Hydrothermal synthesis of chemically stable cross-linked poly-Schiff base for efficient Cr(VI) removal

  • Lili Ren
  • Zhihui Yang
  • Linfeng Jin
  • Weichun Yang
  • Yan Shi
  • Sheng Wang
  • Huimin Yi
  • Dun Wei
  • Haiying WangEmail author
  • Liyuan ZhangEmail author
Chemical routes to materials


A superb adsorbent for Cr(VI) removal with a high adsorption capacity and acidic resistance was facilely synthesized via in situ hydrothermal cross-linking and reduction reaction of poly-Schiff base using m-phenylenediamine and glutaraldehyde as feedstock. The hydrothermal process effectively facilitated the condensation between aldehyde and amine group to strengthen the chemical structure by cross-linking the polymeric chains. Morphological evolution of the polymer via disaggregation and reassembly to finally form regular core–shell configuration was observed. The produced nanoparticles possess the excellent adsorption performance (833.3 mg g−1), far beyond most of the reported adsorbents, and exhibit fine reusability. The possible adsorption mechanism can be attributed to Cr(VI) electrostatic adsorption followed by redox reaction and chelation.








Haiying Wang and Liyuan Zhang thank the financial support by National Key R&D Program of China (2016YFC0403003), and Key R&D Program of Hunan Province (2018SK2026 and 2018SK2043).

Compliance with ethical standards

Conflict of interest

The authors all declare that they have no conflict of interest.

Supplementary material

10853_2019_4191_MOESM1_ESM.docx (1.3 mb)
The FTIR spectrum of hydrothermal poly-Schiff base under various temperature and dosage of GA (Fig. S1); the TEM image of hydrothermal poly-Schiff base under various temperature and dosage of GA (Fig. S2); the AFM image of pS(1:2)-Hred(150) (Fig. S3); formation of nanoparticles with core–shell configuration (Fig. S4); the TEM image of two attached nanoparticles with a joint shell (Fig. S5); the adsorption isotherms of hydrothermal poly-Schiff base (Fig. S6); pH changing in solution after adsorption (Fig. S7) (DOCX 1373 kb)


  1. 1.
    Dhal B, Thatoi HN, Das NN, Pandey BD (2013) Chemical and microbial remediation of hexavalent chromium from contaminated soil and mining/metallurgical solid waste: a review. J Hazard Mater 250:272–291CrossRefGoogle Scholar
  2. 2.
    Zhang C, Cai K, Feng Q, Xu Y, Zhang Z (2019) Chromium(VI) promotes cell migration through targeting epithelial-mesenchymal transition in prostate cancer. Toxicol Lett 300:10–17CrossRefGoogle Scholar
  3. 3.
    Shahid M, Shamshad S, Rafiq M, Khalid S, Bibi I, Niazi NK, Dumat C, Rashid MI (2017) Chromium speciation, bioavailability, uptake, toxicity and detoxification in soil-plant system: a review. Chemosphere 178:513–533CrossRefGoogle Scholar
  4. 4.
    Hausladen DM, Alexander-Ozinskas A, McClain C, Fendorf S (2018) Hexavalent chromium sources and distribution in California Groundwater. Environ Sci Technol 52:8242–8251CrossRefGoogle Scholar
  5. 5.
    Xie B, Shan C, Xu Z, Li X, Zhang X, Chen J, Pan B (2017) One-step removal of Cr(VI) at alkaline pH by UV/sulfite process: reduction to Cr(III) and in situ Cr(III) precipitation. Chem Eng J 308:791–797CrossRefGoogle Scholar
  6. 6.
    Peng H, Guo J, Li B, Liu Z, Tao C (2018) High-efficient recovery of chromium (VI) with lead sulfate. J Taiwan Inst Chem E 85:149–154CrossRefGoogle Scholar
  7. 7.
    Wu Z, Yuan X, Zeng G, Jiang L, Zhong H, Xie Y, Wang H, Chen X, Wang H (2018) Highly efficient photocatalytic activity and mechanism of Yb3+/Tm3+ codoped In2S3 from ultraviolet to near infrared light towards chromium (VI) reduction and rhodamine B oxydative degradation. Appl Catal B-Environ 225:8–21CrossRefGoogle Scholar
  8. 8.
