
29	贾金洁, 刘晓林, 扬刘, 等. 溶剂热法制备纳米Pb(Zr_0.52Ti_0.48)O₃粉体[J]. 稀有金属材料与工程, 2007, 36 (S1): 131- 133.
30	GONELL F , BORONAT M , CORMA A . Structure-reactivity relationship in isolated Zr sites present in Zr-zeolite and ZrO₂ for the Meerwein-Ponndorf-Verley reaction[J]. Catalysis Science & Technology, 2017, 7 (13): 2865- 2873.
31	SHIBAGAKI M , TAKAHASHI K , MATSUSHITA H . The catalytic reduction of aldehydes and ketones with 2-propanol over hydrous zirconium oxide[J]. The Chemical Society of Japan, 1988, 61, 3283- 3288. doi: 10.1246/bcsj.61.3283
32	CHIA M , DUMESIC J A . Liquid-phase catalytic transfer hydrogenation and cyclization of levulinic acid and its esters to gamma-valerolactone over metal oxide catalysts[J]. Chemical Communications, 2011, 47 (44): 12233- 12235. doi: 10.1039/c1cc14748j
33	TANG X , HU L , SUN Y , et al. Conversion of biomass-derived ethyl levulinate into γ-valerolactone via hydrogen transfer from supercritical ethanol over a ZrO₂ catalyst[J]. RSC Advances, 2013, 3 (26): 10277- 10284. doi: 10.1039/c3ra41288a
34	HAO W , LI W , TANG X , et al. Catalytic transfer hydrogenation of biomass-derived 5-hydroxymethyl furfural to the building block 2, 5-bishydroxymethyl furan[J]. Green Chemistry, 2016, 18 (4): 1080- 1088. doi: 10.1039/C5GC01221J
35	LIU S H , JAENICKE S , CHUAH G K . Hydrous zirconia as a selective catalyst for the Meerwein-Ponndorf-Verley reduction of cinnamaldehyde[J]. Journal of Catalysis, 2002, 206 (2): 321- 330. doi: 10.1006/jcat.2001.3480
36	TANG X , ZENG X , LI Z , et al. In situ generated catalyst system to convert biomass-derived levulinic acid to γ-valerolactone[J]. ChemCatChem, 2015, 7 (8): 1372- 1379. doi: 10.1002/cctc.201500115
37	LUO J , ZHANG N , LAI J , et al. Tannic acid functionalized graphene hydrogel for entrapping gold nanoparticles with high catalytic performance toward dye reduction[J]. Journal of Hazardous Materials, 2015, 300, 615- 623. doi: 10.1016/j.jhazmat.2015.07.079
38	SAHINER N , SAGBAS S , AKTAS N . Single step natural poly(tannic acid) particle preparation as multitalented biomaterial[J]. Materials Science & Engineering C-Materials for biological Applications, 2015, 49, 824- 834.
39	XUE Z , JIANG J , LI G , et al. Zirconium-cyanuric acid coordination polymer: Highly efficient catalyst for conversion of levulinic acid to γ-valerolactone[J]. Catalysis Science & Technology, 2016, 6 (14): 5374- 5379.
