, Volume 26, Issue 6, pp 4005–4019 | Cite as

Enhanced heavy metal adsorption ability of lignocellulosic hydrogel adsorbents by the structural support effect of lignin

  • Xiaoping Shen
  • Yanjun XieEmail author
  • Qingwen WangEmail author
  • Xin Yi
  • Julia L. Shamshina
  • Robin D. Rogers
Original Research


Cellulose beads possess some adsorption capacities for heavy metal ions, but the effect of lignin remaining in the beads on the adsorption behavior is not clear yet. In this study, lignocellulosic and cellulosic hydrogel beads were prepared by ionic liquid (IL) dissolution and reconstitution in water and further functionalization through magnetization and carboxymethylation. Compared to pure cellulosic beads made from Kraft pulp and microcrystalline cellulose, the presence of lignin in the lignocellulosic beads from IL-extracted cellulose-rich material (CRM) helped support the porous structure, leading to a higher hydroxyl number and porosity, and thus higher efficacy in magnetization and carboxymethylation. CRM beads, therefore, exhibited greater Cu2+ and Pb2+ uptake than the cellulosic beads both before and after modification. However, excessive lignin in the beads prepared directly from poplar wood powder caused negative effects on the adsorption capacity due to agglomeration and occlusion of the adsorptive sites.

Graphical abstract


Lignocellulosic hydrogel beads Structural support Hydroxyl number Heavy metal adsorption 



Yanjun Xie thanks the financial support from the National Key Research and Development Program of China (2017YFD0600204).

Supplementary material

10570_2019_2328_MOESM1_ESM.pdf (794 kb)
Supplementary material 1 (PDF 794 kb)