    Velegraki G, Miao J, Drivas C, Liu B, Kennou S, Armatas GS (2018) Fabrication of 3D mesoporous networks of assembled CoO nanoparticles for efficient photocatalytic reduction of aqueous Cr(VI). Appl Catal B-Environ 221:635–644CrossRefGoogle Scholar
  9. 9.
    Zhang Y, Xu M, Li H, Ge H, Bian Z (2018) The enhanced photoreduction of Cr(VI) to Cr(III) using carbon dots coupled TiO2 mesocrystals. Appl Catal B-Environ 226:213–219CrossRefGoogle Scholar
  10. 10.
    Chai L, Ding C, Tang C, Yang W, Yang Z, Wang Y, Liao Q, Li J (2018) Discerning three novel chromate reduce and transport genes of highly efficient Pannonibacter phragmitetus BB: from genome to gene and protein. Ecotoxicol Environ Saf 162:139–146CrossRefGoogle Scholar
  11. 11.
    Wang Y, Peng B, Yang Z, Chai L, Liao Q, Zhang Z, Li C (2015) Bacterial community dynamics during bioremediation of Cr(VI)-contaminated soil. Appl Soil Ecol 85:50–55CrossRefGoogle Scholar
  12. 12.
    Chai L, Huang S, Yang Z, Peng B, Huang Y, Chen Y (2009) Cr(VI) remediation by indigenous bacteria in soils contaminated by chromium-containing slag. J Hazard Mater 167:516–522CrossRefGoogle Scholar
  13. 13.
    Wu J, Ma L, Zeng RJ (2018) Role of extracellular polymeric substances in efficient chromium(VI) removal by algae-based Fe/C nano-composite. Chemosphere 211:608–616CrossRefGoogle Scholar
  14. 14.
    Martin-Dominguez A, Rivera-Huerta ML, Perez-Castrejon S, Garrido-Hoyos SE, Villegas-Mendoza IE, Gelover-Santiago SL, Drogui P, Buelna G (2018) Chromium removal from drinking water by redox-assisted coagulation: chemical versus electrocoagulation. Sep Purif Technol 200:266–272CrossRefGoogle Scholar
  15. 15.
    Aoudj S, Khelifa A, Drouiche N, Belkada R, Miroud D (2015) Simultaneous removal of chromium(VI) and fluoride by electrocoagulation–electroflotation: application of a hybrid Fe–Al anode. Chem Eng J 267:153–162CrossRefGoogle Scholar
  16. 16.
    Abyaneh AS, Fazaelipoor MH (2016) Evaluation of rhamnolipid (RL) as a biosurfactant for the removal of chromium from aqueous solutions by precipitate flotation. J Environ Manag 165:184–187CrossRefGoogle Scholar
  17. 17.
    Esmaeili A, Hejazi E, Vasseghian Y (2015) Comparison study of biosorption and coagulation/air flotation methods for chromium removal from wastewater: experiments and neural network modeling. RSC Adv 5:91776–91784CrossRefGoogle Scholar
  18. 18.
    Wang T, Zhang L, Li C, Yang W, Song T, Tang C, Meng Y, Dai S, Wang H, Chai L, Luo J (2015) Synthesis of core–shell magnetic Fe3O4@poly(m-phenylenediamine) particles for chromium reduction and adsorption. Environ Sci Technol 49:5654–5662CrossRefGoogle Scholar
  19. 19.
    Jin L, Huang L, Ren L, He Y, Tang J, Wang S, Yang W, Wang H, Chai L (2019) Preparation of stable and high-efficient poly(m-phenylenediamine)/reduced graphene oxide composites for hexavalent chromium removal. J Mater Sci 54:383–395. CrossRefGoogle Scholar
  20. 20.
    Wang S, Li X, Liu Y, Zhang C, Tan X, Zeng G, Song B, Jiang L (2018) Nitrogen-containing amino compounds functionalized graphene oxide: synthesis, characterization and application for the removal of pollutants from wastewater: a review. J Hazard Mater 342:177–191CrossRefGoogle Scholar
  21. 21.
