화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Korean Journal of Chemical Engineering, Vol.35, No.1, 99-109, January, 2018
DOI10.1007/s11814-017-0238-3  Export Citation
Selective transformation of biomass-derived 5-hydroxymethylfurfural into 2,5-dihydroxymethylfuran via catalytic transfer hydrogenation over magnetic zirconium hydroxides
Lei Hu†, Mei Yang, Ning Xu, Jiaxing Xu, Shouyong Zhou, Xiaozhong Chu, and Yijiang Zhao
  • Jiangsu Key Laboratory for Biomass-based Energy and Enzyme Technology, School of Chemistry and Chemical Engineering, Jiangsu Collaborative Innovation Center of Regional Modern Agriculture & Environmental Protection, Huaiyin Normal University, Huaian 223300, China
E-mail:
An economical and effective approach for the selective transformation of biomass-derived 5-hydroxymethylfurfural (HMF) into 2,5-dihydroxymethylfuran (DHMF) was developed by catalytic transfer hydrogenation over various magnetic zirconium hydroxides (MZHs). As expected, MZH with a moderate Zr/Fe molar ratio of 2 displayed the highest catalytic activity, resulting in 98.4% HMF conversion and 89.6% DHMF yield at 150 °C for 5 h in the presence of 2-butanol that simultaneously acted as the hydrogen donor and reaction solvent, which was ascribed to its appropriate specific surface area, pore size and acid-base content. Moreover, a plausible reaction mechanism for the catalytic transfer hydrogenation of HMF into DHMF over MHZ(Zr/Fe=2) was also proposed, in which the basic hydroxyl groups with the aid of acidic zirconium metal centers were considered to be responsible for the pivotal hydride transfer via a six-membered ring structure.
Keywords:5-Hydroxymethylfurfural;2,5-Dihydroxymethylfuran;2-Butanol;Catalytic Transfer Hydrogenation;Magnetic Zirconium Hydroxides
  1. Besson M, Gallezot P, Pinel C, Chem. Rev., 114(3), 1827 (2014)
  2. Ummartyotin S, Manuspiya H, Renew. Sust. Energ. Rev., 41, 402 (2015)
  3. Hu L, Lin L, Wu Z, Zhou SY, Liu SJ, Appl. Catal. B: Environ., 174-175, 225 (2015)
  4. Kobayashi H, Kaiki H, Shrotri A, Techikawara K, Fukuoka A, Chem. Sci., 7, 692 (2016)
  5. Rosillo-Calle F, J. Chem. Technol. Biotechnol., 91(7), 1933 (2016)
  6. Hu L, Tang X, Wu Z, Lin L, Xu JX, Xu N, Dai BL, Chem. Eng. J., 263, 299 (2015)
  7. Moreno-Recio Mercedes, Santamaria-Gonzalez Jose, Maireles-Torres Pedro, Chem. Eng. J., 303, 22 (2016)
  8. Jae J, Zheng W, Lobo RF, Vlachos DG, ChemSusChem, 6, 1158 (2013)
  9. Jiang N, Qi W, Huang RL, Wang MF, Su RX, He ZM, J. Chem. Technol. Biotechnol., 89(1), 56 (2014)
  10. Zuo M, Le K, Li Z, Jiang YT, Zeng XH, Tang X, Sun Y, Lin L, Ind. Crop. Prod., 99, 1 (2017)
  11. Hao WW, Li WF, Tang X, Zeng XH, Sun Y, Liu SJ, Lin L, Green Chem., 18, 1080 (2016)
  12. Wei ZJ, Lou JT, Li ZB, Liu YX, Catal. Sci. Technol., 6, 6217 (2016)