40	LENG Y , SHI L , DU S , et al. A tannin-derived zirconium-containing porous hybrid for efficient Meerwein-Ponndorf-Verley reduction under mild conditions[J]. Green Chemistry, 2020, 22 (1): 180- 186. doi: 10.1039/C9GC03393A
41	WANG X , HAO J , DENG L , et al. The construction of novel and efficient hafnium catalysts using naturally existing tannic acid for Meerwein-Ponndorf-Verley reduction[J]. RSC Advances, 2020, 10 (12): 6944- 6952. doi: 10.1039/C9RA10317A
42	HU L , LI T , XU J , et al. Catalytic transfer hydrogenation of biomass-derived 5-hydroxymethylfurfural into 2, 5-dihydroxymethylfuran over magnetic zirconium-based coordination polymer[J]. Chemical Engineering Journal, 2018, 352, 110- 119. doi: 10.1016/j.cej.2018.07.007
43	WANG T , HU A , XU G , et al. Porous Zr-thiophenedicarboxylate hybrid for catalytic transfer hydrogenation of bio-based furfural to furfuryl alcohol[J]. Catalysis Letters, 2019, 149 (7): 1845- 1855. doi: 10.1007/s10562-019-02748-0
44	SHA Y , XIAO Z , ZHOU H , et al. Direct use of humic acid mixtures to construct efficient Zr-containing catalysts for Meerwein-Ponndorf-Verley reactions[J]. Green Chemistry, 2017, 19 (20): 4829- 4837. doi: 10.1039/C7GC01925D
45	HAO J , HAN L , SHA Y , et al. Facile use of lignite as robust organic ligands to construct Zr-based catalysts for the conversion of biomass derived carbonyl platforms into alcohols[J]. Fuel, 2019, 239, 1304- 1314. doi: 10.1016/j.fuel.2018.11.129
46	LI H , LIU X , YANG T , et al. Porous zirconium-furandicarboxylate microspheres for efficient redox conversion of biofuranics[J]. ChemSusChem, 2017, 10 (8): 1761- 1770. doi: 10.1002/cssc.201601898
47	DAI F , ZHOU S , QIN X , et al. Surfactant-assisted synthesis of mesoporous hafnium-imidazoledicarboxylic acid hybrids for highly efficient hydrogen transfer of biomass-derived carboxides[J]. Molecular Catalysis, 2019, 479, 110611- 110622. doi: 10.1016/j.mcat.2019.110611
48	XIAO Z , ZHOU H , HAO J , et al. A novel and highly efficient Zr-containing catalyst based on humic acids for the conversion of biomass-derived ethyl levulinate into gamma-valerolactone[J]. Fuel, 2017, 193, 322- 330. doi: 10.1016/j.fuel.2016.12.072
49	ZHANG B , HAO J , SHA Y , et al. Utilization of lignite derivatives to construct Zr-based catalysts for the conversion of biomass-derived ethyl levulinate[J]. Fuel, 2018, 217, 22- 30.
50	LI H , YANG T , FANG Z . Biomass-derived mesoporous Hf-containing hybrid for efficient Meerwein-Ponndorf-Verley reduction at low temperatures[J]. Applied Catalysis B: Environmental, 2018, 227, 79- 89. doi: 10.1016/j.apcatb.2018.01.017
51	ABUTARTOURA, MAJDOUBL E, 史亚赛, 等. 一种新型膦酸锆孔材料的合成及其对金属离子的吸附性质[J]. 无机材料学报, 2017, 32, 305- 312.
52	LIU C , XU G , HU A , et al. Porous zirconium hydroxyphosphonoacetate: Catalyst for conversion of furfural into furfuryl alcohol[J]. ChemistrySelect, 2019, 4 (27): 8000- 8006. doi: 10.1002/slct.201901612
53	LI H , LI Y , FANG Z , et al. Efficient catalytic transfer hydrogenation of biomass-based furfural to furfuryl alcohol with recycable Hf-phenylphosphonate nanohybrids[J]. Catalysis Today, 2019, 319, 84- 92. doi: 10.1016/j.cattod.2018.04.056
54	WANG J , WANG R , ZI H , et al. A porous inorganic zirconyl pyrophosphate as an efficient catalyst for the catalytic transfer hydrogenation of ethyl levulinate to γ-valerolactone[J]. Journal of the Chinese Chemical Society, 2018, 65 (11): 1370- 1378. doi: 10.1002/jccs.201800073
55	SONG J , ZHOU B , ZHOU H , et al. Porous zirconium-phytic acid hybrid: A highly efficient catalyst for Meerwein-Ponndorf-Verley reductions[J]. Angew Chemie International Edition in English, 2015, 54 (32): 9399- 9403. doi: 10.1002/anie.201504001
56	XIE C , SONG J , ZHOU B , et al. Porous hafnium phosphonate: Novel heterogeneous catalyst for conversion of levulinic acid and esters into γ-valerolactone[J]. ACS Sustainable Chemistry & Engineering, 2016, 4 (11): 6231- 6236.