    Burakov AE, Galunin EV, Burakova IV, Kucherova AE, Agarwal S, Tkachev AG, Gupta VK (2018) Adsorption of heavy metals on conventional and nanostructured materials for wastewater treatment purposes: a review. Ecotoxicol Environ Saf 148:702–712CrossRefGoogle Scholar
  22. 22.
    Sherlala AIA, Raman AAA, Bello MM, Asghar A (2018) A review of the applications of organo-functionalized magnetic graphene oxide nanocomposites for heavy metal adsorption. Chemosphere 193:1004–1017CrossRefGoogle Scholar
  23. 23.
    Inyang MI, Gao B, Yao Y, Xue Y, Zimmerman A, Mosa A, Pullammanappallil P, Ok YS, Cao X (2016) A review of biochar as a low-cost adsorbent for aqueous heavy metal removal. Crit Rev Environ Sci Technol 46:406–433CrossRefGoogle Scholar
  24. 24.
    Mortazavian S, An H, Chun D, Moon J (2018) Activated carbon impregnated by zero-valent iron nanoparticles (AC/nZVI) optimized for simultaneous adsorption and reduction of aqueous hexavalent chromium: material characterizations and kinetic studies. Chem Eng J 353:781–795CrossRefGoogle Scholar
  25. 25.
    Mohan D Jr, Pittman CU (2006) Activated carbons and low cost adsorbents for remediation of tri- and hexavalent chromium from water. J Hazard Mater 137:762–811CrossRefGoogle Scholar
  26. 26.
    Gong K, Hu Q, Yao L, Li M, Sun D, Shao Q, Qiu B, Guo Z (2018) Ultrasonic pretreated sludge derived stable magnetic active carbon for Cr(VI) removal from wastewater. ACS Sustain Chem Eng 6:7283–7291CrossRefGoogle Scholar
  27. 27.
    Zhu L, Fu F, Tang B (2018) Coexistence or aggression? Insight into the influence of phosphate on Cr(VI) adsorption onto aluminum-substituted ferrihydrite. Chemosphere 212:408–417CrossRefGoogle Scholar
  28. 28.
    Dinker MK, Kulkarni PS (2015) Recent advances in silica-based materials for the removal of hexavalent chromium: a review. J Chem Eng Data 60:2521–2540CrossRefGoogle Scholar
  29. 29.
    Li J, Wang X, Zhao G, Chen C, Chai Z, Alsaedi A, Hayat T, Wang X (2018) Metal–organic framework-based materials: superior adsorbents for the capture of toxic and radioactive metal ions. Chem Soc Rev 47:2322–2356CrossRefGoogle Scholar
  30. 30.
    Anastopoulos I, Anagnostopoulos VA, Bhatnagar A, Mitropoulos AC, Kyzas GZ (2017) A review for chromium removal by carbon nanotubes. Chem Ecol 33:572–588CrossRefGoogle Scholar
  31. 31.
    Hua M, Zhang S, Pan B, Zhang W, Lv L, Zhang Q (2012) Heavy metal removal from water/wastewater by nanosized metal oxides: a review. J Hazard Mater 211:317–331CrossRefGoogle Scholar
  32. 32.
    Yu W, Zhang L, Wang H, Chai L (2013) Adsorption of Cr(VI) using synthetic poly(m-phenylenediamine). J Hazard Mater 260:789–795CrossRefGoogle Scholar
  33. 33.
    Yang Z, Ren L, Jin L, Huang L, He Y, Tang J, Yang W, Wang H (2018) In-situ functionalization of poly(m-phenylenediamine) nanoparticles on bacterial cellulose for chromium removal. Chem Eng J 344:441–452CrossRefGoogle Scholar
  34. 34.
    Chai LY, Wang X, Wang HY, Yang WC, Liao Q, Wu YJ (2018) Formation of one-dimensional composites of poly(m-phenylenediamine)s based on Streptomyces for adsorption of hexavalent chromium. Int J Environ Sci Technol 15:1411–1422CrossRefGoogle Scholar
  35. 35.
    Su Z, Zhang L, Chai L, Wang H, Yu W, Wang T, Yang J (2014) High-yield synthesis of poly(m-phenylenediamine) hollow nanostructures by a diethanolamine-assisted method and their enhanced ability for Ag+ adsorption. New J Chem 38:3984–3991CrossRefGoogle Scholar
  36. 36.
