pp 1–17 | Cite as

Facile synthesis of triazole and carboxyl-functionalized cellulose-based adsorbent via click chemistry strategy for efficient Gd(III) removal

  • Weiyan YinEmail author
  • Liangyi Liu
  • Sai Tang
  • Haoyue Zhang
  • Xizhi Pan
  • Ruan ChiEmail author
Original Research


Gd(III) containing wastewater has toxic effects on both public health and aquatic life. However, few literature is available using wastes biomass containing cellulose with enough high adsorption capacity to remove Gd(III). Herein, we described a facile synthesis of triazole and carboxyl- functionalized magnetic cellulose-based material from ramie stalk (TCM-RS) through click chemistry strategy for the first time. The synthesized sample (TCM-RS) was used as an efficient adsorbent for the removal of Gd(III) from aqueous solution. The obtained materials were well characterized. Batch adsorption experiments showed that the combination of bifunctional chelating ligand, sufficient specific surface area, and magnetic response endowed the adsorbent with excellent adsorption selectivity, high adsorption capacity and easy separation of adsorbent from solutions, respectively. The maximum Gd(III) uptake of TCM-RS (62.8 mg/g) was reached within 40 min. Adsorption isotherms and kinetics revealed that the Langmuir model and the pseudo-second-order kinetics model could well describe the adsorption process of Gd(III) onto TCM-RS. Moreover, the sorbent can be regenerated and reused for five cycles without significant loss in adsorption capacity. Our study not only provides new insights into the fabrication of TCM-RS through click chemistry strategy, but also reveal that TCM-RS has great potential application for the removal of Gd(III) from wastewater.

Graphic abstract


Ramie stalk Magnetic Gd(III) ions Click chemistry Cellulose-based adsorbent Adsorption 



The work was supported by the Key program of the National Natural Science Foundation of China (No. 51734001), National Natural Science Foundation-Yunnan joint fund Project of China (No. U1802552) and Initial Scientific Research Fund of Young Teachers in Wuhan Textile University (No. 175004).


