Adsorption treatment of wastewater by electrospun nanofiber membranes: A review
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摘要: 静电纺丝纳米纤维膜具有独特的网状结构和相连通的微孔道,作为一种新型吸附材料,具有比表面积大、孔隙率高、易改性、易回收和化学稳定性好等优势,在吸附废水中的污染物方面得到了广泛的应用。本文首先简单介绍了静电纺丝的工作原理,随后,概述了静电纺丝纳米纤维膜作为吸附剂用于水污染处理的最新研究进展,主要包括有机污染物、无机阴离子、重金属离子的吸附去除及在海水淡化方面的应用。同时,讨论了电纺纳米纤维膜对污染物的吸附机制。最后,展望了静电纺丝纳米纤维膜材料在污水处理中存在的挑战和前景。本综述无论从宏观上电纺纳米纤维膜的设计与合成还是微观的吸附去除机制,都可帮助研究者对静电纺丝纳米纤维膜材料有更深刻的理解。Abstract: Electrospun nanofiber membrane has a unique network structure and connected micropores. With the advantages of large specific surface area, high porosity, easy modification, easy recycling and good chemical stability, it has been widely used in wastewater treatment as a new type of adsorption material. In this paper, first, the working principle of electrospinning is briefly introduced. Then, the latest research progress of electrospun nano-fiber membrane as adsorbents in wastewater treatment is reviewed, mainly including the removal of organic pollutants, inorganic anions and heavy metal ions, as well as the application of desalination. Besides, the adsorption mechanisms are summarized. Finally, the challenges and prospects of electrospun nanofiber membrane in wastewater treatment are discussed. This review may help researchers have a deeper understanding of electrospun nanofiber membrane materials, whether in the design and synthesis of nanofibers at the macro level or the adsorption mechanisms microscopically .
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Key words:
- electrospinning nanofiber /
- composite membrane /
- wastewater treatment /
- adsorption /
- mechanism
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图 5 超声处理制备聚偏氟乙烯(PVDF)/氧化石墨烯(GO)复合膜的过程示意图:(a) 通过静电纺丝技术制备的PVDF纤维膜;(b) 在超声处理过程中PVDF膜在GO水溶液中溶胀;(c) GO迁移到溶胀的PVDF膜的孔中;(d) 停止超声处理后GO片被限制在PVDF膜中[36]
Figure 5. Schematic representations showing the preparation process of the composite poly vinylidene fluoride (PVDF)/graphene oxide (GO) membrane with the aid of ultrasonic treatment: (a) PVDF fibrous membrane as prepared through the electrospinning technology; (b) PVDF membrane was swelled in the GO aqueous solution during the ultrasonication process; (c) GO migrated into the pores of the swelled PVDF membrane; (d) Stopping ultrasonic treatment and GO platelets were restricted in the PVDF membrane[36]
表 1 不同吸附剂对废水中污染物的吸附性能比较
Table 1. Comparison of adsorption performance of different adsorbents for pollutants in wastewater
Adsorbent Pollutant Adsorption condition Maximum adsorption
capacity/(mg·g−1)Regeneration rate
after 5 cyclesRef. PVDF/GO membrane MB T=30℃, adsorption time
(24 h),100 mL MB solution
(50 mg/L)621.1 >50% [36] PDA-MPs incorporated electrospun fibers MB pH=9.0, T=55℃ 1 722.1 >80% [37] PDA@DCA-COOH membrane MB, CR dosage membranes (30 mg)
T=25℃
50 mg/L MB, 100 mg/L CR69.89, 67.31 96%, 80% [38] PES nanofibrous membranes MB — 2257.88 81.45% [39] PES composite nanofibrous membranes RB pH=5.0, initial concentration of RB is 5 μmol/L — 95% [40] PQAM MO T=45℃, pH=3 909.8 >85% [41] Electrospun CuO-ZnO composite nanofibers CR dosage of fibers (8 mg)
