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Recyclable carboxylated cellulose beads with tunable pore structure and size for highly efficient dye removal

  • Ranju Meng
  • Lin Liu
  • Yuanyuan Jin
  • Zhenze Luo
  • Huiying Gao
  • Juming YaoEmail author


In this work, carboxylated cellulose beads with highly porous structure were fabricated using phase separation method, and subsequent carboxylation using citrate. The pore structure and average size of the carboxylated cellulose beads could be altered by adjusting reaction temperature and time during carboxylation, in which the average sizes were in the range of 2.08–2.34 mm. Moreover, the resulting porous cellulose beads with open-pore surface exhibited high specific surface area (~ 156.86 m2/g) and high carboxyl group content (~ 4.93 mmol/g). Considering their high specific surface area, surface carboxylation, and eco-friendly, the carboxylated cellulose beads were utilized for removal of cationic dye, methylene blue (MB). The porous, carboxylated cellulose beads exhibited remarkable adsorption performance with a maximum adsorption capacity of 288.81 mg/g, about 8 times higher than unmodified cellulose beads. Also, this porous bead showed a promising application as high-efficient absorbent and its adsorption capacity for MB still retained 250.78 mg/g after ten adsorption–desorption cycles.

Graphic abstract


Cellulose Open-pore bead Surface carboxylation Dye removal Recyclability 



The work was financially supported by the Public Technology Research Plan of Zhejiang Province (LGF18E030003, LY15E030003), National Natural Science Foundation of China (51672251), and 521 Talent Project of Zhejiang Sci-Tech University.

Compliance with ethical standards

Conflict of interest

This is the original work of the authors, and all the authors mutually agree that it should be submitted to Cellulose. All authors declare that they do not have a conflict of interest.


