Citation: Ma Yan-Fu, Wang Hao, Xu Guang-Yue, Liu Xiao-Hao, Zhang Ying, Fu Yao. Selective conversion of furfural to cyclopentanol over cobalt catalysts in one step[J]. Chinese Chemical Letters, ;2017, 28(6): 1153-1158. doi: 10.1016/j.cclet.2017.03.017 shu

Selective conversion of furfural to cyclopentanol over cobalt catalysts in one step

iChEM, CAS Key Laboratory of Urban Pollutant Conversion, Anhui Province Key Laboratory for Biomass Clean Energy and Department of Chemistry, University of Science and Technology of China, Hefei 230026, China

Corresponding author: Zhang Ying, zhzhying@ustc.edu.cn; zhzhying@gmail.com
Received Date: 13 January 2017
Revised Date: 22 February 2017
Accepted Date: 9 March 2017
Available Online: 12 June 2017

Figures(4)

A series of cobalt catalysts with different supports were prepared for the selective conversion of biomassderived furfural to cyclopentanol (CPL) in one step. The best CPL yield was 82 mol% at 160℃, 2 MPa H₂, 4 h when cobalt was supported on ZrO₂-La₂O₃. The supports were characterized by X-ray diffraction (XRD) and temperature-programmed desorption of ammonia (NH₃-TPD). The XRD results indicated that the more stable t-ZrO₂ formed by doping La₂O₃. The amount of acid sites of the catalyst increased, too. The influences of parameters such as reaction temperature, hydrogen pressure, and reaction time on the catalytic activity were also investigated. The polymer formed during the reaction may cause the deactivation of the Co/ZrO₂-La₂O₃ catalyst. This work provides a possibility to prepare the stable t-ZrO₂ and apply with cobalt metal for biomass valorization.
- Furfural,
- Cobalt,
- Cyclopentanol,
- Hydrogenation,
- Tetragonal Zirconia
1. [1]
  van Putten R.J., van der Waal J.C., De Jong E.D.. Hydroxymethylfurfural, a versatile platform chemical made from renewable resources[J]. Chem. Rev., 2013,113:1499-1597. doi: 10.1021/cr300182k
2. [2]
  Gandini A., Lacerda T.M., Carvalho A.J.F., Trovatti E.. Progress of polymers from renewable resources:furans, vegetable oils, and polysaccharides[J]. Chem. Rev., 2015,116:1637-1669.
3. [3]
  Karinen R., Vilonen K., Niemelä M.. Biorefining:heterogeneously catalyzed reactions of carbohydrates for the production of furfural and hydroxymethylfurfural[J]. ChemSusChem, 2011,4:1002-1016. doi: 10.1002/cssc.201000375
4. [4]
  Hu L., Zhao G., Hao W.W.. Catalytic conversion of biomass-derived carbohydrates into fuels and chemicals via furanic aldehydes[J]. RSC Adv., 2012,2:11184-11206. doi: 10.1039/c2ra21811a
5. [5]
  Climent M.J., Corma A., Iborra S.. Converting carbohydrates to bulk chemicals and fine chemicals over heterogeneous catalysts[J]. Green Chem., 2011,13:520-540. doi: 10.1039/c0gc00639d
6. [6]
  Nakagawa Y., Tamura M., Tomishige K.. Catalytic reduction of biomass-derived furanic compounds with hydrogen[J]. ACS Catal., 2013,3:2655-2668. doi: 10.1021/cs400616p
7. [7]
  Gürbüz E.I., Gallo J.M.R., Alonso D.M.. Gallo M.R.[J]. Conversion of hemicellulose into furfural using solid acid catalysts in γ-valerolactone, Angew. Chem. Int. Ed., 2013,52:1270-1274.
8. [8]
  Cui J.L., Tan J.J., Deng T.S.. Conversion of carbohydrates to furfural via selective cleavage of the carbon-carbon bond:the cooperative effects of zeolite and solvent[J]. Green Chem., 2016,18:1619-1624. doi: 10.1039/C5GC01948F
9. [9]
