Hyperbranched magnetic polymer: highly efficient removal of Cr(VI) and application in electroplating wastewater

Abstract

By using a two-step hydrothermal method and trithiocyanuric acid (TTCA), 2,4,6-trihydrazino-1,3,5-triazine (THT), and Fe₃O₄ as raw materials, a spherical magnetic adsorbent polymer (TTCA/THT@Fe₃O₄) was synthesized to achieve the efficient removal of Cr(VI) from wastewater. Under optimal adsorption conditions, the maximum adsorption capacity of TTCA/THT@Fe₃O₄ for Cr(VI) can reach 1340 mg∙g^‒1. Notably, the removal efficiency can approach 98.9%, even at the lower concentration of 20 mg∙L^‒1 Cr(VI). For actual wastewater containing Cr(VI), the Cr(VI) concentration was reduced from 25.8 to 0.4 mg∙L^‒1, a remarkable 20% lower than the current industry discharge standard value. A mechanism for the high adsorption performance of Cr(VI) on TTCA/THT@Fe₃O₄ was investigated using Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and density functional theory. It can be plausibly attributed to the formation of Cr/N and Cr/S coordination bonds. Additionally, surface electrostatic adsorption, reduction effects, and the spherical polymer structure increase the contact area with Cr(VI), maximizing adsorption. The synergistic effect of adsorption and reduction enhances the adsorption performance of TTCA/THT@Fe₃O₄ for Cr(VI) and total chromium in water. The resultant polymer has a simple preparation process, excellent adsorption performance, easy magnetic separation, and promising application for actual wastewater.

Graphical abstract

Keywords

magnetic polymer / chromium removal / hydrogen bonding / recyclability / actual wastewater

References

[1] Cui L, Noerpel M R, Scheckel K, Ippolito J A. Wheat straw biochar reduces environmental cadmium bioavailability. Environment International, 2019, 126: 69–75

[2] Li S, Xu H, Wang L, Ji L, Li X, Qu Z, Yan N. Dual-functional sites for selective adsorption of mercury and arsenic ions in [SnS₄]^4‒/MgFe-LDH from wastewater. Journal of Hazardous Materials, 2021, 403: 123940

[3] Han X, Zhang Y, Zheng C, Yu X, Li S, Wei W. Enhanced Cr(VI) removal from water using a green synthesized nanocrystalline chlorapatite: physicochemical interpretations and fixed-bed column mathematical model study. Chemosphere, 2021, 264(Pt 1): 128421

[4] Esrafili L, Firuzabadi F D, Morsali A, Hu M L. Reuse of predesigned dual-functional metal organic frameworks (DF-MOFs) after heavy metal removal. Journal of Hazardous Materials, 2021, 403: 123696

[5] Maitlo H A, Kim K H, Kumar V, Kim S, Park J W. Nanomaterials-based treatment options for chromium in aqueous environments. Environment International, 2019, 130: 104748

[6] Chen M, Ma L Q, Singh S P, Cao R X, Melamed R. Field demonstration of in situ immobilization of soil Pb using P amendments. Advances in Environmental Research, 2003, 81(1): 93–102

[7] Zhang T, Wei S, Waterhouse G I N, Fu L, Liu L, Shi W, Sun J, Ai S. Chromium (VI) adsorption and reduction by humic acid coated nitrogen-doped magnetic porous carbon. Powder Technology, 2020, 360: 55–64

[8] Shen Z, Zhang J, Hou D, Tsang D C W, Ok Y S, Alessi D S. Synthesis of MgO-coated corncob biochar and its application in lead stabilization in a soil washing residue. Environment International, 2019, 122: 357–362

[9] Abdelwahab N A, Helaly F M. Simulated visible light photocatalytic degradation of Congo red by TiO₂ coated magnetic polyacrylamide grafted carboxymethylated chitosan. Journal of Industrial and Engineering Chemistry, 2017, 50: 162–171

[10] Abdullah N H, Shameli K, Abdullah E, Abdullah L C. Solid matrices for fabrication of magnetic iron oxide nanocomposites: synthesis, properties, and application for the adsorption of heavy metal ions and dyes. Composites Part B: Engineering, 2019, 162: 538–568

[11] Lin G, Wang S, Zhang L, Hu T, Cheng S, Fu L, Xiong C. Enhanced and selective adsorption of Hg²⁺ to a trace level using trithiocyanuric acid-functionalized corn bract. Environmental Pollution, 2019, 244: 938–946

[12] Fiorilli S, Rivoira L, Calì G, Appendini M, Bruzzoniti M C, Coïsson M, Onida B. Iron oxide inside SBA-15 modified with amino groups as reusable adsorbent for highly efficient removal of glyphosate from water. Applied Surface Science, 2017, 411: 457–465

[13] Wang Z, Zhang J, Wu Q, Han X, Zhang M, Liu W, Yao X, Feng J, Dong S, Sun J. Magnetic supramolecular polymer: ultrahigh and highly selective Pb(II) capture from aqueous solution and battery wastewater. Chemosphere, 2020, 248: 126042

