Activated carbon-hybridized and amine-modified polyacrylonitrile nanofibers toward ultrahigh and recyclable metal ion and dye adsorption from wastewater

Abstract

Nanofibers with high specific surface area and chemical stability have broad prospects in the applications of adsorption. However, the adsorption capacity is limited by the scarcity of adsorption groups and storage space. Herein, the activated carbon-hybridized and amine-modified nanofibers are prepared by integrating activated carbon (AC) and polyacrylonitrile (PAN) via electrospinning method and the subsequent amination, which could provide additional storage space and adsorption groups for ultrahigh adsorption capability. Thus, the obtained amine-rich porous PAN nanofibers (APAN/AC) readily realized the ultrahigh adsorption capacity for metal ions and dyes in wastewater. Specifically, the adsorption capacity of APAN/AC nanofibers were 284 mg·g⁻¹ for Cr(VI) and 248 mg·g⁻¹ for methyl orange, which were almost 2 and 4 times than that of amine-modified nanofibers (APAN) and carbon-hybridized nanofibers (PAN/AC), respectively. Moreover, the AC inhibited the chain mobility of polymer matrix and thereby endowing APAN/AC nanofibers with excellent recyclability. The adsorption capability retained 80% after nine adsorption-desorption cycles. The adsorption kinetics and corresponding mechanism were further explored. This strategy combines the advantages of polymer nanofibers and AC, opening a new avenue for developing next-generation absorbent materials.

Graphical abstract

Keywords

carbon-hybridized and amine-modified nanofibers / polyacrylonitrile / metal ions and dyes / wastewater / adsorption kinetics

References

[1] Tian L, Jiang H, Chen P, Wang Q, Niu P, Shi Y, Zhou M, Qing Y, Luo X. A novel GO/PNIPAm hybrid with two functional domains can simultaneously effectively adsorb and recover valuable organic and inorganic resources. Chemical Engineering Journal, 2018, 343: 607–618

[2] Yu J, Zhu S, Chen P, Zhu G T, Jiang X, Di S. Adsorption behavior and mechanism of Pb(II) on a novel and effective porphyrin-based magnetic nanocomposite. Applied Surface Science, 2019, 484: 124–134

[3] Chen C, Li F, Guo Z, Qu X, Wang J, Zhang J. Preparation and performance of aminated polyacrylonitrile nanofibers for highly efficient copper ion removal. Colloids and Surfaces. A, Physicochemical and Engineering Aspects, 2019, 568: 334–344

[4] Wang J, Yi H, Tang X, Zhao S, Gao F. Simultaneous removal of SO₂ and NO_x by catalytic adsorption using g-Al₂O₃ under the irradiation of non-thermal plasma: competitiveness, kinetic, and equilibrium. Chemical Engineering Journal, 2020, 384: 123334

[5] Cheng Y, He P, Dong F, Nie X, Ding C, Wang S, Zhang Y, Liu H, Zhou S. Polyamine and amidoxime groups modified bifunctional polyacrylonitrile-based ion exchange fibers for highly efficient extraction of U(VI) from real uranium mine water. Chemical Engineering Journal, 2019, 367: 198–207

[6] Ju P, Liu Q, Zhang H, Chen R, Liu J, Yu J, Liu P, Zhang M, Wang J. Hyperbranched topological swollen-layer constructs of multi-active sites polyacrylonitrile (PAN) adsorbent for uranium(VI) extraction from seawater. Chemical Engineering Journal, 2019, 374: 1204–1213

[7] Zhang L, Zhou D, Yao Q, Zhou J. Preparation of H₂TiO₃-lithium adsorbent by the sol-gel process and its adsorption performance. Applied Surface Science, 2016, 368: 82–87

[8] Gupta K, Gupta D, Khatri O P. Graphene-like porous carbon nanostructure from bengal gram bean husk and its application for fast and efficient adsorption of organic dyes. Applied Surface Science, 2019, 476: 647–657

[9] Yuan Y, Zhao S, Wen J, Wang D, Guo X, Xu L, Wang X, Wang N. Rational design of porous nanofiber adsorbent by blow-spinning with ultrahigh uranium recovery capacity from seawater. Advanced Functional Materials, 2019, 29(2): 1805380

[10] Zhu Z, Wu P, Liu G, He X, Qi B, Zeng G, Wang W, Sun Y, Cui F. Ultrahigh adsorption capacity of anionic dyes with sharp selectivity through the cationic charged hybrid nanofibrous membranes. Chemical Engineering Journal, 2017, 313: 957–966

[11] Shao Y, Zhou L, Bao C, Ma J, Liu M, Wang F. Magnetic responsive metal-organic frameworks nanosphere with core-shell structure for highly efficient removal of methylene blue. Chemical Engineering Journal, 2016, 283: 1127–1136

