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Cellulose

, Volume 24, Issue 8, pp 3243–3254 | Cite as

Facile one-step extraction and oxidative carboxylation of cellulose nanocrystals through hydrothermal reaction by using mixed inorganic acids

  • Miao Cheng
  • Zongyi Qin
  • Yuanyu Chen
  • Jiaming Liu
  • Zichu Ren
Original Paper

Abstract

A facile and efficient approach to prepare carboxylated cellulose nanocrystals (CCNCs) is presented through a novel one-step hydrothermal procedure by using a mixed acid system of hydrochloric acid and nitric acid (HCl/HNO3). The as-prepared cellulose nanoparticles were characterized by scanning electron microscopy, wide angle X-ray diffraction, conductometric titrations, Fourier transform infrared spectrometry and thermal gravimetric analysis. The results showed that the combination of the mixed acid and hydrothermal reaction can speed up the process of CCNC preparation, and then high quality of the product could be obtained at relatively low acid concentration. It is found that the addition of nitric acid could not only promote the conversion of surface groups on the cellulose nanocrystals (CNCs), but also have significant influences on the yield, particle size and microstructure of CNCs. For the volume ratio of HCl/HNO3 of 7:3, the as-prepared CCNCs exhibited the largest length to diameter ratio and narrowest dimension distributions as well as maximum degree of oxidation of 0.12. In addition, high dispersion stability for the CCNCs could be observed due to the existence of negative carboxyl groups. This approach based on one-step oxidative carboxylation greatly simplified the preparation of CCNCs with high yield and high crystallinity under mild hydrothermal condition.

Keywords

Carboxylated cellulose nanocrystals Mixed acid hydrolysis Hydrothermal reaction One-step oxidative carboxylation 

Notes

Acknowledgments

This work has been financially supported by Key Basic Research Project of Science and Technology of Shanghai (15Q10622). Dr. Miao Cheng kindly acknowledges the support from the Innovation Research Funds for the Doctoral candidate of Donghua University (15D310606).