  13. Perret N, Grigoropoulos A, Zanella M, Manning TD, Claridge JB, Rosseinsky MJ, ChemSusChem, 9, 521 (2016)
  14. Yao SX, Wang XC, Jiang YJ, Wu F, Chen XG, Mu XD, ACS Sustain. Chem. Eng., 2, 173 (2013)
  15. Wang F, Yuan Z, Liu B, Chen S, Zhang Z, J. Ind. Eng. Chem., 38, 181 (2016)
  16. Gao LC, Deng KJ, Zheng JD, Liu B, Zhang ZH, Chem. Eng. J., 270, 444 (2015)
  17. Liu A, Zhang Z, Fang Z, Liu B, Huang K, J. Ind. Eng. Chem., 20(4), 1977 (2014)
  18. Chieffi G, Braun M, Esposito D, ChemSusChem, 8, 3590 (2015)
  19. Xu ZW, Yan PF, Li HX, Liu KR, Liu XM, Jia SY, Zhang ZC, ACS Catal., 6, 3784 (2016)
  20. Liu DJ, Zhang YT, Chen EYX, Green Chem., 14, 2738 (2012)
  21. Mliki K, Trabelsi M, Ind. Crop. Prod., 78, 91 (2015)
  22. Geilen FM, vom Stein T, Engendahl B, Winterle S, Liauw MA, Klankermayer J, Leitner W, Angew. Chem.-Int. Edit., 50, 6831 (2011)
  23. Moreau C, Belgacem MN, Gandini A, Top. Catal., 27, 11 (2014)
  24. Gelmini A, Albonetti S, Cavani F, Cesari C, Lolli A, Zanotti V, Mazzoni R, Appl. Catal. B: Environ., 180, 38 (2016)
  25. Nakagawa Y, Tamura M, Tomishige K, ACS Catal., 3, 2655 (2013)
  26. Kwon Y, de Jong E, Raoufmoghaddam S, Koper MT, ChemSusChem, 6, 1659 (2013)
  27. Jiang Y, Woortman AJJ, van Ekenstein GORA, Petrovic DM, Loos K, Biomacromolecules, 15(7), 2482 (2014)
  28. Jang NR, Kim HR, Hou CT, Kim BS, Polym. Adv. Technol., 24, 814 (2013)
  29. Gandini A, Green Chem., 13, 1061 (2011)
  30. Cao Q, Liang WY, Guan J, Wang L, Qu Q, Zhang XZ, Wang XC, Mu XD, Appl. Catal. A: Gen., 481, 49 (2014)
  31. Balakrishnan M, Sacia ER, Bell AT, Green Chem., 14, 1626 (2012)
  32. Timko JM, Cram DJ, J. Am. Chem. Soc., 96, 7159 (1974)
  33. Hu L, Lin L, Liu SJ, Ind. Eng. Chem. Res., 53(24), 9969 (2014)
  34. Op De Beeck B, Dusselier M, Geboers J, Holsbeek J, Morre E, Oswald S, Giebeler L, Sels BF, Energy Environ. Sci, 8, 230 (2015)
  35. Han JS, Kim YH, Jang HS, Hwang SY, Jegal J, Kim JW, Lee YS, RSC Adv., 6, 93394 (2016)
  36. Alamillo R, Tucker M, Chia M, Pagan-Torres Y, Dumesic J, Green Chem., 14, 1413 (2012)
  37. Chen JZ, Lu F, Zhang JJ, Yu WQ, Wang F, Gao J, Xu J, ChemCatChem, 5, 2822 (2013)
  38. Liu F, Audemar M, De Oliveira Vigier K, Clacens JM, De Campo F, Jerome F, Green Chem., 16, 4110 (2014)
  39. Chatterjee M, Ishizaka T, Kawanami H, Green Chem., 16, 4734 (2014)
  40. Ohyama J, Hayashi Y, Ueda K, Yamamoto Y, Arai S, Satsuma A, J. Phys. Chem., 120, 15129 (2016)
  41. Ohyama J, Esaki A, Yamamoto Y, Arai S, Satsuma A, RSC Adv., 3, 1033 (2013)
  42. Cai HL, Li CZ, Wang AQ, Zhang T, Catal. Today, 234, 59 (2014)
  43. Tamura M, Tokonami K, Nakagawa Y, Tomishige K, Chem. Commun., 49, 7034 (2013)
  44. Kang ES, Chae DW, Kim B, Kim YG, J. Ind. Eng. Chem., 18(1), 174 (2012)
  45. Li G, Sun Z, Yan YE, Zhang YH, Tang Y, ChemSusChem, 10, 494 (2017)
  46. Subbiah S, Simeonov SP, Esperanca JMSS, Rebelo LPN, Afonso CAM, Green Chem., 15, 2849 (2013)