    Li X, Don Q, Huang M (2008) Highly effective sorption of heavy metal ions on polyaniline and its composites. Prog Chem 20:227–232Google Scholar
  37. 37.
    Zhang L, Chai L, Liu J, Wang H, Yu W, Sang P (2011) pH manipulation: a Facile method for lowering oxidation state and keeping good yield of poly(m-phenylenediamine) and its powerful Ag+ adsorption ability. Langmuir 27:13729–13738CrossRefGoogle Scholar
  38. 38.
    Su Z, Zhang L, Chai L, Yu W, Wang H, Shi Y (2013) Methanol-induced formation of 1D poly(m-phenylenediamine) by conventional chemical oxidative polymerization exhibiting superior Ag+ adsorption ability. RSC Adv 3:8660–8665CrossRefGoogle Scholar
  39. 39.
    Meng Y, Zhang L, Chai L, Yu W, Wang T, Dai S, Wang H (2014) Facile and large-scale synthesis of poly(m-phenylenediamine) nanobelts with high surface area and superior dye adsorption ability. RSC Adv 4:45244–45250CrossRefGoogle Scholar
  40. 40.
    Yu W, Zhang L, Meng Y, Dai S, Su Z, Chai L, Wang H (2013) High conversion synthesis of functional poly(m-phenylenediamine) nanoparticles by Cu–OH-assisted method and its superior ability toward Ag+ adsorption. Synth Met 176:78–85CrossRefGoogle Scholar
  41. 41.
    Li X, Ma X, Sun J, Huang M (2009) Powerful reactive sorption of silver(I) and mercury(II) onto poly(o-phenylenediamine) microparticles. Langmuir 25:1675–1684CrossRefGoogle Scholar
  42. 42.
    Chai L, Wang T, Zhang L, Wang H, Yang W, Dai S, Meng Y, Li X (2015) A Cu-m-phenylenediamine complex induced route to fabricate poly(m-phenylenediamine)/reduced graphene oxide hydrogel and its adsorption application. Carbon 81:748–757CrossRefGoogle Scholar
  43. 43.
    Amer I, Young DA (2013) Chemically oxidative polymerization of aromatic diamines: the first use of aluminium-triflate as a co-catalyst. Polymer 54:505–512CrossRefGoogle Scholar
  44. 44.
    Zhang L, Chai L, Wang H, Yang Z (2010) Facile synthesis of one-dimensional self-assembly oligo(o-phenylenediamine) materials by ammonium persulfate in acidic solution. Mater Lett 64:1193–1196CrossRefGoogle Scholar
  45. 45.
    Parsaee Z, Haratipour P, Lariche MJ, Vojood A (2018) A novel high performance nano chemosensor for copper (II) ion based on an ultrasound-assisted synthesized diphenylamine-based Schiff base: design, fabrication and density functional theory calculations. Ultrason Sonochem 41:337–349CrossRefGoogle Scholar
  46. 46.
    Al Zoubi W, Kandil F, Chebani MK (2016) Solvent extraction of chromium and copper using Schiff base derived from terephthaldialdehyde and 5-amino-2-methoxy-phenol. Arab J Chem 9:526–531CrossRefGoogle Scholar
  47. 47.
    Zhang L, Wang R, Liu R, Du X, Meng R, Liu L, Yao J (2018) Rapid capture and visual detection of copper ions in aqueous solutions and biofluids using a novel cellulose-Schiff base. Cellulose 25:6947–6961CrossRefGoogle Scholar
  48. 48.
    Hussain Z, Khalaf M, Adil H, Zageer D, Hassan F, Mohammed S, Yousif E (2016) Metal complexes of Schiff’s bases containing sulfonamides nucleus: a review. Res J Pharm Biol Chem Sci 7:1008–1025Google Scholar
  49. 49.
    Jia Y, Li J (2015) Molecular assembly of Schiff base interactions: construction and application. Chem Rev 115:1597–1621CrossRefGoogle Scholar
  50. 50.
