pp 1–11 | Cite as

A versatile TOCN/CGG self-assembling hydrogel for integrated wastewater treatment

  • Lei DaiEmail author
  • Ting Cheng
  • Xiangju Xi
  • Shuangxi Nie
  • Huizhen KeEmail author
  • Yishan Liu
  • Shuhua Tong
  • Zhirong ChenEmail author
Original Research


Water pollution caused by industrial discharges is a severe threat to our society. Thus, efficient and sustainable materials that can provide potential effective solutions are in high demand. The present work reports the development of a versatile strategy based on TEMPO-oxidized cellulose nanofibers (TOCN)/cationic guar gum (CGG) self-assembling hydrogels to remedy wastewater containing oil, heavy metal ions or organic dyes. The TOCN/CGG hydrogel-coated filter papers, prepared via a layer-by-layer deposition process, show a high oil/water separation efficiency (around 99%), with the coating amount of being as low as 0.032 g m−2 (dry mass). Through gravitational force only, the water flux can be as high as 443 L m−2 h−1. The as-prepared oil/water separation materials exhibited good recyclability. The monolithic TOCN/CGG hydrogel can also efficiently remove copper ions (Cu2+) and dyes (i.e. thioflavin T and methyl orange), based on an adsorption mechanism. The adsorption amount of Cu2+ can be as high as 498.5 mg g−1, while that of thioflavin T and methyl orange can be 430.2 mg g−1 and 134.3 mg g−1, respectively. The mass transfer driving force and the number of active binding sites are the two main factors affecting the adsorption process. This all-polysaccharide hydrogel system may be a promising potential for wastewater remedy, due to its facile/“green” preparation process and high performance, as well as the abundance and environmental-friendliness of its raw materials.

Graphic abstract


TOCN CGG Self-assembling Hydrogel Wastewater 



The authors greatly appreciate Dr. Xuejun Zou and Dr. Joseph Aspler from FPInnovations (Canada) polishing up the English of our manuscript. We also acknowledge the financial support from the Opening Project of Guangxi Key Laboratory of Clean Pulp and Papermaking and Pollution Control (No. KF201819-3), Open Project Program of Fujian Key Laboratory of Novel Functional Textile Fibers and Materials (Minjiang University, No. FKLTFM1814), High-level Foreign Experts Project (GDT20186100425) and Key Scientific Research Group of Shaanxi Province (2017KCT-02).

Supplementary material

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Supplementary material 1 (DOCX 1460 kb)
10570_2019_2834_MOESM2_ESM.mp4 (1 mb)
Supplementary material 2 (MP4 1030 kb)


