Catalytic hydrolysis of cellulose by phosphotungstic acid–supported functionalized metal-organic frameworks with different electronegative groups

  • Jinye Han
  • Yan WangEmail author
  • Jinquan Wan
  • Yongwen Ma
Research Article


It is found that strong electronegative groups can selectively adsorb cellulose by hydrogen bonds. Grafting strong negatively charged groups onto catalysts to achieve the functionalization of the catalyst can give it the ability to selectively adsorb cellulose without affecting its catalysis, which is of great significance for the hydrolysis of cellulose. In this study, PTA@MIL-101–X (X = –Br, –NH2, –Cl, –NO2) materials were synthesized to investigate the effect of grafting different electronegative groups on carriers to the directional hydrolysis of cellulose. The synthesized catalysts used phosphotungstic acid as the catalytic center while treated MIL-101 structure as the carrier. The grafting of different electronegative groups changed the crystal structure of the metal organic framework without affecting its stability during the reaction. The strong negative functional groups can selectively adsorb cellulose by forming hydrogen bonds with cellulose hydroxyl groups and weaken the hydrogen bonds within cellulose molecules. This hydrogen bond can reduce the side reaction of glucose, lighten the difficulty of cellulose hydrolysis, and improve the efficiency of cellulose conversion at the same time. The hydrolysis rate of cellulose increased with the electronegativity enhancement of the grafted functional groups, and the grafted –NO2 catalyst PTA@MIL-101–NO2 obtained the highest glucose yield of 16.2% in the cellulose-directed hydrolysis. The –NH2 can form a chemical linkage with PTA through electrostatic interaction to get the highest immobilization stability and exhibit excellent stability in the recycling of catalysts.

Graphical abstract


Metal-organic frameworks MIL-101 Immobilization Phosphotungstic acid Cellulose hydrolyzation 


Funding information

This work was supported by the National Natural Science Foundation of China (No. 31570568 and No. 31670585), the Science and Technology Planning Project of Guangzhou City, China (Nos. 201607010079 and 201607020007), the Science and Technology Planning Project of Guangdong Province, China (Nos. 2016A020221005 and 2017A040405022).