    Wang S, Wu B, Liu F, Gao Y, Zhang W (2015) A well-defined alternating copolymer based on a salicylaldimine Schiff base for highly sensitive zinc(II) detection and pH sensing in aqueous solution. Polym Chem 6:1127–1136CrossRefGoogle Scholar
  51. 51.
    Kundu A, Hariharan PS, Prabakaran K, Anthony SP (2015) Developing new Schiff base molecules for selective colorimetric sensing of Fe3+ and Cu2+ metal ions: substituent dependent selectivity and colour change. Sens Actuat B-Chem 206:524–530CrossRefGoogle Scholar
  52. 52.
    Zhang H, Yong X, Zhou J, Deng J, Wu Y (2016) Biomass vanillin-derived polymeric microspheres containing functional aldehyde groups: preparation, characterization, and application as adsorbent. ACS Appl Mater Interfaces 8:2753–2763CrossRefGoogle Scholar
  53. 53.
    Kumari S, Chauhan GS (2014) New cellulose–lysine Schiff-base-based sensor-adsorbent for mercury ions. ACS Appl Mater Interfaces 6:5908–5917CrossRefGoogle Scholar
  54. 54.
    Dolatyari L, Yaftian MR, Rostamnia S (2016) Removal of uranium(VI) ions from aqueous solutions using Schiff base functionalized SBA-15 mesoporous silica materials. J Environ Manag 169:8–17CrossRefGoogle Scholar
  55. 55.
    Setoodehkhah M, Momeni S (2018) Water soluble Schiff base functionalized Fe3O4 magnetic nano-particles as a novel adsorbent for the removal of Pb(II) and Cu(II) metal ions from aqueous solutions. J Inorg Organomet Polym Mater 28:1098–1106CrossRefGoogle Scholar
  56. 56.
    Zhao J, Niu Y, Ren B, Chen H, Zhang S, Jin J, Zhang Y (2018) Synthesis of Schiff base functionalized superparamagnetic Fe3O4 composites for effective removal of Pb(II) and Cd(II) from aqueous solution. Chem Eng J 347:574–584CrossRefGoogle Scholar
  57. 57.
    Ceglowski M, Schroeder G (2015) Preparation of porous resin with Schiff base chelating groups for removal of heavy metal ions from aqueous solutions. Chem Eng J 263:402–411CrossRefGoogle Scholar
  58. 58.
    Moftakhar MK, Yaftian MR, Ghorbanloo M (2016) Adsorption efficiency, thermodynamics and kinetics of Schiff base-modified nanoparticles for removal of heavy metals. Int J Environ Sci Technol 13:1707–1722CrossRefGoogle Scholar
  59. 59.
    Zhou J, Gao F, Jiao T, Xing R, Zhang L, Zhang Q, Peng Q (2018) Selective Cu(II) ion removal from wastewater via surface charged self-assembled polystyrene-Schiff base nanocomposites. Colloids Surf A 545:60–67CrossRefGoogle Scholar
  60. 60.
    Afkhami A, Keypour H, Khajavi F, Rezaeivala M (2011) Spectrophotometric and spectrofluorimetric investigation of different equilibria of a recently synthesized Schiff base with the aid of chemometric methods. J Lumin 131:1472–1478CrossRefGoogle Scholar
  61. 61.
    Li G, Zhang B, Yan J, Wang Z (2014) Micro- and mesoporous poly(Schiff-base)s constructed from different building blocks and their adsorption behaviors towards organic vapors and CO2 gas. J Mater Chem A 2:18881–18888CrossRefGoogle Scholar
  62. 62.
    Li G, Zhang B, Wang Z (2014) Microporous poly(Schiff base) constructed from tetraphenyladamantane units for adsorption of gases and organic vapors. Macromol Rapid Commun 35:971–975CrossRefGoogle Scholar
  63. 63.
    Zhang X, Jiao C, Wang J, Liu Q, Li R, Yang P, Zhang M (2012) Removal of uranium(VI) from aqueous solutions by magnetic Schiff base: kinetic and thermodynamic investigation. Chem Eng J 198:412–419CrossRefGoogle Scholar
  64. 64.
    Cao C, Cui Z, Chen C, Song W, Cai W (2010) Ceria hollow nanospheres produced by a template-free microwave-assisted hydrothermal method for heavy metal ion removal and catalysis. J Phys Chem C 114:9865–9870CrossRefGoogle Scholar
  65. 65.