References

  1. Araki J, Wada M, Kuga S, Okano T (1998) Flow properties of microcrystalline cellulose suspension prepared by acid treatment of native cellulose. Colloid Surf A 142(1):75–82CrossRefGoogle Scholar
  2. Bhattacharjee S (2016) DLS and zeta potential—what they are and what they are not? J Control Release 235:337–351CrossRefGoogle Scholar
  3. Camarero Espinosa S, Kuhnt T, Foster EJ, Weder C (2013) Isolation of thermally stable cellulose nanocrystals by phosphoric acid hydrolysis. Biomacromol 14(4):1223–1230CrossRefGoogle Scholar
  4. Castro-Guerrero CF, Gray DG (2014) Chiral nematic phase formation by aqueous suspensions of cellulose nanocrystals prepared by oxidation with ammonium persulfate. Cellulose 21(4):2567–2577CrossRefGoogle Scholar
  5. Chen GY, Yu HY, Zhang CH, Zhou Y, Yao JM (2016a) A universal route for the simultaneous extraction and functionalization of cellulose nanocrystals from industrial and agricultural celluloses. J Nanopart Res 18(2):1–14CrossRefGoogle Scholar
  6. Chen L, Zhu JY, Baez C, Kitin P, Elder T (2016b) Highly thermal-stable and functional cellulose nanocrystals and nanofibrils produced using fully recyclable organic acids. Green Chem 18(13):3835–3843CrossRefGoogle Scholar
  7. Cheng M, Qin ZY, Liu YN, Qin YF, Li T, Chen L, Zhu MF (2014) Efficient extraction of carboxylated spherical cellulose nanocrystals with narrow distribution through hydrolysis of lyocell fibers by using ammonium persulfate as an oxidant. J Mater Chem A 2(1):251–258CrossRefGoogle Scholar
  8. Domingues RM, Gomes ME, Reis RL (2014) The potential of cellulose nanocrystals in tissue engineering strategies. Biomacromol 15(7):2327–2346CrossRefGoogle Scholar
  9. Eyley S, Thielemans W (2014) Surface modification of cellulose nanocrystals. Nanoscale 6(14):7764–7779CrossRefGoogle Scholar
  10. Fujisawa S, Saito T, Kimura S, Iwata T, Isogai A (2013) Surface engineering of ultrafine cellulose nanofibrils toward polymer nanocomposite materials. Biomacromol 14(5):1541–1546CrossRefGoogle Scholar
  11. Habibi Y, Chanzy H, Vignon MR (2006) TEMPO—mediated surface oxidation of cellulose whiskers. Cellulose 13(6):679–687CrossRefGoogle Scholar
  12. Hamid SBA, Zain SK, Das R, Centi G (2016) Synergic effect of tungstophosphoric acid and sonication for rapid synthesis of crystalline nanocellulose. Carbohydr Polym 138:349–355CrossRefGoogle Scholar
  13. Henrique MA, Neto WPF, Silvério HA, Martins DF, Gurgel LVA, da Silva Barud H, de Morais LG, Pasquini D (2015) Kinetic study of the thermal decomposition of cellulose nanocrystals with different polymorphs, cellulose I and II, extracted from different sources and using different types of acids. Ind Crop Prod 76:128–140CrossRefGoogle Scholar
  14. Hosseinidoust Z, Alam MN, Sim G, Tufenkji N, van de Ven TG (2015) Cellulose nanocrystals with tunable surface charge for nanomedicine. Nanoscale 7(40):16647–16657CrossRefGoogle Scholar
  15. Jiang F, Esker AR, Roman M (2010) Acid-catalyzed and solvolytic desulfation of H2SO4—hydrolyzed cellulose nanocrystals. Langmuir 26(23):17919–17925CrossRefGoogle Scholar
  16. Jonoobi M, Oladi R, Davoudpour Y, Oksman K, Dufresne A, Hamzeh Y, Davoodi R (2015) Different preparation methods and properties of nanostructured cellulose from various natural resources and residues: a review. Cellulose 22(2):935–969CrossRefGoogle Scholar
  17. Kumar V, Yang T (2002) HNO3/H3PO4–NaNO2 mediated oxidation of cellulose—preparation and characterization of bioabsorbable oxidized celluloses in high yields and with different levels of oxidation. Carbohydr Polym 48(4):403–412CrossRefGoogle Scholar
  18. Lam E, Male KB, Chong JH, Leung AC, Luong JH (2012a) Applications of functionalized and nanoparticle—modified nanocrystalline cellulose. Trends Biotechnol 30(5):283–290CrossRefGoogle Scholar
  19. Lam E, Leung AC, Liu Y, Majid E, Hrapovic S, Male KB, Luong JH (2012b) Green strategy guided by Raman spectroscopy for the synthesis of ammonium carboxylated nanocrystalline cellulose and the recovery of byproducts. ACS Sustain Chem Eng 1(2):278–283CrossRefGoogle Scholar
