Effect of preparation methods on La3+ adsorption properties of GO/P(NIPAM-MA) hydrogels

YANG Xinwei1,2 SHAN Guorong1,2 CAO Zhihai3 LYU Ting4 PAN Pengju1,2

(1.State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, Zhejiang, China 310027)
(2.Institute of Zhejiang University-Quzhou, Quzhou, Zhejiang, China 324000)
(3.Key Laboratory of Advanced Textile Materials and Manufacturing Technology, Ministry of Education, Zhejiang Sci-Tech University, Hangzhou, Zhejiang, China 310018)
(4.College of Materials and Environmental Engineering, Hangzhou Dianzi University, Hangzhou, Zhejiang, China 310018)

【Abstract】Graphene oxide/poly(N-isopropylacrylamide-maleic acid)[GO/P(NIPAM-MA)] hydrogel was prepared by freeze polymerization and non-freeze polymerization, and the preparation methods were compared in terms of the La3+ adsorption capacity of GO/P(NIPAM-MA) hydrogel. It is found that the hydrogel synthesized by the freeze polymerization method has an excellent swelling-shrinking and adsorption properties. With an equivalent molar ratio of 10:1 for NIPAM:MA and 370 mg/L of LaCl3 solution, the equilibrium adsorption capacity of the hydrogel synthesized by the freeze polymerization method is (29.87 ± 0.073) mg/g, while that of the hydrogel synthesized by the non-freeze polymerization method is only (20.29 ± 0.395) mg/g. The fitting parameter, n, of the Freundlich isotherm increases linearly with the increase in MA content for the hydrogel synthesized by the freeze polymerization method, and the increasing degree is larger than that of the hydrogel synthesized by the non-freeze polymerization method. After five repeated adsorption–desorption cycles, it is found that there is no significant deformation and the adsorption capacity is not obviously decreased for the hydrogel synthesized by the freeze polymerization method, while the hydrogel synthesized by the non-freeze polymerization method is broken after three repeated adsorption–desorption cycles. The GO/P(NIPAM-MA) hydrogel synthesized by the freeze polymerization method has the advantages of large equilibrium adsorption capacity for La3+ and reusability.

【Keywords】 adsorption; desorption; hydrogel; freeze polymerization; La3+;


Download this article


    [1] Rabl S, Haas A, Santi D, et al. Ring opening of cis-decalin on bifunctional Ir/- and Pt/La-X zeolite catalysts [J]. Applied Catalysis a General, 2011, 400 (1): 131–141.

    [2] Wang F C, Zhao J M, Pan F, et al. Adsorption properties toward trivalent rare earths by alginate beads doping with silica [J]. Industrial & Engineering Chemistry Research, 2013, 52 (9): 3453–3461.

    [3] Wilfong W C, Kai B W, Bank T L, et al. Recovering rare earth elements from aqueous solution with porous amine-epoxy networks [J]. ACS Applied Materials & Interfaces, 2017, 9 (21): 18283–18294.

    [4] Tan Q Y, Li J H, Zeng X L. Rare earth elements recovery from waste fluorescent lamps: a review [J]. Critical Reviews in Environmental Science & Technology, 2015, 45 (7): 749–776.

    [5] Brioschi L, Steinmann M, Lucot E, et al. Transfer of rare earth elements (REE) from natural soil to plant systems: implications for the environmental availability of anthropogenic REE [J]. Plant and Soil, 2013, 366 (1/2): 143–163.

    [6] Diniz V, Weber M E, Volesky B, et al. Column biosorption of lanthanum and europium by Sargassum [J]. Water Research, 2008,42 (1/2): 363–371.

    [7] Zhang S Z, Shan X Q. Speciation of rare earth elements in soil and accumulation by wheat with rare earth fertilizer application [J]. Environmental Pollution, 2001, 112 (3): 395–405.

    [8] Zhu S G, He W Z, Li G M, et al. Recovery of Co and Li from spent lithium-ion batteries by combination method of acid leaching and chemical precipitation [J]. Transactions of Nonferrous Metals Society of China, 2012, 22 (9): 2274–2281.

    [9] Matlock M M, Howerton B S, Atwood D A. Chemical precipitation of heavy metals from acid mine drainage [J]. Water Research, 2002, 36 (19): 4757–4764.

    [10] Ramakul P, Mooncluen U, Yanachawakul Y, et al. Mass transport modeling and analysis on the mutual separation of lanthanum (Ⅲ) and cerium (Ⅳ) through a hollow fiber supported liquid membrane [J]. Journal of Industrial and Engineering Chemistry, 2012, 18 (5): 1606–1611.

    [11] Asai S, Watanabe K, Sugo T. Preparation of an extractant-impregnated porous membrane for the high-speed separation of a metal ion [J]. Journal of Chromatography A, 2005, 1094 (1/2): 158–164.

    [12] Lam K F, Kassab H, Pera-titus M, et al. MCM-41 “LUS”: alumina tubular membranes for metal separation in aqueous solution [J]. The Journal of Physical Chemistry C, 2010, 115 (1): 176–187.

    [13] Chevis D A, Johannesson K H, Burdige D J, et al. Submarine groundwater discharge of rare earth elements to a tidally-mixed estuary in Southern Rhode Island [J]. Chemical Geology, 2015,397: 128–142.

    [14] Zhao Z Y, Sun X Q, Dong Y M. Synergistic effect of doped functionalized ionic liquids in silica hybrid material for rare earth adsorption [J]. Industrial & Engineering Chemistry Research,2016, 55 (7): 2221–2229.

    [15] Ghoul M, Bacquet M, Morcellet M. Uptake of heavy metals from synthetic aqueous solutions using modified PEI–silica gels [J]. Water Research, 2003, 37 (4): 729–734.