  1. Banerjee SS, Chen DH (2007) Fast removal of copper ions by gum arabic modified magnetic nano-adsorbent. J Hazard Mater 147:792–799CrossRefGoogle Scholar
  2. Barnett JR, Bonham VA (2004) Cellulose microfibril angle in the cell wall of wood fibres. Biol Rev 79:461–472CrossRefGoogle Scholar
  3. Chatterjee S, Lee MW, Woo SH (2010) Adsorption of congo red by chitosan hydrogel beads impregnated with carbon nanotubes. Bioresour Technol 101:1800–1806CrossRefGoogle Scholar
  4. Chen SY, Zou Y, Yan ZY, Shen W, Shi SK, Zhang X, Wang HP (2009) Carboxymethylated-bacterial cellulose for copper and lead ion removal. J Hazard Mater 161:1355–1359CrossRefGoogle Scholar
  5. Chen P, Yu HP, Liu YX, Chen WS, Wang XQ, Ouyang M (2013) Concentration effects on the isolation and dynamic rheological behavior of cellulose nanofibers via ultrasonic processing. Cellulose 20:149–157CrossRefGoogle Scholar
  6. Cheng FC, Wang H, Rogerst RD (2014) Oxygen enhances polyoxometalate-based catalytic dissolution and delignification of woody biomass in ionic liquids. ACS Sustain Chem Eng 2:2859–2865CrossRefGoogle Scholar
  7. Donia AM, Atia AA, Abouzayed FI (2012) Preparation and characterization of nano-magnetic cellulose with fast kinetic properties towards the adsorption of some metal ions. Chem Eng J 191:22–30CrossRefGoogle Scholar
  8. Driemeier C, Oliveira MM, Curvelo AAS (2016) Lignin contributions to the nanoscale porosity of raw and treated lignocelluloses as observed by calorimetric thermoporometry. Ind Crops Prod 82:114–117CrossRefGoogle Scholar
  9. Duchesne I, Hult E, Molin U, Daniel G, Iversen T, Lennholm H (2001) The influence of hemicellulose on fibril aggregation of kraft pulp fibres as revealed by FE-SEM and CP/MAS 13C-NMR. Cellulose 8:103–111CrossRefGoogle Scholar
  10. Ferrer A, Quintana E, Filpponen I, Solala I, Vidal T, Rodriguez A, Rojas OJ (2012) Effect of residual lignin and heteropolysaccharides in nanofibrillar cellulose and nanopaper from wood fibers. Cellulose 19:2179–2193CrossRefGoogle Scholar
  11. Gan WT, Gao LK, Zhan XX, Li J (2016) Preparation of thiol-functionalized magnetic sawdust composites as an adsorbent to remove heavy metal ions. RSC Adv 6:37600–37609CrossRefGoogle Scholar
  12. Horst MF, Lassalle V, Ferreira ML (2015) Nanosized magnetite in low cost materials for remediation of water polluted with toxic metals, azo- and antraquinonic dyes. Front Environ Sci Eng 9:746–769CrossRefGoogle Scholar
  13. Jeon C, Kim JH (2009) Removal of lead ions using phosphorylated sawdust. J Ind Eng Chem 15:910–913CrossRefGoogle Scholar
  14. Kikuchi Y, Qian QR, Machida M, Tatsumoto H (2006) Effect of ZnO loading to activated carbon on Pb(II) adsorption from aqueous solution. Carbon 44:195–202CrossRefGoogle Scholar
  15. Kim CH, Youn HJ, Lee HL (2017) Preparation of surface-charged CNF aerogels and investigation of their ion adsorption properties. Cellulose 24:2895–2902CrossRefGoogle Scholar
  16. Labbe N, Rials TG, Kelley SS, Cheng ZM, Kim JY, Li Y (2005) FT-IR imaging and pyrolysis-molecular beam mass spectrometry: new tools to investigate wood tissues. Wood Sci Technol 39:61-U19CrossRefGoogle Scholar
  17. Li WY, Sun N, Stoner B, Jiang XY, Lu XM, Rogers RD (2011a) Rapid dissolution of lignocellulosic biomass in ionic liquids using temperatures above the glass transition of lignin. Green Chem 13:2038–2047CrossRefGoogle Scholar
  18. Li LJ, Liu FQ, Jing XS, Ling PP, Li AM (2011b) Displacement mechanism of binary competitive adsorption for aqueous divalent metal ions onto a novel IDA-chelating resin: isotherm and kinetic modeling. Water Res 45:1177–1188CrossRefGoogle Scholar
  19. Liu WJ, Jiang H, Yu HQ (2015) Thermochemical conversion of lignin to functional materials: a review and future directions. Green Chem 17:4888–4907CrossRefGoogle Scholar
  20. Liu S, Yao K, Fu LH, Ma MG (2016) Selective synthesis of Fe3O4, γ-Fe2O3, and α-Fe2O3 using cellulose-based composites as precursors. RSC Adv 6:2135–2140CrossRefGoogle Scholar
  21. Luo XG, Liu SL, Zhou JP, Zhang LN (2009) In situ synthesis of Fe3O4/cellulose microspheres with magnetic-induced protein delivery. J Mater Chem 19:3538–3545CrossRefGoogle Scholar
  22. Mahdavi S, Jalali M, Afkhami A (2012) Removal of heavy metals from aqueous solutions using Fe3O4, ZnO, and CuO nanoparticles. J Nanopart Res 14:171–188CrossRefGoogle Scholar
  23. Nata IF, Sureshkumar M, Lee CK (2011) One-pot preparation of amine-rich magnetite/bacterial cellulose nanocomposite and its application for arsenate removal. RSC Adv 1:625–631CrossRefGoogle Scholar
  24. Ngah WSW, Fatinathan S (2008) Adsorption of Cu(II) ions in aqueous solution using chitosan beads, chitosan-GLA beads and chitosan-alginate beads. Chem Eng J 143:62–72CrossRefGoogle Scholar
  25. Ngah WSW, Fatinathan S (2010) Adsorption characterization of Pb(II) and Cu(II) ions onto chitosan-tripolyphosphate beads: kinetic, equilibrium and thermodynamic studies. J Environ Manag 91:958–969CrossRefGoogle Scholar
