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Cellulose

, Volume 26, Issue 10, pp 5937–5945 | Cite as

Preparation of high-aspect-ratio cellulose nanocrystals by solvothermal synthesis followed by mechanical exfoliation

  • Aiqin Gao
  • Huanghuang Chen
  • Aiqin Hou
  • Kongliang XieEmail author
Original Research
  • 134 Downloads

Abstract

We report a green chemical–physical approach for extracting cellulose nanocrystals (CNCs), using a two-step collaborative process combining solvothermal pretreatment and mechanical exfoliation. This method avoids the use of large volumes of sulfuric acid. The structure, morphology, size distribution, zeta potential, crystallinity, and thermal stability of the CNCs are characterized by Fourier-transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, and scanning electron, transmission electron and atomic force microscopies. The yield and properties of the obtained CNCs are investigated and compared with those obtained by the conventional acid hydrolysis method. A yield of 72.17 ± 2.00% was obtained, which was significantly higher than that of 30–35% for the traditional sulfuric acid hydrolysis method. CNCs are obtained with an aspect ratio of 25 times, average length of 280 nm, and average width of 11 nm. The CNCs obtained by the two-step process exhibit better thermal stability than those obtained by the conventional acid hydrolysis. The combination of solvothermal pretreatment and mechanical exfoliation is an efficient and promising method for the large-scale production of CNCs for industrial application.

Keywords

Solvothermal Mechanical exfoliation Cellulose nanocrystals High aspect ratio 

Notes

Acknowledgments

This work was financially supported by Shanghai Natural Science Foundation (Grant No. 18ZR1400800), the Fundamental Research Funds for the Central Universities (No. 2232019D-3-19) and the Initial Research Funds for Young Teachers of Donghua University to Aiqin Gao. We thank Aidan G. Young, PhD, from Liwen Bianji, Edanz Group China (www.liwenbianji.cn/ac), for editing the English text of a draft of this manuscript.

Compliance with ethical standards

Conflict of interest

There are no conflicts of interest to declare.