  47. Kwon Y, Birdja YY, Raoufmoghaddam S, Koper MT, ChemSusChem, 8, 1745 (2015)
  48. Roylance JJ, Kim TW, Choi KS, ACS Catal., 6, 1840 (2016)
  49. Kwon Y, Schouten KJP, van der Waal JC, De Jong E, Koper MTM, ACS Catal., 6, 6704 (2016)
  50. Guo YY, Chen JZ, RSC Adv., 6, 101968 (2016)
  51. Li YM, Zhang XY, Li N, Xu P, Lou WY, Zong MH, ChemSusChem, 10, 372 (2017)
  52. Gilkey MJ, Xu BJ, ACS Catal., 6, 1420 (2016)
  53. Scholz D, Aellig C, Hermans I, ChemSusChem, 7, 268 (2013)
  54. Li H, Fang Z, He J, Yang S, ChemSusChem, 10, 681 (2017)
  55. Song JL, Zhou BW, Zhou HC, Wu LQ, Meng QL, Liu ZM, Han BX, Angew. Chem.-Int. Edit., 54, 9399 (2015)
  56. Tang X, Chen HW, Hu L, Hao WW, Sun Y, Zeng XH, Lin L, Liu SJ, Appl. Catal. B: Environ., 147, 827 (2014)
  57. Tang X, Hu L, Sun Y, Zhao G, Hao WW, Lin L, RSC Adv., 3, 10277 (2013)
  58. Tang X, Zeng XH, Li Z, Li WF, Jiang YT, Hu L, Liu SJ, Sun Y, Lin L, ChemCatChem, 7, 1372 (2015)
  59. He J, Li H, Lu YM, Liu YX, Wu ZB, Hu DY, Yang S, Appl. Catal. A: Gen., 510, 11 (2016)
  60. Osatiashtiani A, Lee AF, Wilson K, J. Chem. Technol. Biotechnol., 92(6), 1125 (2017)
  61. Xue ZM, Jiang JY, Li GF, Zhao WC, Wang JF, MuTC, Catal. Sci. Technol., 6, 5374 (2016)
  62. Li H, Liu XF, Yang TT, Zhao WF, Saravanamurugan S, Yang S, ChemSusChem, 18, 1761 (2017)
  63. Zheng Z, Wang JL, Chen HL, Feng LB, Jing R, Lu MZ, Hu B, Ji JB, ChemCatChem, 6, 1626 (2014)
  64. Luo MS, Yuan SH, Tong M, Liao P, Xie WJ, Xu XF, Water Res., 48, 190 (2014)
  65. Feng LB, Wang JL, Chen L, Lu MZ, Zheng Z, Jing R, Chen HL, Shen XB, ChemCatChem, 7, 616 (2015)
  66. Wu SL, Hu WT, Ma M, Asian J. Chem., 25, 2474 (2013)
  67. Wu T, Wan JW, Ma XB, Chin. J. Catal., 36, 425 (2015)
  68. Li H, Fang Z, Yang S, ACS Sustain. Chem. Eng., 4, 236 (2016)
  69. Zheng FC, Chen QW, Hu L, Yan N, Kong XK, Dalton Trans., 43, 1220 (2014)
  70. Guo GY, Chen YL, J. Mater. Sci., 39(12), 4039 (2004)
  71. Mondal A, Ram S, J. Am. Ceram. Soc., 87(12), 2187 (2004)
  72. Mondal A, Ram S, Ceram. Int., 30, 239 (2004)
  73. Mao GY, Yang WJ, Bu FX, Jiang DM, Zhao ZJ, Zhang QH, Fang OC, Jiang JS, J. Mater. Chem., 2, 4481 (2014)
  74. Peng HP, Liang RP, Zhang L, Qiu JD, Electrochim. Acta, 56(11), 4231 (2011)
  75. Li W, Deng Q, Fang G, Chen Y, Zhan J, Wang S, J. Mater. Chem., 1, 1947 (2013)
  76. Guo HX, Lian YF, Yan LL, Qi XH, Smith RL, Green Chem., 15, 2167 (2013)
  77. Hertl W, Langmuir, 5, 96 (1989)
  78. van der Waal JC, Kunkeler PJ, Tan K, van Bekkum H, J. Catal., 173(1), 74 (1998)
  79. De Graauw CF, Peters JA, Van Bekkum H, Huskens J, Synthesis, 10, 1007 (1994)
  80. Johnstone RAW, Wilby AH, Entwistle ID, Chem. Rev., 85, 129 (1985)
  81. Stolle A, Gallert T, Schmoger C, Ondruschka B, RSC Adv., 3, 2112 (2013)
  82. Wang D, Astruc D, Chem. Rev., 115(13), 6621 (2015)