57	XIE Y , LI F , WANG J , et al. Catalytic transfer hydrogenation of ethyl levulinate to γ-valerolactone over a novel porous Zirconium trimetaphosphate[J]. Molecular Catalysis, 2017, 442, 107- 114. doi: 10.1016/j.mcat.2017.09.011
58	WU W , LI Y , LI H , et al. Acid-base bifunctional Hf nanohybrids enable high selectivity in the catalytic conversion of ethyl levulinate to γ-valerolactone[J]. Catalysts, 2018, 8 (7): 264- 278. doi: 10.3390/catal8070264
59	HU L , DAI X , LI N , et al. Highly selective hydrogenation of biomass-derived 5-hydroxymethylfurfural into 2, 5-bis(hydroxymethyl)furan over an acid-base bifunctional hafnium-based coordination polymer catalyst[J]. Sustainable Energy & Fuels, 2019, 3 (4): 1033- 1041.
60	LI H , HE J , RIISAGER A , et al. Acid-base bifunctional zirconium N-alkyltriphosphate nanohybrid for hydrogen transfer of biomass-derived carboxides[J]. ACS Catalysis, 2016, 6 (11): 7722- 7727. doi: 10.1021/acscatal.6b02431
61	YANG T , ZHAO W , LI H , et al. Porous Zr-bibenzyldiphosphonate nanohybrid with extra hydroxy species for enhancive upgrading of biomass-based levulinates[J]. ChemistrySelect, 2018, 3 (16): 4252- 4261. doi: 10.1002/slct.201800132
62	LI F , FRANCE L J , CAI Z , et al. Catalytic transfer hydrogenation of butyl levulinate to γ-valerolactone over zirconium phosphates with adjustable Lewis and Brønsted acid sites[J]. Applied Catalysis B: Environmental, 2017, 214, 67- 77. doi: 10.1016/j.apcatb.2017.05.013
63	ZHOU S , DAI F , XIANG Z , et al. Zirconium-lignosulfonate polyphenolic polymer for highly efficient hydrogen transfer of biomass-derived oxygenates under mild conditions[J]. Applied Catalysis B: Environmental, 2019, 248, 31- 43. doi: 10.1016/j.apcatb.2019.02.011
64	ZHOU S , DAI F , CHEN Y , et al. Sustainable hydrothermal self-assembly of hafnium-lignosulfonate nanohybrids for highly efficient reductive upgrading of 5-hydroxymethylfurfural[J]. Green Chemistry, 2019, 21 (6): 1421- 1431. doi: 10.1039/C8GC03710H
65	RODIKOVA Y , ZHIZHINA E . Catalytic oxidation of 5-hydroxymethylfurfural into 2, 5-diformylfuran using V-containing heteropoly acid catalysts[J]. Reaction Kinetics, Mechanisms and Catalysis, 2020, 130 (1): 403- 415. doi: 10.1007/s11144-020-01782-z
66	XU G , LIU C , HU A , et al. Transfer hydrogenation of furfural to furfuryl alcohol over Keggin zirconium-heteropoly acid[J]. Molecular Catalysis, 2019, 475, 110384- 110392. doi: 10.1016/j.mcat.2019.04.013
67	WATANABE A , UCHIDA A T , ITO K , et al. Highly enantioselective Baeyer: Villiger oxidation using Zr(salen) complex as catalyst[J]. Tetrahedron Letters, 2002, 43, 4481- 4485. doi: 10.1016/S0040-4039(02)00831-6
68	SELVAM P , BHATIA S K , SONWANE C G . Recent advances in processing and characterization of periodic mesoporous MCM-41 silicate molecular sieves[J]. Industrial & Engineering Chemistry Research, 2001, 40, 3237- 3261.
