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

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.

Graphical abstract

Keywords

MnO₂-polyethylenimine-tannic acid composite / surface complexation formation model / Cu(II) / Cr(VI) / physicochemical mechanism

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

[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

[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

[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

[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

[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

[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

[8] Wang L, Hu D, Kong X, Liu J, Li X, Zhou K, Zhao H, Zhou C. Anionic polypeptide poly (g-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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[27] Ali S, Chen L, Li Z, Zhang T, Rui L, Bakhtiar S U H, Leng X, Yuan F, Niu X, Zhu Y. Cu_x-Nb_1.1‒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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[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

[38] Moreira 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

[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

[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

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

[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

[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

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.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-020-1958-1 and is accessible for authorized users.

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