  1. Abbas M, Adil M, Ehtisham-ul-Haque S, Munir B, Yameen M, Ghaffar A, Iqbal M (2018) Vibrio fischeri bioluminescence inhibition assay for ecotoxicity assessment: a review. Sci Total Environ 626:1295–1309. CrossRefPubMedGoogle Scholar
  2. Alkherraz AM, Ali AK, Elsherif KM (2012) Equilibrium and thermodynamic studies of Pb(II), Zn(II), Cu(II) and Cd(II) adsorption onto mesembryanthemum activated carbon. J Med Chem Sci 3(1):1–94. CrossRefGoogle Scholar
  3. Bhatti HN, Jabeen A, Iqbal M, Noreen S, Naseem Z (2017) Adsorptive behavior of rice bran-based composites for malachite green dye: isotherm, kinetic and thermodynamic studies. J Mol Liq 237:322–333. CrossRefGoogle Scholar
  4. Chen J, Chen F, Meng Y, Wang S, Long Z (2019) Oxidized microcrystalline cellulose improve thermoplastic starch-based composite films: thermal, mechanical and water-solubility properties. Polymer 168:228–235. CrossRefGoogle Scholar
  5. Cheng Q, Ye D, Chang C, Zhang L (2017) Facile fabrication of superhydrophilic membranes consisted of fibrous tunicate cellulose nanocrystals for highly efficient oil/water separation. J Membr Sci 525:1–8. CrossRefGoogle Scholar
  6. Cong H-P, Qiu J-H, Yu S-H (2015) Thermoresponsive poly(N-isopropylacrylamide)/graphene/Au nanocomposite hydrogel for water treatment by a laser-assisted approach. Small 11(9–10):1165–1170. CrossRefPubMedGoogle Scholar
  7. Dai L, Long Z, Chen J, An X, Cheng D, Khan A, Ni Y-H (2017a) Robust guar gum/cellulose nanofibrils multilayer films with good barrier properties. ACS Appl Mater Interfaces 9(6):5477–5485. CrossRefPubMedGoogle Scholar
  8. Dai L, Wang B, An X, Zhang L, Khan A, Ni Y-H (2017b) Oil/water interfaces of guar gum-based biopolymer hydrogels and application to their separation. Carbohydr Polym 169:9–15. CrossRefPubMedGoogle Scholar
  9. Dai L, Zhang L, Wang B, Yang B-I, Khan A, Ni Y-H (2017c) Multifunctional self-assembling hydrogel from guar gum. Chem Eng J 330:1044–1051. CrossRefGoogle Scholar
  10. Dai L, Cheng T, Duan C, Zhao W, Zhang W, Zou X-J, Aspler Ni Y-H (2019a) 3D printing using plant-derived cellulose and its derivatives: a review. Carbohydr Polym 203:71–86. CrossRefPubMedGoogle Scholar
  11. Dai L, Cheng T, Wang Y, Lu H, Nie S, He H, Duan C, Ni Y-H (2019b) Injectable all-polysaccharide self-assembling hydrogel: a promising scaffold for localized therapeutic proteins. Cellulose 26(11):6891–6901. CrossRefGoogle Scholar
  12. Dai L, Cheng T, Wang Y, Wang B, Duan C, Ke H, Ni Y-H (2019c) A self-assembling guar gum hydrogel for efficient oil/water separation in harsh environments. Sep Purif Technol 225:129–135. CrossRefGoogle Scholar
  13. Du H, Liu W, Zhang M, Si C, Zhang X, Li B (2019) Cellulose nanocrystals and cellulose nanofibrils based hydrogels for biomedical applications. Carbohydr Polym 209:130–144. CrossRefPubMedGoogle Scholar
  14. Eskandari S, Guerin T, Toth I, Stephenson R-J (2017) Recent advances in self-assembled peptides: implications for targeted drug delivery and vaccine engineering. Adv Drug Deliv Rev 110–111:169–187. CrossRefPubMedGoogle Scholar
  15. Gao H, Sun Y, Zhou J, Xu R, Duan H (2013) Mussel-inspired synthesis of polydopamine-functionalized graphene hydrogel as reusable adsorbents for water purification. ACS Appl Mater Interfaces 5(2):425–432. CrossRefPubMedGoogle Scholar
  16. Huang Q, Zou Y, Arno M-C, Chen S, Wang T, Gao J, Dove A-P, Du J (2017) Hydrogel scaffolds for differentiation of adipose-derived stem cells. Chem Soc Rev 46(20):6255–6275. CrossRefPubMedGoogle Scholar
  17. Ilgin P, Ozay H, Ozay O (2019) Selective adsorption of cationic dyes from colored noxious effluent using a novel N-tert-butylmaleamic acid based hydrogels. React Funct Polym 142:189–198. CrossRefGoogle Scholar
  18. Iqbal M (2016) Vicia faba bioassay for environmental toxicity monitoring: a review. Chemosphere 144:785–802. CrossRefPubMedGoogle Scholar
  19. Iqbal M, Abbas M, Nisar J, Nazir A, Qamar A (2019a) Bioassays based on higher plants as excellent dosimeters for ecotoxicity monitoring: a review. Chem Int 5(1):1–80Google Scholar
  20. Iqbal M, Iqbal DN, Hussain EA, Soomro GA, Rizvi H, Nazir A (2019b) Microwave-assisted green synthesis of guar gum esters with enhanced physicochemical properties. Sci Iran 26(3):1474–1484. CrossRefGoogle Scholar
  21. Isobe N, Chen X, Kim U-J, Kimura S, Wada M, Saito T, Isogai A (2013) TEMPO-oxidized cellulose hydrogel as a high-capacity and reusable heavy metal ion adsorbent. J Hazard Mater 260:195–201. CrossRefPubMedGoogle Scholar