  Aida T.M., Sato Y., Watanabe M.. Dehydration of d-glucose in high temperature water at pressures up to 80 MPa[J]. J. Supercrit. Fluids, 2007,40:381-388. doi: 10.1016/j.supflu.2006.07.027
10. [10]
  Jin F.M., Enomoto H.. Rapid and highly selective conversion of biomass into value-added products in hydrothermal conditions:chemistry of acid/basecatalysed and oxidation reactions[J]. Energy Environ. Sci., 2011,4:382-397. doi: 10.1039/C004268D
11. [11]
  Yan K., Wu G., Lafleur T., Jarvis C.. Production[J]. properties and catalytic hydrogenation of furfural to fuel additives and value-added chemicals, Renew. Sustain. Energy Rev., 2014,38:663-676.
12. [12]
  Renz M.. Ketonization of carboxylic acids by decarboxylation:mechanism and scope[J]. Eur. J. Org. Chem., 2005,2005:979-988. doi: 10.1002/(ISSN)1099-0690
13. [13]
  Dubkov K.A., Panov G.I., Starokon E.V., Parmon V.N.. Non-catalytic liquid phase oxidation of alkenes with nitrous oxide. 2. Oxidation of cyclopentene to cyclopentanone[J]. React. Kinet. Catal. Lett., 2002,77:197-205. doi: 10.1023/A:1020372726494
14. [14]
  Marquié J., Laporterie A., Dubac J., Roques N.. Graphite-supported ketodecarboxylation of carboxylic diacids[J]. Synlett, 2001,2001:0493-0496. doi: 10.1055/s-2001-12319
15. [15]
  Hronec M., Fulajtarová K.. Selective transformation of furfural to cyclopentanone[J]. Catal. Commun., 2012,24:100-104. doi: 10.1016/j.catcom.2012.03.020
16. [16]
  Hronec M., Fulajtarová K., Liptaj T.. Effect of catalyst and solvent on the furan ring rearrangement to cyclopentanone[J]. Appl. Catal. A:Gen., 2012,437:104-111.
17. [17]
  Fang R.Q., Liu H.L., Luque R., Li Y.W.. Efficient and selective hydrogenation of biomass-derived furfural to cyclopentanone using Ru catalysts[J]. Green Chem., 2015,17:4183-4188. doi: 10.1039/C5GC01462J
18. [18]
  Hronec M., Fulajtarová K., Vávra I.. Carbon supported Pd-Cu catalysts for highly selective rearrangement of furfural to cyclopentanone[J]. Appl. Catal. B:Environ., 2016,181:210-219. doi: 10.1016/j.apcatb.2015.07.046
19. [19]
  Zhang G.S., Zhu M.M., Zhang Q.. Towards quantitative and scalable transformation of furfural to cyclopentanone with supported gold catalysts[J]. Green Chem., 2016,18:2155-2164. doi: 10.1039/C5GC02528A
20. [20]
  Liu Y.H., Chen Z.H., Wang X.F.. Highly selective and efficient rearrangement of biomass-derived furfural to cyclopentanone over interface-active Ru/carbon nanotubes catalyst in water[J]. ACS Sustain. Chem. Eng., 2017,5:744-751. doi: 10.1021/acssuschemeng.6b02080
21. [21]
  Yang Y.L., Du Z.T., Huang Y.H.. Conversion of furfural into cyclopentanone over Ni-Cu bimetallic catalysts[J]. Green Chem., 2013,15:1932-1940. doi: 10.1039/c3gc37133f
22. [22]
  Zhu H.Y., Zhou M.H., Zeng Z., Xiao G.M., Xiao R.. Selective hydrogenation of furfural to cyclopentanone over Cu-Ni-Al hydrotalcite-based catalysts[J]. Korean J. Chem. Eng., 2014,31:593-597. doi: 10.1007/s11814-013-0253-y
23. [23]
  Wang Y., Sang S.Y., Zhu W., Gao L.J., Xiao G.M.. CuNi@C catalysts with high activity derived from metal-organic frameworks precursor for conversion of furfural to cyclopentanone[J]. Chem. Eng. J., 2016,299:104-111. doi: 10.1016/j.cej.2016.04.068
24. [24]
  Guo J.H., Xu G.Y., Han Z.. Selective conversion of furfural to cyclopentanone with CuZnAl catalysts[J]. ACS Sustain. Chem. Eng., 2014,2:2259-2266. doi: 10.1021/sc5003566
25. [25]
  Hronec M., Fulajtarová K., Soták T.. Highly selective rearrangement of furfuryl alcohol to cyclopentanone[J]. Appl. Catal. B:Environ., 2014,154:294-300.
