Skip to main content
Log in

Adsorption performance and physicochemical mechanism of MnO2-polyethylenimine-tannic acid composites for the removal of Cu(II) and Cr(VI) from aqueous solution

  • Research Article
  • Published:
Frontiers of Chemical Science and Engineering Aims and scope Submit manuscript

Abstract

In this work, an adsorbent, which we call MnPT, was prepared by combining MnO2, polyethylenimine and tannic acid, and exhibited efficient performance for Cu(II) and Cr(VI) removal from aqueous solution. The oxygen/nitrogen-containing functional groups on the surface of MnPT might increase the enrichment of metal ions by complexation. The maximum adsorption capacities of MnPT for Cu(II) and Cr(VI) were 121.5 and 790.2 mg·g−1, respectively. The surface complexation formation model was used to elucidate the physicochemical interplay in the process of Cu(II) and Cr(VI) co-adsorption on MnPT. Electrostatic force, solvation action, adsorbate-adsorbate lateral interaction, and complexation were involved in the spontaneous adsorption process. Physical electrostatic action was dominant in the initial stage, whereas chemical action was the driving force leading to adsorption equilibrium. It should be noted that after adsorption on the surface of MnPT, Cr(VI) reacted with some reducing functional groups (hydroxylamine-NH2) and was converted into Cr(III). The adsorption capacity declined by 12% after recycling five times. Understanding the adsorption mechanism might provide a technical basis for the procedural design of heavy metal adsorbents. This MnPT nanocomposite has been proven to be a low-cost, efficient, and promising adsorbent for removing heavy metal ions from wastewater.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. Huang J, Xu Y, Zhang X, Lei Z, Chen C, Deng Y, Wang C. Polyethylenimine and dithiocarbamate decorated melamine sponges for fast copper (II) ions removal from aqueous solution. Applied Surface Science, 2018, 445: 471–477

    CAS  Google Scholar 

  2. Deng J, Liu Y, Liu S, Zeng G, Tan X, Huang B, Tang X, Wang S, Hua Q, Yan Z. Competitive adsorption of Pb(II), Cd(II) and Cu(II) onto chitosan-pyromellitic dianhydride modified biochar. Journal of Colloid and Interface Science, 2017, 506: 355–364

    CAS  PubMed  Google Scholar 

  3. Shen H, Pan S, Zhang Y, Huang X, Gong H. A new insight on the adsorption mechanism of amino-functionalized nano-Fe3O4 magnetic polymers in Cu(II), Cr(VI) co-existing water system. Chemical Engineering Journal, 2012, 183: 180–191

    CAS  Google Scholar 

  4. Feng Z, Chen N, Feng C, Gao Y. Mechanisms of Cr(VI) removal by FeCl3-modified lotus stem-based biochar (FeCl3@LS-BC) using mass-balance and functional group expressions. Colloids and Surfaces. A, Physicochemical and Engineering Aspects, 2018, 551: 17–24

    CAS  Google Scholar 

  5. Kwak H W, Lee K H. Polyethylenimine-functionalized silk sericin beads for high-performance remediation of hexavalent chromium from aqueous solution. Chemosphere, 2018, 207: 507–516

    CAS  PubMed  Google Scholar 

  6. Ying C, Ma K, Wang J, Yu G, Zhu X, Zhang W. Catalytic activities of two different morphological nano-MnO2 on the thermal decomposition of ammonium perchlorate. Materials Research Bulletin, 2018, 101: 56–60

    Google Scholar 

  7. Xiao X, Chen B, Chen Z, Zhu L, Schnoor J L. Insight into multiple and multi-level structures of biochars and their potential environmental applications: a critical review. Environmental Science & Technology, 2018, 52(9): 5027–5047

    CAS  Google Scholar 

  8. Wang L, Hu D, Kong X, Liu J, Li X, Zhou K, Zhao H, Zhou C. Anionic polypeptide poly (γ-glutamic acid)-functionalized magnetic Fe3O4-GO-(O-MWCNTs) hybrid nanocomposite for high-efficiency removal of Cd(II), Cu(II) and Ni(II) heavy metal ions. Chemical Engineering Journal, 2018, 346: 38–49

    CAS  Google Scholar 

  9. Zhang Z, Gao T, Si S, Liu Q, Wu Y, Zhou G. One-pot preparation of P(TA-TEPA)-PAM-RGO ternary composite for high efficient Cr(VI) removal from aqueous solution. Chemical Engineering Journal, 2018, 343: 207–216

    CAS  Google Scholar 

  10. Li X, Wang Z, Ning J, Gao M, Jiang W, Zhou Z, Li G. Preparation and characterization of a novel polyethyleneimine cation-modified persimmon tannin bioadsorbent for anionic dye adsorption. Journal of Environmental Management, 2018, 217: 305–314

    CAS  PubMed  Google Scholar 

  11. Chen Y, Ma K, Wang J, Gao Y, Zhu X, Zhang W. Catalytic activities of two different morphological nano-MnO2 on the thermal decomposition of ammonium perchlorate. Materials Research Bulletin, 2018, 101: 56–60