  26. Pokhrel D, Viraraghavan T (2004) Treatment of pulp and paper mill wastewater—a review. Sci Total Environ 333:37–58CrossRefGoogle Scholar
  27. Qi HS, Liebert T, Meister F, Heinze T (2009) Homogenous carboxymethylation of cellulose in the NaOH/urea aqueous solution. React Funct Polym 69:779–784CrossRefGoogle Scholar
  28. Qiu W, Zheng Y (2009) Removal of lead, copper, nickel, cobalt, and zinc from water by a cancrinite-type zeolite synthesized from fly ash. Chem Eng J 145:483–488CrossRefGoogle Scholar
  29. Ren H, Gao Z, Daoji W, Jiang J, Sun Y, Luo C (2016) Efficient Pb(II) removal using sodium alginate–carboxymethyl cellulose gel beads: preparation, characterization, and adsorption mechanism. Carbohydr Polym 137:402–409CrossRefGoogle Scholar
  30. Sciban M, Klasnja M, Skrbic B (2006) Modified softwood sawdust as adsorbent of heavy metal ions from water. J Hazard Mater 136:266–271CrossRefGoogle Scholar
  31. Sehaqui H, de Larraya UP, Liu P, Pfenninger N, Mathew AP, Zimmermann T, Tingaut P (2014) Enhancing adsorption of heavy metal ions onto biobased nanofibers from waste pulp residues for application in wastewater treatment. Cellulose 21:2831–2844CrossRefGoogle Scholar
  32. Shen X, Shamshina JL, Berton P, Gurau G, Rogers RD (2016a) Hydrogels based on cellulose and chitin: fabrication, properties, and applications. Green Chem 18:53–75CrossRefGoogle Scholar
  33. Shen X, Shamshina JL, Berton P, Bandomir J, Wang H, Gurau G, Rogers RD (2016b) Comparison of hydrogels prepared with ionic liquid-isolated vs. commercial chitin and cellulose. ACS Sustain Chem Eng 4:471–480CrossRefGoogle Scholar
  34. Song G, Zhu X, Chen R, Liao Q, Ding YD, Chen L (2016) An investigation of CO2 adsorption kinetics on porous magnesium oxide. Chem Eng J 283:175–183CrossRefGoogle Scholar
  35. Sun N, Rahman M, Qin Y, Maxim ML, Rodriguez H, Rogers RD (2009) Complete dissolution and partial delignification of wood in the ionic liquid 1-ethyl-3-methylimidazolium acetate. Green Chem 11:646–655CrossRefGoogle Scholar
  36. Sun N, Jiang XY, Maxim ML, Metlen A, Rogers RD (2011) Use of polyoxometalate catalysts in ionic liquids to enhance the dissolution and delignification of woody biomass. Chemsuschem 4:65–73CrossRefGoogle Scholar
  37. Tang YL, Liang S, Yu SL, Gao NY, Zhang J, Guo HC, Wang YL (2012) Enhanced adsorption of humic acid on amine functionalized magnetic mesoporous composite microspheres. Colloids Surf A 406:61–67CrossRefGoogle Scholar
  38. Tang H, Zhou WJ, Lu A, Zhang LN (2014) Characterization of new sorbent constructed from Fe3O4/chitin magnetic beads for the dynamic adsorption of Cd2+ ions. J Mater Sci 49:123–133CrossRefGoogle Scholar
  39. Thakur S, Govender PP, Mamo MA, Tamulevicius S, Mishra YK, Thakur VK (2017) Progress in lignin hydrogels and nanocomposites for water purification: future perspectives. Vacuum 146:342–355CrossRefGoogle Scholar
  40. Thakur S, Sharma B, Verma A, Chaudhary J, Tamulevicius S, Thakur VK (2018) Recent progress in sodium alginate based sustainable hydrogels for environmental applications. J Clean Prod 198:143–159CrossRefGoogle Scholar
  41. Thakura VK, Thakur MK (2015) Recent advances in green hydrogels from lignin: a review. Int J Biol Macromol 72:834–847CrossRefGoogle Scholar
  42. Togashi T, Naka T, Asahina S, Sato K, Takami S, Adschiri T (2011) Surfactant-assisted one-pot synthesis of superparamagnetic magnetite nanoparticle clusters with tunable cluster size and magnetic field sensitivity. Dalton Trans 40:1073–1078CrossRefGoogle Scholar
  43. Upadhyay RK, Soin N, Roy SS (2014) Role of graphene/metal oxide composites as photocatalysts, adsorbents and disinfectants in water treatment: a review. RSC Adv 4:3823–3851CrossRefGoogle Scholar
  44. Volesky B (2003) Sorption and biosorption. Equilibrium biosorption performance. BV Sorbex, St. Lambert, Québec, pp 103–116Google Scholar
  45. Wang H, Gurau G, Rogers RD (2012) Ionic liquid processing of cellulose. Chem Soc Rev 41:1519–1537CrossRefGoogle Scholar
  46. Wu ZM, Cheng ZH, Ma W (2012) Adsorption of Pb(II) from glucose solution on thiol-functionalized cellulosic biomass. Bioresour Technol 104:807–809CrossRefGoogle Scholar
  47. Yu XL, Tong SR, Ge MF, Wu LY, Zuo JC, Cao CY, Song WG (2013) Adsorption of heavy metal ions from aqueous solution by carboxylated cellulose nanocrystals. J Environ Sci 25:933–943CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Key Laboratory of Bio-based Material Science and Technology (Ministry of Education), College of Material Science and EngineeringNortheast Forestry UniversityHarbinChina
  2. 2.School of EngineeringZhejiang A & F UniversityLin’anChina
  3. 3.College of Materials and EnergySouth China Agricultural UniversityGuangzhouChina
  4. 4.Mari Signum Mid-Atlantic, LLCRockvilleUSA
  5. 5.525 Solutions, Inc.TuscaloosaUSA

Personalised recommendations