    Li X, Liu Y, Zhang C, Wen T, Zhuang L, Wang X, Song G, Chen D, Ai Y, Hayat T, Wang X (2018) Porous Fe2O3 microcubes derived from metal organic frameworks for efficient elimination of organic pollutants and heavy metal ions. Chem Eng J 336:241–252CrossRefGoogle Scholar
  66. 66.
    Kumari V, Sasidharan M, Bhaumik A (2015) Mesoporous BaTiO3@SBA-15 derived via solid state reaction and its excellent adsorption efficiency for the removal of hexavalent chromium from water. Dalton Trans 44:1924–1932CrossRefGoogle Scholar
  67. 67.
    Kaya I, Yildirim M, Avci A, Kamaci M (2011) Synthesis and thermal characterization of novel poly(azomethine-urethane)s derived from azomethine containing phenol and polyphenol species. Macromol Res 19:286–293CrossRefGoogle Scholar
  68. 68.
    Zhang Q, Li Y, Yang Q, Chen H, Chen X, Jiao T, Peng Q (2018) Distinguished Cr(VI) capture with rapid and superior capability using polydopamine microsphere: behavior and mechanism. J Hazard Mater 342:732–740CrossRefGoogle Scholar
  69. 69.
    Chen JH, Xing HT, Guo HX, Weng W, Hu SR, Li SX, Huang YH, Sun X, Su ZB (2014) Investigation on the adsorption properties of Cr(VI) ions on a novel graphene oxide (GO) based composite adsorbent. J Mater Chem A 2:12561–12570CrossRefGoogle Scholar
  70. 70.
    Kumar A, Jena HM (2017) Adsorption of Cr(VI) from aqueous solution by prepared high surface area activated carbon from Fox nutshell by chemical activation with H3PO4. J Environ Chem Eng 5:2032–2041CrossRefGoogle Scholar
  71. 71.
    Da Silva Lage AL, Moreira ADS, Pereira MG, Speziali KM, Novack LV, Gurgel Alves, Gil LF (2018) Bifunctionalized chitosan: a versatile adsorbent for removal of Cu(II) and Cr(VI) from aqueous solution. Carbohydr Polym 201:218–227CrossRefGoogle Scholar
  72. 72.
    Huang M, Lu H, Li X (2012) Synthesis and strong heavy-metal ion sorption of copolymer microparticles from phenylenediamine and its sulfonate. J Mater Chem 22:17685–17699CrossRefGoogle Scholar
  73. 73.
    Agathian K, Kannammal L, Meenarathi B, Kailash S, Anbarasan R (2018) Synthesis, characterization and adsorption behavior of cotton fiber based Schiff base. Int J Biol Macromol 107:1102–1112CrossRefGoogle Scholar
  74. 74.
    Huang M, Peng Q, Li X (2006) Rapid and effective adsorption of lead ions on fine poly(phenylenediamine) microparticles. Chem-Eur J 12:4341–4350CrossRefGoogle Scholar
  75. 75.
    Li XG, Liu R, Huang MR (2005) Facile synthesis and highly reactive silver ion adsorption of novel microparticles of sulfodiphenylamine and diaminonaphthalene copolymers. Chem Mater 17:5411–5419CrossRefGoogle Scholar
  76. 76.
    Li X, Feng H, Huang M (2009) Strong adsorbability of mercury ions on aniline/sulfoanisidine copolymer nanosorbents. Chem-Eur J 15:4573–4581CrossRefGoogle Scholar
  77. 77.
    Li X, Feng H, Huang M (2010) Redox sorption and recovery of silver ions as silver nanocrystals on poly(aniline-co-5-sulfo-2-anisidine) nanosorbents. Chem-Eur J 16:10113–10123CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of Environmental Engineering, School of Metallurgy and EnvironmentCentral South UniversityChangshaChina
  2. 2.Department of Colloid ChemistryMax Planck Institute of Colloids and InterfacesPotsdam-GolmGermany
  3. 3.Chinese National Engineering Research Center for Control and Treatment of Heavy Metals PollutionChangshaChina

Personalised recommendations