  1. Altintas O, Hizal G, Tunca U (2006) ABC-type hetero-arm star terpolymers through “Click” chemistry. Polym Chem 44:5699–5707. CrossRefGoogle Scholar
  2. Anirudhan TS, Nima J, Divya PL (2013) Adsorption of chromium(VI) from aqueous solutions by glycidylmethacrylate-grafted-densified cellulose with quaternary ammonium groups. Appl Surf Sci 279:441–449. CrossRefGoogle Scholar
  3. Babu CM, Binnemans K, Roosen J (2018) Ethylenediaminetriacetic acid-functionalized activated carbon for the adsorption of rare earths from aqueous solutions. Ind Eng Chem Res 57:1487–1497. CrossRefGoogle Scholar
  4. Bai L, Hu H, Zhang W, Fu J, Lu Z, Liu M, Jiang H, Zhang L, Chen Q, Tan P (2012) Amine/acid catalyzed synthesis of a new silica-aminomethyl pyridine material as a selective adsorbent of copper. J Mater Chem 22:17293–17301. CrossRefGoogle Scholar
  5. Başarır SŞ, Bayramgil NP (2013) The uranium recovery from aqueous solutions using amidoxime modified cellulose derivatives. III. Modification of hydroxypropylmethylcellulose with amidoxime groups. Cellulose 20:1511–1522. CrossRefGoogle Scholar
  6. Bourikas K, Vakros J, Kordulis C, Lycourghiotis A (2003) Potentiometric mass titrations: experimental and theoretical establishment of a new technique for determining the point of zero charge (PZC) of metal (Hydr)oxides. J Phys Chem B 107:9441–9451. CrossRefGoogle Scholar
  7. Chen W, Wang L, Zhuo M, Liu Y, Wang Y, Li Y (2014) Facile and highly efficient removal of trace Gd(III) by adsorption of colloidal graphene oxide suspensions sealed in dialysis bag. J Hazard Mater 279:546–553. CrossRefGoogle Scholar
  8. Chen J, Teng ZY, Wu JJ (2015) Recycling of waste FRP and corn straw in wood plastic composite. Polym Compos 38:2410–2415. Google Scholar
  9. Chi R, Tian J (2008) Weathered crust elution-deposited rare earth ores. Nova Science Publishers, New YorkGoogle Scholar
  10. Deng G, Liu L, Zhong XY, Lao C, Wang H, Wang B, Zhu C, Shah F, Peng D (2014) Comparative proteome analysis of the response of ramie under N, P and K deficiency. Planta 239:1175–1186. CrossRefGoogle Scholar
  11. Fallah Z, Isfahani HN, Tajbakhsh M, Tashakkorian H, Amouei A (2018) TiO2-grafted cellulose via click reaction: an efficient heavy metal ions bioadsorbent from aqueous solutions. Cellulose 25:639–660. CrossRefGoogle Scholar
  12. Fallah Z, Isfahani HN, Tajbakhsh M (2019) Cyclodextrin-triazole-titanium based nanocomposite: preparation, characterization and adsorption behavior investigation. Process Saf Environ Prot 124:251–265. CrossRefGoogle Scholar
  13. Freundlich HMF (1906) Über die adsorption in lösungen. Z Phys Chem Frankfurt 57A:385–470Google Scholar
  14. Gan W, Gao L, Zhan X, Li J (2016) Removal of Cu2 + ions from aqueous solution by amino-functionalized magnetic sawdust composites. Wood Sci Technol 51:207–225. CrossRefGoogle Scholar
  15. Gao Q, Xia JF, Shao YT, Chen C, Han B, Xia KS, Zhou CG (2017) Ultrafast and high-capacity adsorption of Gd(III) onto inorganic phosphorous acid modified mesoporous SBA-15. Chem Eng J 313:197–206. CrossRefGoogle Scholar
  16. Ge F, Ye H, Li MM, Zhao BX (2012) Efficient removal of cationic dyes from aqueous solution by polymer-modified magnetic nanoparticles. Chem Eng J 198–199:11–17. CrossRefGoogle Scholar
  17. Ge HY, Wang CC, Liu SS, Huang Z (2016) Synthesis of citric acid functionalized magnetic graphene oxide coated corn straw for methylene blue adsorption. Bioresour Technol 221:419–429. CrossRefGoogle Scholar
  18. Guo L, Xu Y, Zhuo M, Liu L, Xu Q, Wang L, Shi C, Ye B, Fan X, Chen W (2018) Highly efficient removal of Gd(III) using hybrid hydrosols of carbon nanotubes/graphene oxide in dialysis bags and synergistic enhancement effect. Chem Eng J 348:535–545. CrossRefGoogle Scholar
  19. Hamed MM, Rizk SE, Nayl AA (2016) Adsorption kinetics and modeling of gadolinium and cobalt ions sorption by an ion-exchange resin. Particul Sci Technol 34:716–724. CrossRefGoogle Scholar
  20. He S, Zhang F, Cheng S, Wang W (2016) Synthesis of sodium acrylate and acrylamide copolymer/GO hydrogels and their effective adsorption for Pb2+ and Cd2+. ACS Sustain Chem Eng 4:3948–3959. CrossRefGoogle Scholar