[14] Li M. C C. The syuthesis of 2,4,6-trihydrazino-1,3,5-triazine. Guangdong Chemical Industry, 2014, 41(274): 13–14 (in Chinese)

[15] Perdew J P, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Physical Review Letters, 1996, 77(18): 3865–3868

[16] Wang Z, Zhang J, Wen T, Liu X, Wang Y, Yang H, Sun J, Feng J, Dong S, Sun J. Highly effective remediation of Pb(II) and Hg(II) contaminated wastewater and soil by flower-like magnetic MoS₂ nanohybrid. Science of the Total Environment, 2020, 699: 134341

[17] Anito D A, Wang T X, Liu Z W, Ding X, Han B H. Iminodiacetic acid-functionalized porous polymer for removal of toxic metal ions from water. Journal of Hazardous Materials, 2020, 400: 123188

[18] Huang D, Wu J, Wang L, Liu X, Meng J, Tang X, Tang C, Xu J. Novel insight into adsorption and co-adsorption of heavy metal ions and an organic pollutant by magnetic graphene nanomaterials in water. Chemical Engineering Journal, 2019, 358: 1399–1409

[19] Li X, Bian C, Meng X, Xiao F S. Design and synthesis of an efficient nanoporous adsorbent for Hg²⁺ and Pb²⁺ ions in water. Journal of Materials Chemistry A, 2016, 416(16): 5999–6005

[20] Fu W, Huang Z. One-pot synthesis of a two-dimensional porous Fe₃O₄/Poly(C₃N₃S₃) network nanocomposite for the selective removal of Pb(II) and Hg(II) from synthetic wastewater. ACS Sustainable Chemistry & Engineering, 2018, 611(11): 14785–14794

[21] Jun Y S, Lee E Z, Wang X, Hong W H, Stucky G D, Thomas A. From melamine-cyanuric acid supramolecular aggregates to carbon nitride hollow spheres. Advanced Functional Materials, 2013, 2329(29): 3661–3667

[22] Zhu M, Zhang W, Li Y, Gai L, Zhou J, Ma W. Multishell structured magnetic nanocomposites carrying a copolymer of pyrrole-thiophene for highly selective Au(III) recovery. Journal of Materials Chemistry A, 2016, 448(48): 19060–19069

[23] Zhu S, Ho S H, Huang X, Wang D, Yang F, Wang L, Wang C, Cao X, Ma F. Magnetic nanoscale zerovalent iron assisted biochar: interfacial chemical behaviors and heavy metals remediation performance. ACS Sustainable Chemistry & Engineering, 2017, 511(11): 9673–9682

[24] Zhao F, Tang W Z, Zhao D, Meng Y, Yin D, Sillanpää M. Adsorption kinetics, isotherms and mechanisms of Cd(II), Pb(II), Co(II) and Ni(II) by a modified magnetic polyacrylamide microcomposite adsorbent. Journal of Water Process Engineering, 2014, 4: 47–57

[25] Yang Z K, Lin L, Liu Y N, Zhou X, Yuan C Z, Xu A W. Supramolecular polymers-derived nonmetal N, S-codoped carbon nanosheets for efficient oxygen reduction reaction. RSC Advances, 2016, 658(58): 52937–52944

[26] Feng L L, Zou Y, Li C, Gao S, Zhou L J, Sun Q, Fan M, Wang H, Wang D, Li G D, Zou X. Nanoporous sulfur-doped graphitic carbon nitride microrods: a durable catalyst for visible-light-driven H₂ evolution. International Journal of Hydrogen Energy, 2014, 3928(28): 15373–15379

[27] Ko D, Mines P D, Jakobsen M H, Yavuz C T, Hansen H C B, Andersen H R. Disulfide polymer grafted porous carbon composites for heavy metal removal from stormwater runoff. Chemical Engineering Journal, 2018, 348: 685–692

[28] Zhu S, Wang S, Yang X, Tufail S, Chen C, Wang X, Shang J. Green sustainable and highly efficient hematite nanoparticles modified biochar-clay granular composite for Cr(VI) removal and related mechanism. Journal of Cleaner Production, 2020, 276: 123009

[29] Zhang Y, Xu Q, Zhang S, Liu J, Zhou J, Xu H, Xiao H, Li J. Preparation of thiol-modified Fe₃O₄@SiO₂ nanoparticles and their application for gold recovery from dilute solution. Separation and Purification Technology, 2013, 116: 391–397

[30] Yao T, Guo S, Zeng C, Wang C, Zhang L. Investigation on efficient adsorption of cationic dyes on porous magnetic polyacrylamide microspheres. Journal of Hazardous Materials, 2015, 292: 90–97

[31] Zheng X, Zheng H, Xiong Z, Zhao R, Liu Y, Zhao C, Zheng C. Novel anionic polyacrylamide-modify-chitosan magnetic composite nanoparticles with excellent adsorption capacity for cationic dyes and pH-independent adsorption capability for metal ions. Chemical Engineering Journal, 2020, 392: 123706