26. [26]
  Ohyama J., Kanao R., Ohira Y., Satsuma A.. The effect of heterogeneous acid-base catalysis on conversion of 5-hydroxymethylfurfural into a cyclopentanone derivative[J]. Green Chem., 2016,18:676-680. doi: 10.1039/C5GC01723H
27. [27]
  Zhou M.H., Zhu H.Y., Niu L., Xiao G.M., Xiao R.. Catalytic hydroprocessing of furfural to cyclopentanol over Ni/CNTs catalysts:model reaction for upgrading of bio-oil[J]. Catal. Lett., 2014,144:235-241. doi: 10.1007/s10562-013-1149-5
28. [28]
  Zhou M.H., Zeng Z., Zhu H.Y., Xiao G.M., Xiao R.. Aqueous-phase catalytic hydrogenation of furfural to cyclopentanol over Cu-Mg-Al hydrotalcites derived catalysts:model reaction for upgrading of bio-oil[J]. J. Energy Chem., 2014,23:91-96. doi: 10.1016/S2095-4956(14)60109-1
29. [29]
  Wang Y., Zhou M.H., Wang T.Z., Xiao G.M.. Conversion of furfural to cyclopentanol on Cu/Zn/Al catalysts derived from hydrotalcite-like materials[J]. Catal Lett., 2015,145:1557-1565. doi: 10.1007/s10562-015-1539-y
30. [30]
  Li X.L., Deng J., Shi J.. Selective conversion of furfural to cyclopentanone or cyclopentanol using different preparation methods of Cu-Co catalysts[J]. Green Chem., 2015,17:1038-1046. doi: 10.1039/C4GC01601G
31. [31]
  Xua Y., Qiu S.B., Long J.X.. In situ hydrogenation of furfural with additives over a RANEY^®Ni catalyst[J]. RSC Adv., 2015,5:91190-91195. doi: 10.1039/C5RA12844G
32. [32]
  Zhang G., Vasudevan K.V., Scott B.L., Hanson S.K.. Understanding the mechanisms of cobalt-catalyzed hydrogenation and dehydrogenation reactions[J]. J. Am. Chem. Soc., 2013,135:8668-8681. doi: 10.1021/ja402679a
33. [33]
  Liu X.H., Xu L.J., Xu G.Y.. Selective hydrodeoxygenation of lignin-derived phenols to cyclohexanols or cyclohexanes over magnetic CoNx@NC catalysts under mild conditions[J]. ACS Catal., 2016,6:7611-7620. doi: 10.1021/acscatal.6b01785
34. [34]
  Conley R.T., Metil I.. An investigation of the structure of furfuryl alcohol polycondensates with infrared spectroscopy[J]. J. Appl. Polym. Sci., 1963,7:37-52. doi: 10.1002/app.1963.070070104
35. [35]
  Wewerka E.M.. An investigation of the polymerization of furfuryl alcohol with gel permeation chromatography[J]. J. Appl. Polym. Sci., 1968,12:1671-1681. doi: 10.1002/app.1968.070120716
36. [36]
  Wewerka E.M.. Study of the γ-alumina polymerization of furfuryl alcohol[J]. J. Polym. Sci. Part A:Polym. Chem., 1971,9:2703-2715. doi: 10.1002/pol.1971.150090923
37. [37]
  Kim T., Assary R.S., Pauls R.E.. Thermodynamics and reaction pathways of furfuryl alcohol oligomer formation[J]. Catal. Commun., 2014,46:66-70. doi: 10.1016/j.catcom.2013.11.030
38. [38]
  Guigo N., Mija A., Vincent L., Sbirrazzuoli N.. Chemorheological analysis and model-free kinetics of acid catalysed furfuryl alcohol polymerization[J]. Phys. Chem. Chem. Phys., 2007,9:5359-5366. doi: 10.1039/b707950h
39. [39]
  Lee J., Burt S.P., Carrero C.A.. Stabilizing cobalt catalysts for aqueousphase reactions by strongmetal-support interaction[J]. J. Catal., 2015,330:19-27. doi: 10.1016/j.jcat.2015.07.003
40. [40]
  Kumar P., Srivastava V.C., Mishra I.M.. Dimethyl carbonate synthesis from propylene carbonate with methanol using Cu-Zn-Al catalyst[J]. Energy Fuels, 2015,29:2664-2675. doi: 10.1021/ef502856z
41. [41]
  de Souza P.M., Rabelo-Neto R.C., Borges L.E.. Effect of zirconia morphology on hydrodeoxygenation of phenol over Pd/ZrO₂[J]. ACS Catal., 2015,5:7385-7398. doi: 10.1021/acscatal.5b01501