  21. Ho YS, McKay G (1999) Pseudo-second order model for sorption processes. Process Biochem 34:451–465. CrossRefGoogle Scholar
  22. Huang X, Yan X, Xia L, Wang P, Wang Q, Zhang X, Zhong B, Zhao H, Wen G (2016) A three-dimensional graphene/Fe3O4/carbon microtube of sandwich-type architecture with improved wave absorbing performance. Scr Mater 120:107–111. CrossRefGoogle Scholar
  23. Langmuir I (1918) The adsorption of gases on plane surfaces of glass, mica and platinum. J Am Chem Soc 143:1361–1403. CrossRefGoogle Scholar
  24. Li J, Hu J, Sheng G, Zhao G, Huang Q (2009) Effect of pH, ionic strength, foreign ions and temperature on the adsorption of Cu(II) from aqueous solution to GMZ bentonite. Colloid Surf A 349:195–201. CrossRefGoogle Scholar
  25. Li W, Xu Y, Zhou Y, Ma W, Wang S, Dai Y (2012) Silica nanoparticles functionalized via click chemistry and ATRP for enrichment of Pb(II) ion. Nanoscale Res Lett 7:1–7. CrossRefGoogle Scholar
  26. Li K, Gao Q, Yadavalli G, Shen X, Lei HW, Han B, Xia KS, Zhou CG (2015) Selective adsorption of Gd3 + on a magnetically retrievable imprinted chitosan/carbon nanotube composite with high capacity. ACS Appl Mater Interfaces 7:21047–21055. CrossRefGoogle Scholar
  27. Lin H, Han S, Dong Y, He Y (2017) The surface characteristics of hyperbranched polyamide modified corncob and Its adsorption property for Cr(VI). Appl Surf Sci 412:152–159. CrossRefGoogle Scholar
  28. Metwally SS, Rizk HE (2014) Preparation and characterization of nano-sized iron–titanium mixed oxide for removal of some lanthanides from aqueous solution. Sep Sci Technol 49:2426–2436. CrossRefGoogle Scholar
  29. Mohamed WR, Metwally SS, Ibrahim HA, El-Sherief EA, Mekhamer HS, Moustafa IMI, Mabrouk EM (2017) Impregnation of task-specific ionic liquid into a solid support for removal of neodymium and gadolinium ions from aqueous solution. J Mol Liq 236:9–17. CrossRefGoogle Scholar
  30. Moldoveanu GA, Papangelakis VG (2012) Recovery of rare earth elements adsorbed on clay minerals: I. Desorption mechanism. Hydrometallurgy 117:71–78. CrossRefGoogle Scholar
  31. Nguyen TAH, Ngo HH, Guo W, Zhang J, Liang S, Yue Q, Li Q, Nguyen TV (2013) Applicability of agricultural waste and by-products for adsorptive removal of heavy metals from wastewater. Bioresour Technol 148:574–585. CrossRefGoogle Scholar
  32. Pirbazari AE, Saberikhah E, Kozani SSH (2014) Fe3O4-wheat straw: preparation, characterization and its application for methylene blue adsorption. Water Resour Ind 7–8:23–37. CrossRefGoogle Scholar
  33. Qin X, Zhou J, Huang A, Guan J, Zhang Q, Huang Z, Hu H, Zhang Y, Yang M, Wu J, Qin Y, Feng Z (2016) A green technology for the synthesis of cellulose succinate for efficient adsorption of Cd(II) and Pb(II) ions. RSC Adv 6:26817–26825. CrossRefGoogle Scholar
  34. Rashad G, Mahmoud M, Sheha R (2018) Impregnated activated carbon for the adsorption of Gd(III) radionuclides from aqueous solutions. Sep Sci Technol 36:609–617. Google Scholar
  35. Segal L, Creely JJ, Martin AE, Conrad CM (1959) An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Textile Res J 29:786–794CrossRefGoogle Scholar
  36. Shi Y, Pan Y, Zhong J, Yang J, Zheng J, Cheng J, Song R, Yi C (2015) Facile synthesis of gadolinium (III) chelates functionalized carbon quantum dots for fluorescence and magnetic resonance dual-modal bioimaging. Carbon 93:742–750. CrossRefGoogle Scholar
  37. Song W, Gao B, Zhang T, Xu X, Huang X, Huang Y, Yue Q (2015) High-capacity adsorption of dissolved hexavalent chromium using amine-functionalized magnetic corn stalk composites. Bioresour Technol 190:550–557. CrossRefGoogle Scholar
  38. Song W, Gao B, Xu X, Xing L, Han S, Duan P, Song W, Jia R (2016) Adsorption-desorption behavior of magnetic amine/Fe3O4 functionalized biopolymer resin towards anionic dyes from wastewater. Bioresour Technol 210:123–130. CrossRefGoogle Scholar
  39. Sun X, Yang LR, Li Q, Zhao J, Li X, Wang X, Liu H (2014) Amino-functionalized magnetic cellulose nanocomposite as adsorbent for removal of Cr(VI): synthesis and adsorption studies. Chem Eng J 241:175–183. CrossRefGoogle Scholar