69	WANG R , WANG J , ZI H , et al. Catalytic transfer hydrogenation of ethyl levulinate to γ-valerolactone over zirconium (IV) Schiff base complexes on mesoporous silica with isopropanol as hydrogen source[J]. Molecular Catalysis, 2017, 441, 168- 178. doi: 10.1016/j.mcat.2017.07.026
70	STOCK N , BISWAS S . Synthesis of metal-organic frameworks (MOFs): Routes to various MOF topologies, morphologies, and composites[J]. Chemical Reviews, 2012, 112 (2): 933- 969. doi: 10.1021/cr200304e
71	LI W , CAI Z , LI H , et al. Hf-based metal organic frameworks as bifunctional catalysts for the one-pot conversion of furfural to γ-valerolactone[J]. Molecular Catalysis, 2019, 472, 17- 26. doi: 10.1016/j.mcat.2019.04.010
72	ROJAS-BUZO S , GARCÍA-GARCÍA P , CORMA A . Hf-based metal-organic frameworks as acid-base catalysts for the transformation of biomass-derived furanic compounds into chemicals[J]. Green Chemistry, 2018, 20 (13): 3081- 3091. doi: 10.1039/C8GC00806J
73	ROJAS-BUZO S , GARCIA-GARCIA P , CORMA A . Catalytic transfer hydrogenation of biomass-derived carbonyls over hafnium-based metal-organic frameworks[J]. ChemSusChem, 2018, 11 (2): 432- 438. doi: 10.1002/cssc.201701708
74	KURISINGAL J F , RACHURI Y , PALAKKAL A S , et al. Water-tolerant DUT-series metal-organic frameworks: A theoretical-experimental study for the chemical fixation of CO₂ and catalytic transfer hydrogenation of ethyl levulinate to γ-valerolactone[J]. ACS Applied Materials & Interfaces, 2019, 11 (44): 41458- 41471.
75	KOEHLE M , LOBO R F . Lewis acidic zeolite Beta catalyst for the Meerwein-Ponndorf-Verley reduction of furfural[J]. Catalysis Science & Technology, 2016, 6 (9): 3018- 3026.
76	BUI L , LUO H , GUNTHER W R , et al. Domino reaction catalyzed by zeolites with Bronsted and Lewis acid sites for the production of gamma-valerolactone from furfural[J]. Angewandte Chemie International Edition in English, 2013, 52 (31): 8022- 8025. doi: 10.1002/anie.201302575
77	WANG J , JAENICKE S , CHUAH G K . Zirconium-Beta zeolite as a robust catalyst for the transformation of levulinic acid to γ-valerolactone via Meerwein-Ponndorf-Verley reduction[J]. RSC Advances, 2014, 4 (26): 13481- 13489. doi: 10.1039/C4RA01120A
78	BORONAT M , CORMA A , RENZ M . Mechanism of the Meerwein-Ponndorf-Verley-Oppenauer (MPVO) redox equilibrium on Sn- and Zr-beta zeolite catalysts[J]. The Journal of Physical Chemistry B, 110, 21168- 21174. doi: 10.1021/jp063249x
79	LI F , JIANG S , HUANG J , et al. Catalytic transfer hydrogenation of furfural to furfuryl alcohol over a magnetic Fe₃O₄@C catalyst[J]. New Journal of Chemistry, 2020, 44 (2): 478- 486. doi: 10.1039/C9NJ04698D
80	JAIN A B , VAIDYA P D . Kinetics of catalytic hydrogenation of 5-hydroxymethylfurfural to 2, 5-bis-hydroxymethylfuran in aqueous solution over Ru/C[J]. International Journal of Chemical Kinetics, 2016, 48 (6): 318- 328. doi: 10.1002/kin.20992