  22. Jiang C, Wang X, Wang G, Hao C, Li X, Li T (2019) Adsorption performance of a polysaccharide composite hydrogel based on crosslinked glucan/chitosan for heavy metal ions. Compos B 169:45–54. CrossRefGoogle Scholar
  23. Jonker AM, Löwik DWPM, van Hest JCM (2012) Peptide- and protein-based hydrogels. Chem Mater 24(5):759–773. CrossRefGoogle Scholar
  24. Kang L, Li J, Zeng J, Gao W, Xu J, Cheng Z, Chen K, Wang B (2019) A water solvent-assisted condensation polymerization strategy of superhydrophobic lignocellulosic fibers for efficient oil/water separation. J Mater Chem A 7(27):16447–16457. CrossRefGoogle Scholar
  25. Kausar A, Iqbal M, Javed A, Aftab K, Bhatti HN, Nouren S (2018) Dyes adsorption using clay and modified clay: a review. J Mol Liq 256:395–407. CrossRefGoogle Scholar
  26. Legrouri K, Khouya E, Hannache H, El Hartti M, Ezzine M, Naslain R (2017) Activated carbon from molasses efficiency for Cr(VI), Pb(II) and Cu(II) adsorption: a mechanistic study. Chem Int 3:301–310Google Scholar
  27. Li J, Kang L, Wang B, Chen K, Tian X, Ge Z, Gao W (2018) Controlled release and long-term antibacterial activity of dialdehyde nanofibrillated cellulose/silver nanoparticle composites. ACS Sustain Chem Eng 7(1):1146–1158. CrossRefGoogle Scholar
  28. Li M, Li B, Zhou L, Zhang Y, Cao Q, Wang R, Xiao H (2019a) Fluorescence-sensitive adsorbent based on cellulose using for mercury detection and removal from aqueous solution with selective “on-off” response. Int J Biol Macromol 132:1185–1192. CrossRefPubMedGoogle Scholar
  29. Li Y, Xiao H, Pan Y, Zhang M, Jin Y (2019b) Thermal and pH dual-responsive cellulose microfilament spheres for dye removal in single and binary systems. J Hazard Mater 377:88–97. CrossRefPubMedGoogle Scholar
  30. Liu J, Su D, Yao J, Huang Y, Shao Z, Chen X (2017) Soy protein-based polyethylenimine hydrogel and its high selectivity for copper ion removal in wastewater treatment. J Mater Chem A 5(8):4163–4171. CrossRefGoogle Scholar
  31. Liu K, Pan X, Chen L, Huang L, Ni Y, Liu J, Cao S, Wang H (2018) Ultrasoft self-healing nanoparticle-hydrogel composites with conductive and magnetic properties. ACS Sustain Chem. Eng 6(5):6395–6403. CrossRefGoogle Scholar
  32. Mushtaq M, Bhatti HN, Iqbal M, Noreen S (2016) Eriobotrya japonica seed biocomposite efficiency for copper adsorption: isotherms, kinetics, thermodynamic and desorption studies. J Environ Manag 176:21–33. CrossRefGoogle Scholar
  33. Pan X, Wang Q, He P, Liu K, Ni Y, Ouyang X, Chen L, Huang L, Wang H, Tan Y (2019) Mussel-inspired nanocomposite hydrogel-based electrodes with reusable and injectable properties for human electrophysiological signals detection. ACS Sustain Chem Eng 7(8):7918–7925. CrossRefGoogle Scholar
  34. Pang Z, Wang P, Dong C (2018) Ultrasonic pretreatment of cellulose in ionic liquid for efficient preparation of cellulose nanocrystals. Cellulose 25(12):7053–7064. CrossRefGoogle Scholar
  35. Peng X-W, Zhong L-X, Ren J-L, Sun R-C (2012) Highly effective adsorption of heavy metal ions from aqueous solutions by macroporous xylan-rich hemicelluloses-based hydrogel. J Agric Food Chem 60(15):3909–3916. CrossRefPubMedGoogle Scholar
  36. Rizzi V, Fiorini F, Lamanna G, Gubitosa J, Prasetyanto E-A, Fini P, Fanelli F, Nacci A, De Cola L, Cosma P (2018) Polyamidoamine-based hydrogel for removal of blue and red dyes from wastewater. Adv Sustain Syst 2(6):1700146. CrossRefGoogle Scholar
  37. Rohrbach K, Li Y, Zhu H, Liu Z, Dai J, Andreasen J, Hu L (2014) A cellulose based hydrophilic, oleophobic hydrated filter for water/oil separation. Chem Commun 50(87):13296–13299. CrossRefGoogle Scholar
  38. Sharma G, Kumar A, Naushad M, García-Peñas A, Al-Muhtaseb AAH, Ghfar AA, Sharma V, Ahamad T, Stadler FJ (2018) Fabrication and characterization of gum arabic-cl-poly(acrylamide) nanohydrogel for effective adsorption of crystal violet dye. Carbohydr Polym 202:444–453. CrossRefPubMedGoogle Scholar
  39. Shen C, Shen Y, Wen Y, Wang H, Liu W (2011) Fast and highly efficient removal of dyes under alkaline conditions using magnetic chitosan-Fe(III) hydrogel. Water Res 45(16):5200–5210. CrossRefPubMedGoogle Scholar
  40. Tahir N, Bhatti HN, Iqbal M, Noreen S (2017) Biopolymers composites with peanut hull waste biomass and application for crystal violet adsorption. Int J Biol Macromol 94:210–220. CrossRefPubMedGoogle Scholar