  1. Albadarin AB, Collins MN, Naushad M et al (2017) Activated lignin-chitosan extruded blends for efficient adsorption of methylene blue. Chem Eng J 307:264–272CrossRefGoogle Scholar
  2. Bai J, Huang Y, Gong Q et al (2018) Preparation of porous carbon nanotube/carbon composite spheres and their adsorption properties. Carbon 137:493–501CrossRefGoogle Scholar
  3. Cheng W, Jiang Y, Xu X et al (2016) Easily recoverable titanosilicate zeolite beads with hierarchical porosity: Preparation and application as oxidation catalysts. J Catal 333:139–148CrossRefGoogle Scholar
  4. Correia A, Shahbazi MA, Mäkilä E et al (2015) Cyclodextrin-modified porous silicon nanoparticles for efficient sustained drug delivery and proliferation inhibition of breast cancer cells. ACS Appl Mater Interfaces 7(41):23197–23204CrossRefGoogle Scholar
  5. Dai H, Huang Y, Huang H (2018) Eco-friendly polyvinyl alcohol/carboxymethyl cellulose hydrogels reinforced with graphene oxide and bentonite for enhanced adsorption of methylene blue. Carbohydr Polym 185:1–11CrossRefGoogle Scholar
  6. Ding D, Zhang Z, Chen R, Cai T (2017) Selective removal of cesium by ammonium molybdophosphate–polyacrylonitrile bead and membrane. J Hazard Mater 324:753–761CrossRefGoogle Scholar
  7. Du K, Li S, Zhao L et al (2018) One-step growth of porous cellulose beads directly on bamboo fibers via oxidation-derived method in aqueous phase and their potential for heavy metal ions adsorption. ACS Sustain Chem Eng 6(12):17068–17075CrossRefGoogle Scholar
  8. Han P, Shi J, Nie T et al (2016) Conferring natural-derived porous microspheres with surface multifunctionality through facile coordination-enabled self-assembly process. ACS Appl Mater Interfaces 8(12):8076–8085CrossRefGoogle Scholar
  9. Krüner B, Schreiber A, Tolosa A et al (2018) Nitrogen-containing novolac-derived carbon beads as electrode material for supercapacitors. Carbon 132:220–231CrossRefGoogle Scholar
  10. Lin F, You Y, Yang X et al (2017) Microwave-assisted facile synthesis of TEMPO-oxidized cellulose beads with high adsorption capacity for organic dyes. Cellulose 24(11):5025–5040CrossRefGoogle Scholar
  11. Lindh J, Ruan C, Strømme M, Mihranyan A (2016) Preparation of porous cellulose beads via introduction of diamine spacers. Langmuir 32(22):5600–5607CrossRefGoogle Scholar
  12. Liu L, Gao ZY, Su XP et al (2015) Adsorption removal of dyes from single and binary solutions using a cellulose-based bioadsorbent. ACS Sustain Chem Eng 3(3):432–442CrossRefGoogle Scholar
  13. Liu L, Liao Q, Xie J et al (2016) Synthetic control of three-dimensional porous cellulose-based bioadsorbents: correlation between structural feature and metal ion removal capability. Cellulose 23(6):3819–3835CrossRefGoogle Scholar
  14. Masruchin N, Park BD, Causin V, Um IC (2015) Characteristics of TEMPO-oxidized cellulose fibril-based hydrogels induced by cationic ions and their properties. Cellulose 22(3):1993–2010CrossRefGoogle Scholar
  15. Qu JB, Huan GS, Chen YL et al (2014) Coating gigaporous polystyrene microspheres with cross-linked poly(vinyl alcohol) hydrogel as a rapid protein chromatography matrix. ACS Appl Mater Interfaces 6(15):12752–12760CrossRefGoogle Scholar
  16. Vu HC, Dwivedi AD, Le TT et al (2017) Magnetite graphene oxide encapsulated in alginate beads for enhanced adsorption of Cr(VI) and As(V) from aqueous solutions: Role of crosslinking metal cations in pH control. Chem Eng J 307:220–229CrossRefGoogle Scholar
  17. Wang S, Wang L, Kong W et al (2013) Preparation, characterization of carboxylated bamboo fibers and their adsorption for lead(II) ions in aqueous solution. Cellulose 20(4):2091–2100CrossRefGoogle Scholar
  18. Wang D, Yu H, Fan X et al (2018) High aspect ratio carboxylated cellulose nanofibers cross-linked to robust aerogels for superabsorption–flocculants: paving way from nanoscale to macroscale. ACS Appl Mater Interfaces 10(24):20755–20766CrossRefGoogle Scholar
  19. Wang K, Ma H, Pu S et al (2019) Hybrid porous magnetic bentonite-chitosan beads for selective removal of radioactive cesium in water. J Hazard Mater 362:160–169CrossRefGoogle Scholar
  20. Wu Z, Kong L, Hu H et al (2015) Adsorption performance of hollow spherical sludge carbon prepared from sewage sludge and polystyrene foam wastes. ACS Sustain Chem Eng 3(3):552–558CrossRefGoogle Scholar
  21. Yu W, Yuan P, Liu D et al (2015) Facile preparation of hierarchically porous diatomite/MFI-type zeolite composites and their performance of benzene adsorption: the effects of NaOH etching pretreatment. J Hazard Mater 285:173–181CrossRefGoogle Scholar
  22. Zhang DY, Zhang N, Song P et al (2018) Functionalized cellulose beads with three dimensional porous structure for rapid adsorption of active constituents from pyrolaincarnata. Carbohydr Polym 181:560–569CrossRefGoogle Scholar
  23. Zhuang S, Cheng R, Kang M et al (2018) Kinetic and equilibrium of U(VI) adsorption onto magnetic amidoxime-functionalized chitosan beads. J Clean Prod 188:655–661CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  • Ranju Meng
    • 1
    • 2
  • Lin Liu
    • 1
  • Yuanyuan Jin
    • 1
  • Zhenze Luo
    • 1
  • Huiying Gao
    • 2
  • Juming Yao
    • 1
    Email author
  1. 1.The Key Laboratory of Advanced Textile Materials and Manufacturing Technology of Ministry of Education, College of Materials and TextilesZhejiang Sci-Tech UniversityHangzhouChina
  2. 2.Jiaxing Vocational Technical CollegeJiaxingChina

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