  40. Tian J, Yin J, Chen K, Rao G, Jiang M, Chi R (2011a) Extraction of rare earths from the leach liquor of the weathered crust elution-deposited rare earth ore with non-precipitation. Int J Miner Process 98:125–131. CrossRefGoogle Scholar
  41. Tian Y, Wu M, Lin B, Huang P, Huang Y (2011b) Synthesis of magnetic wheat straw for arsenic adsorption. J Hazard Mater 193:10–16. CrossRefGoogle Scholar
  42. Toutianoush A, Ehashani A, Schnepf J, Tieke B (2005) Multilayer membranes of p-sulfonato-calix[8]arene and polyvinylamine and their use for selective enrichment of rare earth metal ions. Appl Surf Sci 246:430–436. CrossRefGoogle Scholar
  43. Vijayaraghavan K, Sathishkumar M, Balasubramanian R (2010) Biosorption of lanthanum, cerium, europium, and ytterbium by a brown marine alga, Turbinaria Conoides. Ind Eng Chem 49:4405–4411. CrossRefGoogle Scholar
  44. Wang J, Wei J, Li J (2015) Rice straw modified by click reaction for selective extraction of noble metal ions. Bioresour Technol 177:182–187. CrossRefGoogle Scholar
  45. Wang Y, Wang X, Xie Y, Zhang K (2018) Functional nanomaterials through esterification of cellulose: a review of chemistry and application. Cellulose 25:3703–3731. CrossRefGoogle Scholar
  46. Wu Y, Fan Y, Zhang M, Ming Z, Yang S, Arkin A, Fang P (2016) Functionalized agricultural biomass as a low-cost adsorbent: utilization of rice straw incorporated with amine groups for the adsorption of Cr(VI) and Ni(II) from single and binary systems. Biochem Eng J 105:27–35. CrossRefGoogle Scholar
  47. Xu S, Gong XF, Zou HL, Liu CY, Chen CL, Zeng XX (2015a) Recycling agriculture wastes of ramie stalk as bioadsorbents for Cd2+ removal: a kinetic and thermodynamic study. Water Sci Technol 73:396–404. CrossRefGoogle Scholar
  48. Xu S, Gong XF, Zou HL, Liu CY, Chen CL, Zeng XX (2015b) Mechanism of the adsorption process: Cu2+ adsorpted by ramie stalk. J Chin Chem Soc 62:1072–1078. CrossRefGoogle Scholar
  49. Yu JX, Chi RA, Zhang YF, Xu ZG, Xiao CQ, Guo J (2012) A situ co-precipitation method to prepare magnetic PMDA modified sugarcane bagasse and its application for competitive adsorption of methylene blue and basic magenta. Bioresour Technol 110:160–166. CrossRefGoogle Scholar
  50. Yu C, Geng J, Zhuang Y, Zhao J, Chu L, Luo X, Zhao Y, Guo Y (2016) Preparation of the chitosan grafted poly (quaternary ammonium)/Fe3O4 nanoparticles and its adsorption performance for food yellow 3. Carbohydr Polym 152:327–336. CrossRefGoogle Scholar
  51. Yuan Q, Chi Y, Yu N, Zhao Y, Yan W, Li X, Dong B (2014) Amino-functionalized magnetic mesoporous microspheres with good adsorption properties. Mater Res Bull 49:279–284. CrossRefGoogle Scholar
  52. Zhan Y, Fu LJ, Li JX, Yang XG, Yang XD, Wang K (2009) Gadolinium promoted proliferation and enhanced survival in human cervical carcinoma cells. Biometals 22:511–5199. CrossRefGoogle Scholar
  53. Zhao T, Yao Y, Li D, Wu F, Zhang C, Bin Gao (2018) Facile low-temperature one-step synthesis of pomelo peel biochar under air atmosphere and its adsorption behaviors for Ag(I) and Pb(II). Sci Total Environ 640–641:73–79. CrossRefGoogle Scholar
  54. Zheng X, Wang C, Dai J, Shi W, Yan Y (2015) Design of mesoporous silica hybrid materials as sorbents for the selective recovery of rare earth metals. J Mater Chem A 3:10327–10335. CrossRefGoogle Scholar
  55. Zheng L, Peng D, Meng P (2018) Promotion effects of nitrogenous and oxygenic functional groups on cadmium(II) removal by carboxylated corn stalk. J Clean Prod 201:609–623. CrossRefGoogle Scholar
  56. Zhu HY, Fu YQ, Jiang R, Jiang JH, Xiao L, Zeng GM, Zhao SL, Wang Y (2011) Adsorption removal of congo red onto magnetic cellulose/Fe3O4/activated carbon composite: equilibrium, kinetic and thermodynamic studies. Chem Eng J 173:494–502. CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Hubei Key Laboratory of Biomass Fibers and Eco-dyeing and Finishing, School of Chemistry and Chemical EngineeringWuhan Textile UniversityWuhanChina
  2. 2.Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and PharmacyWuhan Institute of TechnologyWuhanChina

Personalised recommendations