    CAS  Google Scholar 

  12. Ejima H, Richardson J J, Liang K, Best J P, van Koeverden M P, Such G K, Cui J W, Caruso F. One-step assembly of coordination complexes for versatile film and particle engineering. Science, 2013, 341(6142): 154–157

    CAS  PubMed  Google Scholar 

  13. Chen Q Y, Chen J Z, Zhou Y Y, Song C, Tian Q H, Xu J L, Wong C P. Enhancing pseudocapacitive kinetics of nanostructured MnO2 through anchoring onto biomass-derived porous carbon. Applied Surface Science, 2018, 440: 1027–1036

    CAS  Google Scholar 

  14. Chen R, Yu J, Wei X J. Hierarchically porous MnO2 microspheres with enhanced adsorption performance. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2013, 1 (38): 11682–11690

    CAS  Google Scholar 

  15. Wang S, Zhang J, Cai W, Shao X. Titanium dioxide as an adsorbent to enhance the detection ability of near-infrared diffuse reflectance spectroscopy. Chinese Chemical Letters, 2019, 30(5): 1024–1026

    CAS  Google Scholar 

  16. Qian X, Yang J, Fei Z, Liu Q, Qiao X. A simple strategy to improve PEI dispersion on MCM-48 with long-Alkyl chains template for efficient CO2 adsorption. Industrial & Engineering Chemistry Research, 2019, 58(25): 10975–10983

    CAS  Google Scholar 

  17. Díez N, Ferrero G A, Sevilla M, Fuertes A B. A sustainable approach to hierarchically porous carbons from tannic acid and their utilization in supercapacitive energy storage systems. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2019, 7(23): 14280–14290

    Google Scholar 

  18. Yurtsever M, Sengi L I A. Biosorption of Pb(II) ions by modified quebracho tannin resin. Journal of Hazardous Materials, 2009, 163 (1): 58–64

    CAS  PubMed  Google Scholar 

  19. Zhao C, Zheng H, Sun Y, Liu B, Zhou Y, Liu Y, Zheng X. Fabrication of tannin-based dithiocarbamate biosorbent and its application for Ni(II) ion removal. Water, Air, and Soil Pollution, 2017, 228(11): 409

    Google Scholar 

  20. Bacelo H A, Santos S C, Botelho C M. Tannin-based biosorbents for environmental applications—a review. Chemical Engineering Journal, 2016, 303: 575–587

    CAS  Google Scholar 

  21. Wagner A, Ferraria A M, Rego A M, Mateus M, Azevedo A M. Purification of monoclonal antibodies in a stirred cell with polyethyleneimine-modified polyethersulfone ultrafiltration membrane. Journal of Chemical Technology and Biotechnology (Oxford, Oxfordshire), 2019, 94(11): 3548–3558

    CAS  Google Scholar 

  22. Dinh V P, Le N C, Tuyen L A, Hung N Q, Nguyen V D, Nguyen N T. Insight into adsorption mechanism of lead(II) from aqueous solution by chitosan loaded MnO2 nanoparticles. Materials Chemistry and Physics, 2018, 207: 294–302

    CAS  Google Scholar 

  23. Zhang Y, Liu C, Xu B, Qi F, Chu W. Degradation of benzotriazole by a novel Fenton-like reaction with mesoporous Cu/MnO2: combination of adsorption and catalysis oxidation. Applied Catalysis B: Environmental, 2016, 199: 447–457

    CAS  Google Scholar 

  24. Son H Y, Jun H, Kim K R, Hong C A, Nam Y S. Tannin-mediated assembly of gold-titanium oxide hybrid nanoparticles for plasmonic photochemical applications. Journal of Industrial and Engineering Chemistry, 2018, 63: 420–425

    CAS  Google Scholar 

  25. Li L, Wang F, Lv Y, Liu J, Zhang D, Shao Z. Halloysite nanotubes and Fe3O4 nanoparticles enhanced adsorption removal of heavy metal using electrospun membranes. Applied Clay Science, 2018, 161: 225–234

    CAS  Google Scholar 

  26. Lv M, Yan L, Liu C, Su C, Zhou Q, Zhang X, Lan Y, Zheng Y, Lai L, Liu X, Ye Z. Non-covalent functionalized graphene oxide (GO) adsorbent with an organic gelator for co-adsorption of dye endocrine-disruptor pharmaceutical and metal ion. Chemical Engineering Journal, 2018, 349: 791–799

    CAS  Google Scholar 

  27. Ali S, Chen L, Li Z, Zhang T, Rui L, Bakhtiar S U H, Leng X, Yuan F, Niu X, Zhu Y. Cux-Nb11−x(x = 0.45, 0.35, 0.25, 0.15) bimetal oxides catalysts for the low temperature selective catalytic reduction of NO with NH3. Applied Catalysis B: Environmental, 2018, 236: 25–35

    CAS  Google Scholar 

  28. Akhavan O, Azimirad R, Safa S, Hasani E J. CuO/Cu(OH)2 hierarchical nanostructures as bactericidal photocatalysts. Journal of Materials Chemistry, 2011, 21(26): 9634–9640