81	LONG J , ZHOU Y , LI Y . Transfer hydrogenation of unsaturated bonds in the absence of base additives catalyzed by a cobalt-based heterogeneous catalyst[J]. Chemical Communications, 2015, 51 (12): 2331- 2334. doi: 10.1039/C4CC08946D
82	PANAGIOTOPOULOU P , MARTIN N , VLACHOS D G . Effect of hydrogen donor on liquid phase catalytic transfer hydrogenation of furfural over a Ru/RuO₂/C catalyst[J]. Journal of Molecular Catalysis A: Chemical, 2014, 392, 223- 228. doi: 10.1016/j.molcata.2014.05.016
83	VILLAVERDE M M , BERTERO N M , GARETTO T F , et al. Selective liquid-phase hydrogenation of furfural to furfuryl alcohol over Cu-based catalysts[J]. Catalysis Today, 2013, 213, 87- 92. doi: 10.1016/j.cattod.2013.02.031
84	GAO X , ZHU S , DONG M , et al. Ru nanoparticles deposited on ultrathin TiO₂ nanosheets as highly active catalyst for levulinic acid hydrogenation to γ-valerolactone[J]. Applied Catalysis B: Environmental, 2019, 259, 118076- 118084. doi: 10.1016/j.apcatb.2019.118076
85	MERLO A B , VETERE V , RAMALLO-LÓPEZ J M , et al. Liquid-phase furfural hydrogenation employing silica-supported PtSn and PtGe catalysts prepared using surface organometallic chemistry on metals techniques[J]. Reaction Kinetics, Mechanisms and Catalysis, 2011, 104 (2): 467- 482. doi: 10.1007/s11144-011-0374-4
86	YAN K , CHEN A . Selective hydrogenation of furfural and levulinic acid to biofuels on the ecofriendly Cu-Fe catalyst[J]. Fuel, 2014, 115, 101- 108. doi: 10.1016/j.fuel.2013.06.042
87	MARISCAL R , MAIRELES-TORRES P , OJEDA M , et al. Furfural: A renewable and versatile platform molecule for the synthesis of chemicals and Fuels[J]. Energy & Environmental Science, 2016, 9, 1144- 1189.
88	CHIMENTÃO R J , OLIVA H , BELMAR J , et al. Selective hydrodeoxygenation of biomass derived 5-hydroxymethylfurfural over silica supported iridium catalysts[J]. Applied Catalysis B: Environmental, 2019, 241, 270- 283. doi: 10.1016/j.apcatb.2018.09.026
89	ORTIZ-CERVANTES C , FLORES-ALAMO M , GARCÍA J J . Hydrogenation of biomass-derived levulinic acid into γ-valerolactone catalyzed by palladium complexes[J]. ACS Catalysis, 2015, 5 (3): 1424- 1431. doi: 10.1021/cs5020095
90	HE J , LI H , LU Y M , et al. Cascade catalytic transfer hydrogenation-cyclization of ethyl levulinate to γ-valerolactone with Al-Zr mixed oxides[J]. Applied Catalysis A: General, 2016, 510, 11- 19. doi: 10.1016/j.apcata.2015.10.049
91	GU J, ZHANG J, WANG Y H, et al. Efficient transfer hydrogenation of biomass derived furfural and levulinic acid via magnetic zirconium nanoparticles: Experimental and kinetic study[J/OL]. Industrial Crops and Products, 2020, 145: 112133[2020-09-11]. https://doi.or/10.1016/j.indcrop.2020.112133