  20. Leung AC, Hrapovic S, Lam E, Liu Y, Male KB, Mahmoud KA, Luong JH (2011) Characteristics and properties of carboxylated cellulose nanocrystals prepared from a novel one-step procedure. Small 7(3):302–305CrossRefGoogle Scholar
  21. Mascheroni E, Rampazzo R, Ortenzi MA, Piva G, Bonetti S, Piergiovanni L (2016) Comparison of cellulose nanocrystals obtained by sulfuric acid hydrolysis and ammonium persulfate, to be used as coating on flexible food-packaging materials. Cellulose 23(1):779–793CrossRefGoogle Scholar
  22. Montanari S, Roumani M, Heux L, Vignon MR (2005) Topochemistry of carboxylated cellulose nanocrystals resulting from TEMPO—mediated oxidation. Macromolecules 38(5):1665–1671CrossRefGoogle Scholar
  23. Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40(7):3941–3994CrossRefGoogle Scholar
  24. Qin ZY, Tong G, Chin YF, Zhou JC (2011) Preparation of ultrasonic-assisted high carboxylate content cellulose nanocrystals by TEMPO oxidation. BioResources 6(2):1136–1146Google Scholar
  25. Sharma PR, Varma AJ (2014) Functionalized celluloses and their nanoparticles: morphology, thermal properties, and solubility studies. Carbohydr Polym 104:135–142CrossRefGoogle Scholar
  26. Sirviö JA, Honkaniemi S, Visanko M, Liimatainen H (2015) Composite films of poly (vinyl alcohol) and bifunctional cross-linking cellulose nanocrystals. ACS Appl Mater Int 7(35):19691–19699CrossRefGoogle Scholar
  27. Sirviö JA, Visanko M, Liimatainen H (2016) Acidic deep eutectic solvents as hydrolytic media for cellulose nanocrystal production. Biomacromol 17(9):3025–3032CrossRefGoogle Scholar
  28. Sun B, Yu HY, Zhou Y, Huang Z, Yao JM (2016a) Single-step extraction of functionalized cellulose nanocrystal and polyvinyl chloride from industrial wallpaper wastes. Ind Crop Prod 89:66–77CrossRefGoogle Scholar
  29. Sun B, Zhang M, Hou Q, Liu R, Wu T, Si C (2016b) Further characterization of cellulose nanocrystal (CNC) preparation from sulfuric acid hydrolysis of cotton fibers. Cellulose 23(1):439–450CrossRefGoogle Scholar
  30. Xiong R, Zhang X, Tian D, Zhou Z, Lu C (2012) Comparing microcrystalline with spherical nanocrystalline cellulose from waste cotton fabrics. Cellulose 19(4):1189–1198CrossRefGoogle Scholar
  31. Xu YH, Liu X, Liu X, Tan JL, Zhu HL (2014) Influence of HNO3/H3PO4–NaNO2 mediated oxidation on the structure and properties of cellulose fibers. Carbohydr Polym 111:955–963CrossRefGoogle Scholar
  32. Yang H, Alam MN, van de Ven TG (2013) Highly charged nanocrystalline cellulose and dicarboxylated cellulose from periodate and chlorite oxidized cellulose fibers. Cellulose 20(4):1865–1875CrossRefGoogle Scholar
  33. Yu HY, Qin ZY, Liang BL, Liu N, Zhou Z, Chen L (2013a) Facile extraction of thermally stable cellulose nanocrystals with a high yield of 93% through hydrochloric acid hydrolysis under hydrothermal conditions. J Mater Chem A 1(12):3938–3944CrossRefGoogle Scholar
  34. Yu XL, Tong S, Ge M, Wu L, Zuo J, Cao C, Song W (2013b) Adsorption of heavy metal ions from aqueous solution by carboxylated cellulose nanocrystals. J Environ Sci 25(5):933–943CrossRefGoogle Scholar
  35. Yu HY, Zhang DZ, Lu FF, Yao J (2016) New approach for single − step extraction of carboxylated cellulose nanocrystals for their use as adsorbents and flocculants. ACS Sustain Chem Eng 4(5):2632–2643CrossRefGoogle Scholar
  36. Zhang K, Sun P, Liu H, Shang S, Song J, Wang D (2016) Extraction and comparison of carboxylated cellulose nanocrystals from bleached sugarcane bagasse pulp using two different oxidation methods. Carbohydr Polym 138:237–243CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2017

Authors and Affiliations

  • Miao Cheng
    • 1
  • Zongyi Qin
    • 1
  • Yuanyu Chen
    • 1
  • Jiaming Liu
    • 1
  • Zichu Ren
    • 1
  1. 1.State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, and College of Material Science and EngineeringDonghua UniversityShanghaiChina

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