42. [42]
  Bandura A.V., Lvov S.N.. The ionization constant of water over wide ranges of temperature and density[J]. J. Phys. Chem. Ref. Data, 2006,35:15-30. doi: 10.1063/1.1928231
43. [43]
  Xia S.Q., Li Y., Shang Q.Y., Zhang C.W., Ma P.S.. Liquid-phase catalytic hydrogenation of furfural in variable solvent media[J]. Trans. Tianjin Univ., 2016,22:202-210. doi: 10.1007/s12209-016-2804-x
44. [44]
  Choura M., Belgacem N.M., Gandini A.. Acid-catalyzed polycondensation of furfuryl alcohol:mechanisms of chromophore formation and cross-linking[J]. Macromolecules, 1996,29:3839-3850. doi: 10.1021/ma951522f
45. [45]
  Hronec M., Fulajtárova K., Mičušik M.. Influence of furanic polymers on selectivity of furfural rearrangement to cyclopentanone[J]. Appl. Catal. A:Gen., 2013,468:426-431. doi: 10.1016/j.apcata.2013.08.052
46. [46]
  Zhang X.H., Wang T.J., Ma L.L., Wu C.Z.. Aqueous-phase catalytic process for production of pentane from furfural over nickel-based catalysts[J]. Fuel, 2010,89:2697-2702. doi: 10.1016/j.fuel.2010.05.043
1. [1]
  Peng Guo , Shicheng Dong , Xiang-Gui Zhang , Bing-Bin Yang , Jun Zhu , Ke-Yin Ye . Cobalt-catalyzed migratory carbon-carbon cross-coupling of borabicyclo[3.3.1]nonane (9-BBN) borates. Chinese Chemical Letters, 2025, 36(4): 110052-. doi: 10.1016/j.cclet.2024.110052
2. [2]
  Lingyun Shen , Shenxiang Yin , Qingshu Zheng , Zheming Sun , Wei Wang , Tao Tu . A rechargeable and portable hydrogen storage system grounded on soda water. Chinese Chemical Letters, 2025, 36(3): 110580-. doi: 10.1016/j.cclet.2024.110580
3. [3]
  Minghui Zhang , Na Zhang , Qian Zhao , Chao Wang , Alexander Steiner , Jianliang Xiao , Weijun Tang . Cobalt pincer complex-catalyzed highly enantioselective hydrogenation of quinoxalines. Chinese Chemical Letters, 2025, 36(4): 110081-. doi: 10.1016/j.cclet.2024.110081
4. [4]
  Hailian Tang , Siyuan Chen , Qiaoyun Liu , Guoyi Bai , Botao Qiao , Fei Liu . Stabilized Rh/hydroxyapatite Catalyst for Furfuryl Alcohol Hydrogenation: Application of Oxidative Strong Metal-Support Interactions in Reducing Conditions. Acta Physico-Chimica Sinica, 2025, 41(4): 100036-. doi: 10.3866/PKU.WHXB202408004
5. [5]
  Ming Huang , Xiuju Cai , Yan Liu , Zhuofeng Ke . Base-controlled NHC-Ru-catalyzed transfer hydrogenation and α-methylation/transfer hydrogenation of ketones using methanol. Chinese Chemical Letters, 2024, 35(7): 109323-. doi: 10.1016/j.cclet.2023.109323
6. [6]
  Rui HUANG , Shengjie LIU , Qingyuan WU , Nanfeng ZHENG . Enhanced selectivity of catalytic hydrogenation of halogenated nitroaromatics by interfacial effects. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 201-212. doi: 10.11862/CJIC.20240356
7. [7]
  Mengjun Zhao , Yuhao Guo , Na Li , Tingjiang Yan . Deciphering the structural evolution and real active ingredients of iron oxides in photocatalytic CO2 hydrogenation. Chinese Journal of Structural Chemistry, 2024, 43(8): 100348-100348. doi: 10.1016/j.cjsc.2024.100348
8. [8]
  Shaoming Dong , Yiming Niu , Yinghui Pu , Yongzhao Wang , Bingsen Zhang . Subsurface carbon modification of Ni-Ga for improved selectivity in acetylene hydrogenation reaction. Chinese Chemical Letters, 2024, 35(12): 109525-. doi: 10.1016/j.cclet.2024.109525
9. [9]