92	SAKAKIBARA K , ENDO K , OSAWA T . Facile synthesis of γ-valerolactone by transfer hydrogenation of methyl levulinate and levulinic acid over Ni/ZrO₂[J]. Catalysis Communications, 2019, 125, 52- 55. doi: 10.1016/j.catcom.2019.03.021
93	YANG T , LI H , HE J , et al. Porous Ti/Zr microspheres for efficient transfer hydrogenation of biobased ethyl levulinate to gamma-valerolactone[J]. ACS Omega, 2017, 2 (3): 1047- 1054. doi: 10.1021/acsomega.6b00469

催化剂种类 catalyst	氢源 hydrogen donor	温度/℃ temperature	时间/h time	反应物 substrate	转化率/% conversion	产物 product	产率/% yield	参考文献 reference
ZrO₂	2-丁醇2-butanol	150	16	乙酰丙酸酯 levulinate	99.9	γ-戊内酯 γ-valerolactone	84.7	[32]
ZrO₂	乙醇 ethanol	250	3	乙酰丙酸乙酯 ethyl levulinate	95.5	γ-戊内酯 γ-valerolactone	81.5	[33]
ZrO(OH)₂·xH₂O	异丙醇 2-isopropanol	200	1	乙酰丙酸乙酯 ethyl levulinate	93.6	γ-戊内酯 γ-valerolactone	88.5	[25]
ZrO(OH)₂	乙醇 ethanol	150	2.5	5 -羟甲基糠醛 5-hydroxymethyl furfural	94.1	2, 5-羟甲基呋喃 2, 5-hydroxymethylfuran	83.6	[34]
ZrO₂	异丙醇 2-isopropanol	250	2	肉桂醛 cinnamic aldehyde	75.0	肉桂醇 cinnamyl alcohol	72.0	[35]
ZrOCl₂·8H₂O	2 -丁醇 2-butanol	240	2	乙酰丙酸 levulinic acid	99.9	γ-戊内酯 γ-valerolactone	92.4	[36]

催化剂种类¹⁾ catalyst	温度/℃ temperature	时间/h time	转化率/% conversion	产率/% yield	NH₃-TPD/(mmol·g^-1)	CO₂-TPD/(mmol·g^-1)	参考文献 reference
Zr-CA	130	10	99.8	97.1	1.034	2.375	[39]
MZCCP	160	6	96.9	95.1	1.394	2.105	[42]
Zr-TA	150	14	93.0	96.0	0.114	0.332	[40]
Hf-TA	160	46	92.2	84.4	2.077	1.1957	[41]

催化剂catalyst		温度/℃ temperature	时间/h time	转化率/% conversion	产率/% yield	TOF值 TOF value	参考文献 reference
金属元素 metal	配体 ligand	温度/℃ temperature	时间/h time	转化率/% conversion	产率/% yield	TOF值 TOF value	参考文献 reference
Zr		70	9	98.0^a	80.0 ^a	—	[44]
Zr		90	6	93.4^a	80.9 ^a	0.82	[45]
Zr		140	4	98.0^a	96.0 ^a	3.5	[46]
Zr		120	4	95.9^a	92.2 ^a	—	[43]
Hf		120	1	100.0^a	99.0 ^a	0.55	[47]
Zr		150	11	99.5^a	84.2 ^a	0.1	[48]
Zr		150	9	92.7 ^b	90.1 ^b	0.09	[49]
Hf		160	4	>99.0 ^b	98.0^b	1.53	[50]
Hf		150	5	95.5 ^b	87.7^b	3.51	[11]

催化剂catalyst		温度/℃ temperature	时间/h time	转化率/% conversion	产率/% yield	S_BET/(m²·g^-1)	V_pore/(cm³·g^-1)	D_mean/nm	参考文献 reference
金属元素matal	配体 ligand	温度/℃ temperature	时间/h time	转化率/% conversion	产率/% yield	S_BET/(m²·g^-1)	V_pore/(cm³·g^-1)	D_mean/nm	参考文献 reference
Zr		150	6	100.0^a	96.7 ^a	215	0.42	8.5	[53]
Hf		150	7	>99.0 ^a	97.0 ^a	222.6	0.25	16.7	[54]
Zr		160	8	100.0 ^a	96.2 ^a	361	0.28	3.7	[55]
Hf		160	6	100.0 ^a	85.0 ^a	215	0.16	3.4	[56]
Hf		140	4	97.6 ^a	96.2 ^a	241	0.52	10.0	[57]
Zr		160	10	93.0 ^a	92.0 ^a	154	0.46	12.4	[58]
Zr		180	8	99.0 ^a	95.0 ^a	267	0.48	8.2	[59]
Zr		210	2	98.1 ^b	95.7 ^b	248	—	—	[60]
Hf		120	2	99.2 ^c	97.6 ^c	214	0.21	3.4	[61]
Zr		150	1.5	98.0 ^c	96.5 ^c	168	0.30	12.4	[52]

催化剂 catalyst	温度/℃ temperature	时间/h time	转化率/% conversion	产率/% yield	S_BET/(m²·g^-1)	参考文献 reference
MOF-808(Hf)	120	8	—	94.0	458	[73]
CH₃OH-MOF-808(Zr)	82	24	90.7	82.8	1252	[23]
DUT-52(Zr)	160	5	>99	94.0	1208	[74]
UiO-66(Zr)	200	2	>99	92.7	1046	[22]