    [16] Dragan E S. Design and applications of interpenetrating polymer network hydrogels. A review [J]. Chemical Engineering Journal,2014, 243 (5): 572–590.

    [17] Demirbilek C, Dinc CÖ. Synthesis of diethylaminoethyl dextran hydrogel and its heavy metal ion adsorption characteristics [J]. Carbohydrate Polymers, 2012, 90 (2): 1159–1167.

    [18] Ma J, Yang M X, Yu F, et al. Water-enhanced removal of ciprofloxacin from water by porous graphene hydrogel [J]. Scientific Reports, 2015, 5: 13578.

    [19] Kumar R, Jain S K, Verma S, et al. Mercapto functionalized silica entrapped polyacrylamide hydrogel: arsenic adsorption behaviour from aqueous solution [J]. Journal of Colloid and Interface Science, 2015, 456: 241–245.

    [20] Niyogi S, Bekyarova E, Itkis M E, et al. Solution properties of graphite and graphene [J]. Journal of the American Chemical Society, 2006, 128 (24): 7720–7721.

    [21] Geng H J. Preparation and characterization of cellulose/N,N'-methylene bisacrylamide/graphene oxide hybrid hydrogels and aerogels [J]. Carbohydrate Polymers, 2018, 196: 289–298.

    [22] Lerf A, He H Y, Forster M, et al. Structure of graphite oxide revisited [J]. Journal of Physical Chemistry B, 1998, 102 (23): 4477–4482.

    [23] Liu M C, Chen C L, Hu J, et al. Synthesis of magnetite/graphene oxide composite and application for cobalt (Ⅱ) removal [J]. Journal of Physical Chemistry C, 2011, 115 (51): 25234–25240.

    [24] Zhu C H, Lu Y, Peng J, et al. Photothermally sensitive poly(N-isopropylacrylamide)/graphene oxide nanocomposite hydrogels as remote light–controlled liquid microvalves [J]. Advanced Functional Materials, 2012, 22 (19): 4017–4022.

    [25] Yamashita K, Nishimura T, Ohashi K, et al. Two-step imprinting procedure of inter-penetrating polymer network-type stimuliresponsive hydrogel-adsorbents [J]. Polymer Journal, 2003, 35 (7): 545–550.

    [26] Zhang X Z, Yang Y Y, Chung T S. Effect of mixed solvents on characteristics of poly(N-isopropylacrylamide) gels [J]. Langmuir,2002, 18 (7): 2538–2542.

    [27] Kim J H, Lee S L, Kim S J, et al. Rapid temperature/pH response of porous alginate-g-poly(N-isopropylacrylamide) hydrogels [J]. Polymer, 2002, 43 (26): 7549–7558.

    [28] Wu J J, Zhao Q, Sun J Z, et al. Preparation of poly(ethylene glycol) aligned porous cryogels using a unidirectional freezing technique [J]. Soft Matter, 2012, 8 (13): 3620–3626.

    [29] Wu D B, Gao Y W, Li W J, et al. Selective adsorption of La3+ using a tough alginate-clay poly(N-isopropylacrylamide) hydrogel with hierarchical pores and reversible re-deswelling/swelling cycles [J]. ACS Sustainable Chemistry & Engineering, 016, 4 (12): 6732–6743.

    [30] Kirsebom H, Mattiasson B. Cryostructuration as a tool for preparing highly porous polymer materials [J]. Polymer Chemistry, 2011, 2 (5): 1059–1062.

    [31] Barrow M, Zhang H F. Aligned porous stimuli-responsive hydrogels via directional freezing and frozen UV initiated polymerization [J]. Soft Matter, 2013, 9 (9): 2723–2729.

    [32] Cheng C, Zhang X L, Meng Y B, et al. Multiresponsive and biocompatible self-healing hydrogel: its facile synthesis in water, characterization and properties [J]. Soft Matter, 2017, 13 (16): 3003–3012.

    [33] Liu L, Li L, Qing Y, et al. Mechanically strong and thermosensitive hydrogels reinforced with cellulose nanofibrils [J]. Polymer Chemistry, 2016, 7 (46): 7142–7151.

    [34] Wang E, Desai M S, Lee S W. Light-controlled graphene–elastin composite hydrogel actuators [J]. Nano Letters, 2013, 13 (6): 2826–2830.

    [35] Xue W, Champ S, Huglin M B, et al. Rapid swelling and deswelling in cryogels of crosslinked poly(N-isopropylacrylamideacrylic acid) [J]. European Polymer Journal, 2004, 40 (4): 703–712.

    [36] Cheng J J, Shan G R, Pan P J. Temperature and pH-dependent swelling and copper (Ⅱ) adsorption of poly (N-isopropylacrylamide) copolymer hydrogel [J]. RSC Advances, 2015, 5 (76): 62091–62100.

    [37] Cheng J J, Shan G R, Pan P J. Triple stimuli-responsive Nisopropylacrylamide copolymer toward metal ion recognition and adsorption via a thermally induced sol–gel transition [J]. Industrial & Engineering Chemistry Research, 2017, 56 (5): 1223–1232.

    [38] Arvidsson P, Plieva F M, Lozinsky V I, et al. Direct chromatographic capture of enzyme from crude homogenate using immobilized metal affinity chromatography on a continuous supermacroporous adsorbent [J]. Journal of Chromatography A,2003, 986 (2): 275–290.

This Article


CN: 11-1946/TQ

Vol 70, No. 10, Pages 4072-4079+3612

October 2019


Article Outline


  • Introduction
  • 1 Experimental
  • 2 Results and discussion
  • 3 Conclusions
  • Symbol description
  • References