[12] Yuan X, Zhou C, Jin Y, Jing Q, Yang Y, Shen X, Tang Q, Mu Y, Du A K. Facile synthesis of 3D porous thermally exfoliated g-C₃N₄ nanosheet with enhanced photocatalytic degradation of organic dye. Journal of Colloid and Interface Science, 2016, 468: 211–219

[13] Liu Y, Xu L, Liu J, Liu X, Chen C, Li G, Meng Y. Graphene oxides cross-linked with hyperbranched polyethylenimines: preparation, characterization and their potential as recyclable and highly efficient adsorption materials for lead(II) ions. Chemical Engineering Journal, 2016, 285: 698–708

[14] Xiao J, Xu G, Wang L, Li P, Zhang W, Ma N, Tao M. Polyacrylonitrile fiber with strongly acidic electrostatic microenvironment: highly efficient and recyclable heterogeneous catalyst for the synthesis of heterocyclic compounds. Journal of Industrial and Engineering Chemistry, 2019, 77: 65–75

[15] Zhu H, Xu G, Du H, Zhang C, Ma N, Zhang W. Prolinamide functionalized polyacrylonitrile fiber with tunable linker length and surface microenvironment as efficient catalyst for knoevenagel condensation and related multicomponent tandem reactions. Journal of Catalysis, 2019, 374: 217–229

[16] Zheng L, Li P, Tao M, Zhang W. Regulation of polar microenvironment on the surface of tertiary amines functionalized polyacrylonitrile fiber and its effect on catalytic activity in Knoevenagel condensation. Catalysis Communications, 2019, 118: 19–24

[17] Zhao R, Li X, Sun B, Li Y, Li Y, Yang R, Wang C. Branched polyethylenimine grafted electrospun polyacrylonitrile fiber membrane: a novel and effective adsorbent for Cr(VI) remediation in wastewater. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2017, 5(3): 1133–1144

[18] Dai L, Cui L, Zhou D, Huang J, Yuan S. Resource recovery of Cr(VI) from electroplating wastewater: laboratory and pilot-scale investigation using fibrous weak anion exchanger. Journal of the Taiwan Institute of Chemical Engineers, 2015, 54: 170–177

[19] Deng S, Wang P, Zhang G, Dou Y. Polyacrylonitrile-based fiber modified with thiosemicarbazide by microwave irradiation and its adsorption behavior for Cd(II) and Pb(II). Journal of Hazardous Materials, 2016, 307: 64–72

[20] Xiao J, Wang L, Ran J, Zhao J, Tao M, Zhang W. Highly selective removal of cationic dyes from water by acid-base regulated anionic functionalized polyacrylonitrile fiber: fast adsorption, low detection limit, reusability. Reactive & Functional Polymers, 2020, 146: 104394

[21] Wang B, Chen P Y, Zhao R X, Zhang L, Chen Y, Yu L P. Carbon-dot modified polyacrylonitrile fibers: recyclable materials capable of selectively and reversibly adsorbing small-sized anionic dyes. Chemical Engineering Journal, 2019, 391: 123484

[22] Liu J, Su D, Yao J, Huang Y, Shao Z, Chen X. Soy protein-based polyethylenimine hydrogel and its high selectivity for copper ion removal in wastewater treatment. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2017, 5(8): 4163–4171

[23] Deng S, Zhang G, Wang X, Zheng T, Wang P. Preparation and performance of polyacrylonitrile fiber functionalized with iminodiacetic acid under microwave irradiation for adsorption of Cu(II) and Hg(II). Chemical Engineering Journal, 2015, 276: 349–357

[24] Bai H, Li Y, Zhang H, Chen H, Wu W, Wang J, Liu J. Anhydrous proton exchange membranes comprising of chitosan and phosphorylated graphene oxide for elevated temperature fuel cells. Journal of Membrane Science, 2015, 495: 48–60

[25] Hughes D L, Afsar A, Harwood L M, Jiang T, Laventine D M, Shaw L J, Hodson M E. Adsorption of Pb and Zn from binary metal solutions and in the presence of dissolved organic carbon by DTPA-functionalised, silica-coated magnetic nanoparticles. Chemosphere, 2017, 183: 519–527

[26] Abdi J, Vossoughi M, Mahmoodi N M, Alemzadeh I. Synthesis of metal-organic framework hybrid nanocomposites based on GO and CNT with high adsorption capacity for dye removal. Chemical Engineering Journal, 2017, 326: 1145–1158

[27] Chen D, Sun H, Wang Y, Quan H, Ruan Z, Ren Z, Luo X. UiO-66 derived zirconia/porous carbon nanocomposites for efficient removal of carbamazepine and adsorption mechanism. Applied Surface Science, 2020, 507: 145054

[28] Li X, Yuan H, Quan X, Chen S, You S. Effective adsorption of sulfamethoxazole, bisphenol A and methyl orange on nanoporous carbon derived from metal-organic frameworks. Journal of Environmental Sciences (China), 2018, 63: 250–259