  41. Thakur S, Govender PP, Mamo MA, Tamulevicius S, Mishra YK, Thakur VK (2017a) Progress in lignin hydrogels and nanocomposites for water purification: future perspectives. Vac. 146:342–355. CrossRefGoogle Scholar
  42. Thakur S, Govender PP, Mamo MA, Tamulevicius S, Thakur VK (2017b) Recent progress in gelatin hydrogel nanocomposites for water purification and beyond. Vac. 146:396–408. CrossRefGoogle Scholar
  43. Thakur S, Sharma B, Verma A, Chaudhary J, Tamulevicius S, Thakur VK (2018a) Recent approaches in guar gum hydrogel synthesis for water purification. Int J Polym Anal Charact 23(7):621–632. CrossRefGoogle Scholar
  44. Thakur S, Sharma B, Verma A, Chaudhary J, Tamulevicius S, Thakur VK (2018b) Recent progress in sodium alginate based sustainable hydrogels for environmental applications. J Clean Prod 198:143–159. CrossRefGoogle Scholar
  45. Thakur S, Chaudhary J, Kumar V, Thakur VK (2019) Progress in pectin based hydrogels for water purification: trends and challenges. J Environ Manag 238:210–223. CrossRefGoogle Scholar
  46. Tu H, Yu Y, Chen J, Shi X, Zhou J, Deng H, Du Y (2017) Highly cost-effective and high-strength hydrogels as dye adsorbents from natural polymers: chitosan and cellulose. Polym Chem 8(19):2913–2921. CrossRefGoogle Scholar
  47. Wang B, Liang W, Guo Z, Liu W (2015) Biomimetic super-lyophobic and super-lyophilic materials applied for oil/water separation: a new strategy beyond nature. Chem Soc Rev 44(1):336–361. CrossRefPubMedGoogle Scholar
  48. Xue Z, Wang S, Lin L, Chen L, Liu M, Feng L, Jiang L (2011) A novel superhydrophilic and underwater superoleophobic hydrogel-coated mesh for oil/water separation. Adv Mater 23(37):4270–4273. CrossRefPubMedGoogle Scholar
  49. Yang X, Bakaic E, Hoare T, Cranston E-D (2013) Injectable polysaccharide hydrogels reinforced with cellulose nanocrystals: morphology, rheology, degradation, and cytotoxicity. Biomacromolecules 14(12):4447–4455. CrossRefPubMedGoogle Scholar
  50. Yuan T, Meng J, Hao T, Wang Z, Zhang Y (2015) A scalable method toward superhydrophilic and underwater superoleophobic PVDF membranes for effective oil/water emulsion separation. ACS Appl Mater Interfaces 7(27):14896–14904. CrossRefPubMedGoogle Scholar
  51. Yuk H, Lin S, Ma C, Takaffoli M, Fang N-X, Zhao X (2017) Hydraulic hydrogel actuators and robots optically and sonically camouflaged in water. Nat Commun 8:14230. CrossRefPubMedPubMedCentralGoogle Scholar
  52. Zhan H, Peng N, Lei X, Huang Y, Li D, Tao R, Chang C (2018a) UV-induced self-cleanable TiO2/nanocellulose membrane for selective separation of oil/water emulsion. Carbohydr Polym 201:464–470. CrossRefPubMedGoogle Scholar
  53. Zhan H, Zuo T, Tao R, Chang C (2018b) Robust tunicate cellulose nanocrystal/palygorskite nanorod membranes for multifunctional oil/water emulsion separation. ACS Sustain Chem Eng 6(8):10833–10840. CrossRefGoogle Scholar
  54. Zhao Y, Chen Y, Zhao J, Tong Z, Jin S (2017a) Preparation of SA-g-(PAA-co-PDMC) polyampholytic superabsorbent polymer and its application to the anionic dye adsorption removal from effluents. Sep Purif Technol 188:329–340. CrossRefGoogle Scholar
  55. Zhao Z, Chen H, Zhang H, Ma L, Wang Z (2017b) Polyacrylamide-phytic acid-polydopamine conducting porous hydrogel for rapid detection and removal of copper(II) ions. Biosens Bioelectron 91:306–312. CrossRefPubMedGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.College of Bioresources Chemical and Materials Engineering, Shaanxi Provincial Key Laboratory of Papermaking Technology and Specialty Paper Development, Key Laboratory of Paper Based Functional Materials of China National Light Industry, National Demonstration Center for Experimental Light Chemistry Engineering EducationShaanxi University of Science and TechnologyXi’anChina
  2. 2.Guangxi Key Laboratory of Clean Pulp and Papermaking and Pollution Control, College of Light Industry and Food EngineeringGuangxi UniversityNanningChina
  3. 3.College of Chemical and Biological EngineeringZhejiang UniversityHangzhouChina
  4. 4.Fujian Key Laboratory of Novel Functional Textile Fibers and MaterialsMinjiang UniversityFuzhouChina
  5. 5.Zhejiang Jinchang Specialty Paper Co., Ltd.QuzhouChina
  6. 6.Sichuan Technology and Business CollegeDujiangyanChina

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