    CAS  Google Scholar 

  29. Alqadami A A, Mu N, Abdalla M A, Ahamad T, Alothman Z A, Alsehri S M, Ghfar A A. Efficient removal of toxic metal ions from wastewater using a recyclable nanocomposite: a study of adsorption parameters and interaction mechanism. Journal of Cleaner Production, 2017, 156: 426–436

    Google Scholar 

  30. Jović M, Šljivić-Ivanović M, Dimović S, Marković J, Smičiklas I J G. Sorption and mobility of Co(II) in relation to soil properties. Geoderma, 2017, 297: 38–47

    Google Scholar 

  31. Ke F, Jiang J, Li Y, Liang J, Wan X, Ko S. Highly selective removal of Hg2+ and Pb2+ by thiol-functionalized Fe3O4@metal-organic framework core-shell magnetic microspheres. Applied Surface Science, 2017, 413: 266–274

    CAS  Google Scholar 

  32. Aghagoli M J, Beyki M H, Shemirani F. Application of dahlia-like molybdenum disulfide nanosheets for solid phase extraction of Co(II) in vegetable and water samples. Food Chemistry, 2017, 223: 8–15

    CAS  PubMed  Google Scholar 

  33. Alyuz B, Veli S. Kinetics and equilibrium studies for the removal of nickel and zinc from aqueous solutions by ion exchange resins. Journal of Hazardous Materials, 2009, 167(1–3): 482–488

    PubMed  Google Scholar 

  34. Park S W, Huang C P. The surface acidity of hydrous CdS(s). Journal of Colloid and Interface Science, 1987, 117(2): 431–441

    CAS  Google Scholar 

  35. Weng C H, Huang C P, Allen H E, Leavens P B, Sanders P F. Chemical interactions between Cr(VI) and hydrous concrete particles. Environmental Science & Technology, 1996, 30(2): 371–376

    CAS  Google Scholar 

  36. Weng C H, Huang C, Allen H, Sanders P F. Cr(VI) adsorption onto hydrous concrete particles from groundwater. Journal of Environmental Engineering, 2001, 127(12): 1124–1131

    CAS  Google Scholar 

  37. Gan M, Sun S, Zheng Z, Tang H, Sheng J, Zhu J, Liu X. Adsorption of Cr(VI) and Cu(II) by AlPO4 modified biosynthetic schwertmannite. Applied Surface Science, 2015, 356: 986–997

    CAS  Google Scholar 

  38. Moreirav A L D S L, Pereira A D S, Speziali M G, Novack K M, Gurgel L V A, Gil L F. Bifunctionalized chitosan: a versatile adsorbent for removal of Cu(II) and Cr(VI) from aqueous solution. Carbohydrate Polymers, 2018, 201: 218–227

    Google Scholar 

  39. Yu S, Liu Y, Ai Y, Wang X, Zhang R, Chen Z, Chen Z, Zhao G, Wang X. Rational design of carbonaceous nanofiber/Ni-Al layered double hydroxide nanocomposites for high-efficiency removal of heavy metals from aqueous solutions. Environmental Pollution, 2018, 242: 1–11

    CAS  PubMed  Google Scholar 

  40. Hao P, Ma X, Xie J, Lei F, Li L, Zhu W, Cheng X, Cui G, Tang B. Removal of toxic metal ions using chitosan coated carbon nanotube composites for supercapacitors. Science China. Chemistry, 2018, 61 (7): 797–805

    CAS  Google Scholar 

  41. Weng C H. Modeling Pb(II) adsorption onto sandy loam soil. Journal of Colloid and Interface Science, 2004, 272(2): 262–270

    CAS  PubMed  Google Scholar 

  42. Farokhi M, Parvareh A, Moraveji M K. Performance of ceria/iron oxide nano-composites based on chitosan as an effective adsorbent for removal of Cr(VI) and Co(II) ions from aqueous systems. Environmental Science and Pollution Research International, 2018, 25(27): 27059–27073

    CAS  PubMed  Google Scholar 

  43. Tran H N, Lin C C, Woo S H, Chao H P. Efficient removal of copper and lead by Mg/Al layered double hydroxides intercalated with organic acid anions: adsorption kinetics, isotherms, and thermodynamics. Applied Clay Science, 2018, 154: 17–27

    CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos. 41573103, 41340037), the Shandong Provincial Key Research and Development Program (Grant Nos. 2017GSF16105, 2018GGX102004, 2018GSF117007), and the Taishan Scholar Program (Grant No. ts201712045) of Shandong Province of China.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Hongtao Gao.

Electronic Supplementary Material

11705_2020_1958_MOESM1_ESM.pdf

Adsorption performance and physicochemical mechanism of MnO2-polyethylenimine-tannic acid composites for the removal of Cu(II) and Cr(VI) from aqueous solution

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Deng, X., Wang, L., Xiu, Q. et al. Adsorption performance and physicochemical mechanism of MnO2-polyethylenimine-tannic acid composites for the removal of Cu(II) and Cr(VI) from aqueous solution. Front. Chem. Sci. Eng. 15, 538–551 (2021). https://doi.org/10.1007/s11705-020-1958-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11705-020-1958-1

Keywords

Navigation