[29] Li Y, Qi B, Wan Y. Separation of monosaccharides from pretreatment inhibitors by nanofiltration in lignocellulosic hydrolysate: fouling mitigation by activated carbon adsorption. Biomass and Bioenergy, 2020, 136: 105527

[30] Onuki S, Koziel J A, Jenks W S, Cai L, Rice S, van Leeuwen J. Ethanol purification with ozonation, activated carbon adsorption, and gas stripping. Separation and Purification Technology, 2015, 151: 165–171

[31] Guillossou R, Le Roux J, Mailler R, Pereira-Derome C S, Varrault G, Bressy A, Vulliet E, Morlay C, Nauleau F, Rocher V, Gasperi J. Influence of dissolved organic matter on the removal of 12 organic micropollutants from wastewater effluent by powdered activated carbon adsorption. Water Research, 2020, 172: 115487

[32] Zhao L, Li Y, Zhang H, Wu W, Liu J, Wang J. Constructing proton-conductive highways within an ionomer membrane by embedding sulfonated polymer brush modified graphene oxide. Journal of Power Sources, 2015, 286: 445–457

[33] Zhang H, He Y, Zhang J, Ma L, Li Y, Wang J. Constructing dual-interfacial proton-conducting pathways in nanofibrous composite membrane for efficient proton transfer. Journal of Membrane Science, 2016, 505: 108–118

[34] Jones B, Britton J, Mafukidze D, Nyokong T. Photodegradation of 4-chlorophenol using Zn and In phthalocyanines substituted with pyrrole without hetero atoms linkers and supported on polyacrylonitrile electrospun fibres. Polyhedron, 2020, 178: 114329

[35] Liu Z T, Yang Y, Zhang L, Sun P, Liu Z W, Lu J, Xiong H, Peng Y, Tang S. Study on the performance of ramie fiber modified with ethylenediamine. Carbohydrate Polymers, 2008, 71(1): 18–25

[36] Neghlani P K, Rafizadeh M, Taromi F A. Preparation of aminated-polyacrylonitrile nanofiber membranes for the adsorption of metal ions: comparison with microfibers. Journal of Hazardous Materials, 2011, 186(1): 182–189

[37] Yuan Z, Wu X, Jiang Y, Li Y, Huang J, Hao L, Zhang J, Wang J. Carbon dots-incorporated composite membrane towards enhanced organic solvent nanofiltration performance. Journal of Membrane Science, 2018, 549: 1–11

[38] Bouchoum H, Benmoussa D, Jada A, Tahiri M, Cherkaoui O. Synthesis of amidoximated polyacrylonitrile fibers and its use as adsorbent for Cr(VI) ions removal from aqueous solutions. Environmental Progress & Sustainable Energy, 2019, 38(5): 13196

[39] Liu X, Tian J, Li Y, Sun N, Mi S, Xie Y, Chen Z. Enhanced dyes adsorption from wastewater via Fe₃O₄ nanoparticles functionalized activated carbon. Journal of Hazardous Materials, 2019, 373: 397–407

[40] Ma Y, Zhang B, Ma H, Yu M, Li L, Li J. Electrospun nanofibrous polyethyleneimine mat: a potential adsorbent for removal of chromate and arsenate from drinking water. RSC Advances, 2016, 6(36): 30739–30746

[41] Weckhuysen B M, Wachs I E, Schoonheydt R A. Surface chemistry and spectroscopy of chromium in inorganic oxides. Chemical Reviews, 1996, 96(8): 3327–3350

[42] Chen S, Xie F. Selective adsorption of Copper (II) ions in mixed solution by Fe₃O₄-MnO₂-EDTA magnetic nanoparticles. Applied Surface Science, 2020, 507: 145090

[43] Jiang X, Xiang X, Peng S, Hou L. Facile preparation of nitrogen-doped activated mesoporous carbon aerogel from chitosan for methyl orange adsorption from aqueous solution. Cellulose (London, England), 2019, 26(7): 4515–4527

[44] Li Y, Zhao R, Chao S, Sun B, Wang C, Li X. Polydopamine coating assisted synthesis of MnO₂ loaded inorganic/organic composite electrospun fiber adsorbent for efficient removal of Pb²⁺ from water. Chemical Engineering Journal, 2018, 344: 277–289

[45] Qiu J, Liu F, Cheng S, Zong L, Zhu C, Ling C, Li A. Recyclable nanocomposite of flowerlike MoS₂@Hybrid acid-doped PANI immobilized on porous PAN nanofibers for the efficient removal of Cr(VI). ACS Sustainable Chemistry & Engineering, 2018, 6(1): 447–456

Acknowledgements

This work is supported by Natural Science Foundation of Henan Province (Grant No. 182300410276), the National Natural Science Foundation of China (Grant No. 51904274) and Program for Innovative Research Team (in Science and Technology) in University of Henan Province (Grant No. 19IRTSTHN028).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-020-2000-3 and is accessible for authorized users.

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