References

  1. Aparna R, Sivakumar N, Balakrishnan A, Sreekumar Nair A, Nair SV, Subramanian K (2013) An effective route to produce few-layer graphene using combinatorial ball milling and strong aqueous exfoliants. J Renew Sustain Energy 5:033123CrossRefGoogle Scholar
  2. Bossa N, Carpenter AW, Kumar N, Lannoy CF, Wiesner M (2017) Cellulose nanocrystal zero-valent iron nanocomposites for groundwater remediation. Environ Sci Nano 4:1294–1303CrossRefGoogle Scholar
  3. Chen L, Wang Q, Hirth K, Baez C, Agarwal UP, Zhu J (2015) Tailoring the yield and characteristics of wood cellulose nanocrystals (CNC) using concentrated acid hydrolysis. Cellulose 22:1753–1762CrossRefGoogle Scholar
  4. Deepa B, Abraham E, Cordeiro N, Mozetic M, Mathew AP, Oksman K, Faria M, Thomas S, Pothan LA (2015) Utilization of various lignocellulosic biomass for the production of nanocellulose: a comparative study. Cellulose 22:1075–1090CrossRefGoogle Scholar
  5. Del Rio-Castillo AE, Merino C, Díez-Barra E, Vázquez E (2014) Selective suspension of single layer graphene mechanochemically exfoliated from carbon nanofibres. Nano Res 7:963–972CrossRefGoogle Scholar
  6. Driscoll M, Stipanovic A, Winter W, Cheng K, Manning M, Spiese J, Galloway RA, Cleland MR (2009) Electron beam irradiation of cellulose. Radiat Phys Chem 78:539–542CrossRefGoogle Scholar
  7. Filson PB, Dawson-Andoh BE (2009) Sono-chemical preparation of cellulose nanocrystals from lignocellulose derived materials. Bioresour Technol 100:2259–2264CrossRefPubMedGoogle Scholar
  8. Frka-Petesic B, Radavidson H, Jean B, Heux L (2017) Dynamically controlled iridescence of cholesteric cellulose nanocrystal suspensions using electric fields. Adv Mater 29:1606208CrossRefGoogle Scholar
  9. Gao Y, Wang X, Yang H, Chen H (2012) Characterization of products from hydrothermal treatments of cellulose. Energy 42:457–465CrossRefGoogle Scholar
  10. Gencer A, Schutz C, Thielemans W (2017) Influence of the particle concentration and marangoni flow on the formation of cellulose nanocrystal films. Langmuir 33:228–234CrossRefPubMedGoogle Scholar
  11. Guidetti G, Atifi S, Vignolini S, Hamad WY (2016) Flexible photonic cellulose nanocrystal films. Adv Mater 28:10042–10047CrossRefPubMedPubMedCentralGoogle Scholar
  12. Hu L, Luo Y, Cai B, Li J, Tong D, Hu C (2014) The degradation of the lignin in Phyllostachys heterocycla cv. pubescens in an ethanol solvothermal system. Green Chem 16:3107–3116CrossRefGoogle Scholar
  13. Jeon IY, Shin YR, Sohn GJ, Choi HJ, Bae SY, Mahmood J, Jung SM, Seo JM, Kim MJ, Wook Chang D, Dai L, Baek JB (2012) Edge-carboxylated graphene nanosheets via ball milling. Proc Natl Acad Sci USA 109(15):5588–5593CrossRefPubMedGoogle Scholar
  14. 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 22:935–969CrossRefGoogle Scholar
  15. Kaushik M, Moores A (2016) Nanocelluloses as versatile supports for metal nanoparticles and their applications in catalysis. Green Chem 18:622–637CrossRefGoogle Scholar
  16. Lee WJ, Clancy AJ, Kontturi E, Bismarck A, Shaffer MS (2016) Strong and stiff: high-performance cellulose nanocrystal/poly(vinyl alcohol) composite fibers. ACS Appl Mater Interfaces 8:31500–31504CrossRefPubMedGoogle Scholar
  17. Li R, Fei J, Cai Y, Li Y, Feng J, Yao J (2009) Cellulose whiskers extracted from mulberry: a novel biomass production. Carbohydr Polym 76:94–99CrossRefGoogle Scholar
  18. Li Y, Liu Y, Chen W, Wang Q, Liu Y, Li J, Yu H (2016) Facile extraction of cellulose nanocrystals from wood using ethanol and peroxide solvothermal pretreatment followed by ultrasonic nanofibrillation. Green Chem 18:1010–1018CrossRefGoogle Scholar
  19. Lu Z, Fan L, Zheng H, Lu Q, Liao Y, Huang B (2013) Preparation, characterization and optimization of nanocellulose whiskers by simultaneously ultrasonic wave and microwave assisted. Bioresour Technol 146:82–88CrossRefPubMedGoogle Scholar