  1. Biswal D, Kusalik PG (2017) Probing molecular mechanisms of self-assembly in metal-organic frameworks. ACS Nano 11:258–268. CrossRefGoogle Scholar
  2. Buragohain A, Couck S, Van Der Voort P et al (2016) Synthesis, characterization and sorption properties of functionalized Cr-MIL-101-X (X=-F, -Cl, -Br, -CH3, -C6H4, -F2, -(CH3)2) materials. J Solid State Chem 238:195–202. CrossRefGoogle Scholar
  3. Chen H, Chen S, Yuan X, Zhang Y (2013) Facile synthesis of metal-organic framework MIL-101 from 4-NIm-Cr(NO3)3-H2BDC-H2O. Mater Lett 100:230–232. CrossRefGoogle Scholar
  4. Fazaeli R, Aliyan H, Masoudinia M, Heidari Z (2014) Building MOF bottles (MIL-101 family as heterogeneous single-site catalysts) around H3PW12O40 ships: an efficient catalyst for selective oxidation of sulfides to sulfoxides and sulfones. J Mater Chem EngGoogle Scholar
  5. Férey C, Mellot-Draznieks C, Serre C, et al (2005a) Chemistry: a chromium terephthalate-based solid with unusually large pore volumes and surface area. Science (80- ).
  6. Férey G, Mellot-Draznieks C, Serre C, et al (2005b) A chromium terephthalate-based solid with unusually large pore volumes and surface area. Science (80- ).
  7. Hara M (2010) Biodiesel production by amorphous carbon bearing SO3H, COOH and phenolic OH groups, a solid Brønsted acid catalyst. Top Catal 53:805–810. CrossRefGoogle Scholar
  8. Herbst A, Khutia A, Janiak C (2014) Brønsted instead of Lewis acidity in functionalized MIL-101Cr MOFs for efficient heterogeneous (nano-MOF) catalysis in the condensation reaction of aldehydes with alcohols. Inorg Chem 53:7319–7333. CrossRefGoogle Scholar
  9. Hu X, Lu Y, Dai F, Liu C, Liu Y (2013) Host-guest synthesis and encapsulation of phosphotungstic acid in MIL-101 via “bottle around ship”: an effective catalyst for oxidative desulfurization. Microporous Mesoporous Mater 170:36–44. CrossRefGoogle Scholar
  10. Jia SY, Zhang YF, Liu Y, Qin FX, Ren HT, Wu SH (2013) Adsorptive removal of dibenzothiophene from model fuels over one-pot synthesized PTA@MIL-101(Cr) hybrid material. J Hazard Mater 262:589–597. CrossRefGoogle Scholar
  11. Khutia A, Rammelberg HU, Schmidt T et al (2013) Water sorption cycle measurements on functionalized MIL-101Cr for heat transformation application.
  12. Kim JK, Choi JH, Song JH, Yi J, Song IK (2012) Etherification of n-butanol to di-n-butyl ether over HnXW12O40 (XCo2+, B3+, Si4+, and P5+) Keggin heteropolyacid catalysts. Catal Commun 27:5–8. CrossRefGoogle Scholar
  13. Lammert M, Bernt S, Vermoortele F, de Vos DE, Stock N (2013) Single- and mixed-linker Cr-MIL-101 derivatives: a high-throughput investigation. Inorg Chem 52:8521–8528. CrossRefGoogle Scholar
  14. Lin Y, Kong C, Chen L (2012) Direct synthesis of amine-functionalized MIL-101(Cr) nanoparticles and application for CO<inf>2</inf> capture. RSC Adv 2.
  15. Luo G, Kang L, Zhu M, Dai B (2014) Highly active phosphotungstic acid immobilized on amino functionalized MCM-41 for the oxidesulfurization of dibenzothiophene. Fuel Process Technol 118:20–27. CrossRefGoogle Scholar
  16. Masmoudi F, Bessadok A, Dammak M, Jaziri M, Ammar E (2016) Biodegradable packaging materials conception based on starch and polylactic acid (PLA) reinforced with cellulose. Environ Sci Pollut Res 23:20904–20914. CrossRefGoogle Scholar
  17. Molavi H, Hakimian A, Shojaei A, Raeiszadeh M (2018) Selective dye adsorption by highly water stable metal-organic framework: long term stability analysis in aqueous media. Appl Surf Sci 445:424–436. CrossRefGoogle Scholar
  18. Pang J, Wang A, Zheng M, Zhang T (2010) Hydrolysis of cellulose into glucose over carbons sulfonated at elevated temperatures. Chem Commun 46:6935–6937. CrossRefGoogle Scholar
  19. Qi B, Liu Y, Zheng T, Gao Q, Yan X, Jiao Y, Yang Y (2018) Highly efficient capture of iodine by cu/MIL-101. J Solid State Chem 258:49–55. CrossRefGoogle Scholar
  20. Qu H, Zhou Y, Ma Y et al (2018) A green catalyst for hydrolysis of cellulose : amino acid protic ionic liquid. J Taiwan Inst Chem Eng 93:667–673. CrossRefGoogle Scholar
  21. Ramos-Fernandez EV, Pieters C, Van Der Linden B et al (2012) Highly dispersed platinum in metal organic framework NH 2-MIL- 101(Al) containing phosphotungstic acid - characterization and catalytic performance. J Catal 289:42–52. CrossRefGoogle Scholar
  22. Serra-Crespo P, Ramos-Fernandez EV, Gascon J, Kapteijn F (2011) Synthesis and characterization of an amino functionalized MIL-101(Al): separation and catalytic properties. Chem Mater 23:2565–2572. CrossRefGoogle Scholar
  23. Shrotri A, Kobayashi H, Fukuoka A (2016) Air oxidation of activated carbon to synthesize a biomimetic catalyst for hydrolysis of cellulose. 1299–1303.
  24. Shuai L, Pan X (2012) Hydrolysis of cellulose by cellulase-mimetic solid catalyst. Energy Environ Sci 5:6889–6894. CrossRefGoogle Scholar
  25. Suganuma S, Nakajima K, Kitano M, Yamaguchi D, Kato H, Hayashi S, Hara M (2008) Hydrolysis of cellulose by amorphous carbon bearing SO3H, COOH, and OH groups. J Am Chem Soc 130:12787–12793. CrossRefGoogle Scholar
  26. Tian J, Wang J, Zhao S, Jiang C, Zhang X, Wang X (2010) Hydrolysis of cellulose by the heteropoly acid H3PW12O40. Cellulose. 17:587–594. CrossRefGoogle Scholar
  27. Wang XS, Huang YB, Lin ZJ, Cao R (2014) Phosphotungstic acid encapsulated in the mesocages of amine-functionalized metal-organic frameworks for catalytic oxidative desulfurization. Dalton Trans 43:11950–11958. CrossRefGoogle Scholar
  28. Zhang C, Fu Z, Liu YC, et al (2012) Green chemistry ionic liquid-functionalized biochar sulfonic acid as a biomimetic catalyst for hydrolysis of cellulose and bamboo under microwave irradiation. 1928–1934.
  29. Zhang Y, Wan J, Wang Y, Ma Y (2015) Synthesis of phosphotungstic acid-supported versatile metal-organic framework PTA@MIL-101(Fe)-NH2-Cl. RSC Adv 5:97589–97597. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Jinye Han
    • 1
  • Yan Wang
    • 1
    • 2
    Email author
  • Jinquan Wan
    • 1
    • 2
    • 3
  • Yongwen Ma
    • 1
    • 2
    • 3
  1. 1.College of Environment and EnergySouth China University of TechnologyGuangzhouChina
  2. 2.The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of EducationSouth China University of TechnologyGuangzhouChina
  3. 3.State Key Laboratory of Pulp and Paper EngineeringSouth China University of TechnologyGuangzhouChina

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