[32] Wei Z, Zhang Y, Ma X, Wang W. Insight into the high-efficiency adsorption of pyrene by Schiff base porous polymers: modelling and mechanism. Polymer, 2021, 220: 123576

[33] Wang Z, Wu Q, Zhang J, Zhang H, Feng J, Dong S, Sun J. In situ polymerization of magnetic graphene oxide-diaminopyridine composite for the effective adsorption of Pb(II) and application in battery industry wastewater treatment. Environmental Science and Pollution Research International, 2019, 2632(32): 33427–33439

[34] Zhang W, Lan Y, Ma M, Chai S, Zuo Q, Kim K H, Gao Y. A novel chitosan-vanadium-titanium-magnetite composite as a superior adsorbent for organic dyes in wastewater. Environment International, 2020, 142: 105798

[35] Cai W, Zhu F, Liang H, Jiang Y, Tu W, Cai Z, Wu J, Zhou J. Preparation of thiourea-modified magnetic chitosan composite with efficient removal efficiency for Cr(VI). Chemical Engineering Research & Design, 2019, 144: 150–158

[36] Othmani A, Magdouli S, Senthil Kumar P, Kapoor A, Chellam P V, Gokkus O. Agricultural waste materials for adsorptive removal of phenols, chromium(VI) and cadmium(II) from wastewater: a review. Environmental Research, 2022, 204(Pt A): 111916

[37] Pavithra S, Thandapani G, Sugashini S, Sudha P N, Alkhamis H H, Alrefaei A F, Almutairi M H. Batch adsorption studies on surface tailored chitosan/orange peel hydrogel composite for the removal of Cr(VI) and Cu(II) ions from synthetic wastewater. Chemosphere, 2021, 271: 129415

[38] Naicker C, Nombona N, van Zyl W E. Fabrication of novel magnetic chitosan/graphene-oxide/metal oxide nanocomposite beads for Cr(VI) adsorption. Chemical Papers, 2019, 74(2): 529–541

[39] Wang Z, Li T T, Peng H K, Ren H T, Lou C W, Lin J H. Low-cost hydrogel adsorbent enhanced by trihydroxy melamine and beta-cyclodextrin for the removal of Pb(II) and Ni(II) in water. Journal of Hazardous Materials, 2021, 411: 125029

[40] Yang H R, Li S S, Yang C, An Q D, Zhai S R, Xiao Z Y. Bi-layered hollow amphoteric composites: rational construction and ultra-efficient sorption performance for anionic Cr(VI) and cationic Cu(II) ions. Journal of Colloid and Interface Science, 2022, 607: 556–567

[41] Li R, An Q D, Xiao Z Y, Zhai B, Zhai S R, Shi Z. Preparation of PEI/CS aerogel beads with a high density of reactive sites for efficient Cr(VI) sorption: batch and column studies. RSC Advances, 2017, 7(64): 40227–40236

[42] Guo D M, An Q D, Xiao Z Y, Zhai S R, Yang D J. Efficient removal of Pb(II), Cr(VI) and organic dyes by polydopamine modified chitosan aerogels. Carbohydrate Polymers, 2018, 202: 306–314

[43] Yan Y Z, An Q D, Xiao Z Y, Zheng W, Zhai S G. Flexible core-shell/bead-like alginate@PEI with exceptional adsorption capacity, recycling performance toward batch and column sorption of Cr(VI). Chemical Engineering Journal, 2017, 313: 475–486

[44] Yan Y Z, An Q D, Xiao Z Y, Zhai S R, Zhai B, Shi Z. Interior multi-cavity/surface engineering of alginate hydrogels with polyethylenimine for highly efficient chromium removal in batch and continuous aqueous systems. Journal of Materials Chemistry A, 2017, 5(32): 17073–17087

[45] Yang H R, Yang C, Li S S, Shan X C, Song G L, An Q D, Zhai S R, Xiao Z Y. Site-imprinted hollow composites with integrated functions for ultra-efficient capture of hexavalent chromium from water. Separation and Purification Technology, 2022, 284: 120240

[46] Yang H R, Li S S, Shan X C, Yang C, An Q D, Zhai S R, Xiao Z Y. Hollow polyethyleneimine/carboxymethyl cellulose beads with abundant and accessible sorption sites for ultra-efficient chromium (VI) and phosphate removal. Separation and Purification Technology, 2022, 278: 119607

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos. 22076039 and 22176051), Science Foundation for Outstanding Youth of Henan Province (Grant No. 222300420054), and Excellent Science and Technology Innovation Team of Henan Normal University (Grant No. 2021TD03). The calculations were conducted on resources provided by the High Performance Computing Center of Henan Normal University.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-023-2303-2 and is accessible for authorized users.

RIGHTS & PERMISSIONS

2023 Higher Education Press