  20. Lyu H, Gao B, He F, Ding C, Tang J, Crittenden JC (2017) Ball-milled carbon nanomaterials for energy and environmental applications. ACS Sustain Chem Eng 5:9568–9585CrossRefGoogle Scholar
  21. Nascimento DM, Almeida JS, Dias AF, Figueirêdo MCB, Morais JPS, Feitosa JPA, Rosa MDF (2014) A novel green approach for the preparation of cellulose nanowhiskers from white coir. Carbohydr Polym 110:456–463CrossRefPubMedGoogle Scholar
  22. Novo LP, Bras J, García A, Belgacem N, Curvelo AA (2015) Subcritical water: a method for green production of cellulose nanocrystals. ACS Sustain Chem Eng 3:2839–2846CrossRefGoogle Scholar
  23. Shao L, Sun H, Miao L, Chen X, Han M, Sun J, Liu S, Li L, Cheng F, Chen J (2018) Facile preparation of NH2-functionalized black phosphorene for the electrocatalytic hydrogen evolution reaction. J Mater Chem A 6:2494–2499CrossRefGoogle Scholar
  24. Soares O, Rocha RP, Gonçalves A, Figueiredo JL, Órfão J, Pereira MFR (2015) Easy method to prepare N-doped carbon nanotubes by ball milling. Carbon 91:114–121CrossRefGoogle Scholar
  25. Tang L, Huang B, Ou W, Chen X, Chen Y (2011) Manufacture of cellulose nanocrystals by cation exchange resin-catalyzed hydrolysis of cellulose. Bioresour Technol 102:10973–10977CrossRefPubMedGoogle Scholar
  26. Tong WY, Abdullah AYK, Rozman NAS, Bin Wahid MIA, Hossain MS, Ring LC, Lazim Y, Tan W (2018) Antimicrobial wound dressing film utilizing cellulose nanocrystal as drug delivery system for curcumin. Cellulose 25:631–638CrossRefGoogle Scholar
  27. Xu J, Jeon IY, Seo JM, Dou S, Dai L, Baek JB (2014a) Edge-selectively halogenated graphene nanoplatelets (XGnPs, X = Cl, Br, or I) prepared by ball-milling and used as anode materials for lithium-ion batteries. Adv Mater 26(43):7317–7323CrossRefPubMedGoogle Scholar
  28. Xu J, Shui J, Wang J, Wang M, Liu H, Dou SX, Jeon IY, Seo JM, Baek J, Dai L (2014b) Sulfur–graphene nanostructured cathodes via ball-milling for high-performance lithium–sulfur batteries. ACS Nano 8:10920–10930CrossRefPubMedGoogle Scholar
  29. Yang X, Cranston ED (2014) Chemically cross-linked cellulose nanocrystal aerogels with shape recovery and superabsorbent properties. Chem Mater 26:6016–6025CrossRefGoogle Scholar
  30. Yi M, Shen Z (2015) A review on mechanical exfoliation for the scalable production of graphene. J Mater Chem A 3:11700–11715CrossRefGoogle Scholar
  31. Yu H, Qin Z, Liu L, Yang X, Zhou Y, Yao J (2013a) Comparison of the reinforcing effects for cellulose nanocrystals obtained by sulfuric and hydrochloric acid hydrolysis on the mechanical and thermal properties of bacterial polyester. Compos Sci Technol 87:22–28CrossRefGoogle Scholar
  32. Yu H, Qin Z, Liang B, Liu N, Zhou Z, Chen L (2013b) Facile extraction of thermally stable cellulose nanocrystals with a high yield of 93% through hydrochloric acid hydrolysis under hydrothermal conditions. J Mater Chem A 1:3938–3944CrossRefGoogle Scholar
  33. Yu H, Sun B, Zhang D, Chen G, Yang X, Yao J (2014) Reinforcement of biodegradable poly (3-hydroxybutyrate-co-3-hydroxyvalerate) with cellulose nanocrystal/silver nanohybrids as bifunctional nanofillers. J Mater Chem B 2:8479–8489CrossRefGoogle Scholar
  34. Zhang Z, Sun J, Lai C, Wang Q, Hu C (2017) High-yield ball-milling synthesis of extremely concentrated and highly conductive graphene nanoplatelet inks for rapid surface coating of diverse substrates. Carbon 120:411–418CrossRefGoogle Scholar
  35. Zhou S, Liu P, Wang M, Zhao H, Yang J, Xu F (2016) Sustainable, reusable, and superhydrophobic aerogels from microfibrillated cellulose for highly effective oil/water separation. ACS Sustain Chem Eng 4:6409–6416CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Key Lab of Science and Technology of Eco-textile, Ministry of Education, College of Chemistry, Chemical Engineering and BiotechnologyDonghua UniversityShanghaiPeople’s Republic of China
  2. 2.National Engineering Research Center for Dyeing and Finishing of TextilesDonghua UniversityShanghaiPeople’s Republic of China

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