  Jinyuan Cui , Tingting Yang , Teng Xu , Jin Lin , Kunlong Liu , Pengxin Liu . Hydrogen spillover enhances the selective hydrogenation of α,β-unsaturated aldehydes on the Cu-O-Ce interface. Chinese Journal of Structural Chemistry, 2025, 44(1): 100438-100438. doi: 10.1016/j.cjsc.2024.100438
10. [10]
  Sanmei Wang , Dengxin Yan , Wenhua Zhang , Liangbing Wang . Graphene-supported isolated platinum atoms and platinum dimers for CO₂ hydrogenation: Catalytic activity and selectivity variations. Chinese Chemical Letters, 2025, 36(4): 110611-. doi: 10.1016/j.cclet.2024.110611
11. [11]
  Yuanjin Chen , Xianghui Shi , Dajiang Huang , Junnian Wei , Zhenfeng Xi . Synthesis and reactivity of cobalt dinitrogen complex supported by nonsymmetrical pincer ligand. Chinese Chemical Letters, 2024, 35(7): 109292-. doi: 10.1016/j.cclet.2023.109292
12. [12]
  Jiayi Guo , Liangxiong Ling , Qinwei Lu , Yi Zhou , Xubiao Luo , Yanbo Zhou . Degradation of chloroxylenol by CoS_x activated peroxomonosulfate: Role of cobalt-sulfur ratio. Chinese Chemical Letters, 2025, 36(4): 110380-. doi: 10.1016/j.cclet.2024.110380
13. [13]
  Jun-Jie Fang , Yun-Peng Xie , Xing Lu . Organooxotin and cobalt/manganese heterometallic nanoclusters exhibiting single-molecule magnetism. Chinese Journal of Structural Chemistry, 2025, 44(4): 100515-100515. doi: 10.1016/j.cjsc.2025.100515
14. [14]
  Zixuan Zhu , Xianjin Shi , Yongfang Rao , Yu Huang . Recent progress of MgO-based materials in CO₂ adsorption and conversion: Modification methods, reaction condition, and CO₂ hydrogenation. Chinese Chemical Letters, 2024, 35(5): 108954-. doi: 10.1016/j.cclet.2023.108954
15. [15]
  Ruixue Liu , Xiaobing Ding , Qiwei Lang , Gen-Qiang Chen , Xumu Zhang . Enantioselective and divergent construction of chiral amino alcohols and oxazolidin-2-ones via Ir-f-phamidol-catalyzed dynamic kinetic asymmetric hydrogenation. Chinese Chemical Letters, 2025, 36(3): 110037-. doi: 10.1016/j.cclet.2024.110037
16. [16]
  Xue Xin , Qiming Qu , Islam E. Khalil , Yuting Huang , Mo Wei , Jie Chen , Weina Zhang , Fengwei Huo , Wenjing Liu . Hetero-phase zirconia encapsulated with Au nanoparticles for boosting electrocatalytic nitrogen reduction. Chinese Chemical Letters, 2024, 35(5): 108654-. doi: 10.1016/j.cclet.2023.108654
17. [17]
  Xinyu Huai , Jingxuan Liu , Xiang Wu . Cobalt-Doped NiMoO4 Nanosheet for High-performance Flexible Supercapacitor. Chinese Journal of Structural Chemistry, 2023, 42(10): 100158-100158. doi: 10.1016/j.cjsc.2023.100158
18. [18]
  Abiduweili Sikandaier , Yukun Zhu , Dongjiang Yang . In-situ decorated cobalt phosphide cocatalyst on Hittorf's phosphorus triggering efficient photocatalytic hydrogen production. Chinese Journal of Structural Chemistry, 2024, 43(2): 100242-100242. doi: 10.1016/j.cjsc.2024.100242
19. [19]
  Ling Fang , Sha Wang , Shun Lu , Fengjun Yin , Yujie Dai , Lin Chang , Hong Liu . Efficient electroreduction of nitrate via enriched active phases on copper-cobalt oxides. Chinese Chemical Letters, 2024, 35(4): 108864-. doi: 10.1016/j.cclet.2023.108864
20. [20]
  Xiaoling WANG , Hongwu ZHANG , Daofu LIU . Synthesis, structure, and magnetic property of a cobalt(Ⅱ) complex based on pyridyl-substituted imino nitroxide radical. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 407-412. doi: 10.11862/CJIC.20240214

Get Citation

PDF

XML

Metrics

PDF Downloads(5)
Abstract views(863)
HTML views(22)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142