5 mL CR solution (50 mg/L)126.4 — [42] Hierarchical C/NiO-ZnO nanocomposite fibers CR T=30℃, pH=6-7 613 >98% [43] p(NIPAM-co-MAA)/β-CD fibers CV T=55℃, pH=9 1 253.78 >73% [44] AN-co-ST electrospun nanofibers BV 14 pH=6.2, 50 mL dye solution,
0.1g fibers67.11 — [45] Fe3O4/PAN composite electrospun nanofiber mat TC pH=6, T=25℃
10 mg fibers, 20 mL TC solution257.07 — [46] MMT-CA-NFM CIP — 13.8 73% [48] 9%Ni@CNF SDZ T=45℃
SDZ solution (2.5 mg/L)103.21 — [49] PAF-45-PP modified electrospun fiber membrane IBPF, CLXN, DEET PPCPs solution (50 mg/L)
Dosage of membrane
(0.2 g/L)613.50, 429.18, 384.61 >98% [52] PAN/o-CNTs electrospun nanofibers Pyrene Dosage of fibers (0.25 mg)
Pyrene solution (0.2 g/L)1.488 98% [53] MgSi/PAN composite fibers Diquat pH=8 197.53 [54] MWCNTs-LCEFMs Phenolic pollutants — — — [55] One-dimension ZrO2 mesoporous fibers F− pH=3, 30 mg fibers
50 mL fluoride solution297.70 — [62] CNF-NiO Cl− 0.5 g/L NaCl solution
Voltage=1.2 V6.2 >95% [63] Hydrophilic carbon nanofiber fabric Cl− Voltage=1.2 V 19.34 >94% [64] CNFZIF Cl− Voltage=1.2 V,
flow rate=20 mL/min50.88 — [65] CNF@Mn2O3 Cl− Voltage=1.2 V 27.43 >94% [66] Graphene hydrogel and ZrO2−doped TiO2 nanofibers Cl− Voltage=1.2 V 9.34 — [67] Ultrathin MnOx−modified porous carbon nanofiber Cl− 0.5 g/L NaCl solution,
flow rate= 10 mL/min,
voltage=1.2 V9.23 — [68] LNPPM PO3- 4 0.4 g fibers
100 mL phosphate solution
pH=7165.9 — [70] Chitosan/Al2O3/Fe3O4 composite nanofibrous NO- 3 50 mg fibers, pH=3, T=20℃
100 mL nitrate solution
(20 mg/L)160.7 — [71] ABN/TPU-NFM NO- 3 Nitrate solution (25 mg/L) 14.9 — [72] PAN/TiO2 composite nanofibers Pb2+ pH=5
Pb2+ initial concentration is 600 mg/L193 — [74] The crosslinked PVA nanofibers Pb2+ Pb2+ initial concentration is 100 mg/L 168.3 — [75] DR-EDTA/PAN membrane Cu2+ pH=6.5,T=60℃
Adsorption time is 12 h47.6 >99% [77] MgAl-EDTA-LDH@PAN composite membrane Cu2+ Cu2+ initial concentration (64 mg/L)
Dosage of membrane
(1.50 g/L)120.77 — [13] PVC/TNT composite membranes Cu2+ — — 94% [78] PS fibrous mats coated with CS-REC nanospheres Cu2+ pH=3
Cu2+ initial concentration (50 mg/L)134 — [79] PAN/TiO2 electrospun nanofibers Cd2+ pH=7
Cd2+ initial concentration (600 mg/L)91 — [74] EDTA-EDA-PAN modified nanofibers Cd2+ T=25℃ 32.68 >55% [81] PAN/MOF-808“hydractivated” composite membrane Cd2+ pH=4.6±0.2
Dosage of membrane
(20 mg)
30 mL Cd2+ solution225.055 — [82] EDTA-EDA-PAN modified nanofibers Cr(VI) T=25℃ 66.24 90% [81] Nanosized chitosan fibers Cr(VI) pH=3 131.58 — [83] PAN/PEI/Ppy nanofiber membrane Cr(VI) pH=3
Cr(VI) initial concentration (400 mg/L)368 >76% [84] ZCNs As(III), As(V) T=40℃ 28.61, 106.57 90% [85] Ce-CHT/PVA complex fiber As(III) — 18.0 — [86] PAN/SiO2/APTES composite nanofiber membrane Th4+, U6+ T=45℃ 249.4, 193.1 >88% [87] PAN/CNS nanofibrous membrane La3+ — 174.5 80% [88] PAA-S HNFs La3+, Eu3+, Tb3+ pH=6
Initial concentration is
250 mg/L232.6, 268.8, 250.0 70% [89] Notes: PVDF/GO—Poly vinylidene fluoride/graphene oxide; PDA-MPs—Polydopamine microspheres; PES—Polyethersulfone; PQAM—Poly(quaternary ammonium) modified nanofibrous membranes; p(NIPAM-co-MAA)/β-CD—Poly(N-isopropylacrylamide-co-methacrylic acid)/β-cyclodextrin; AN-co-ST—Acrylonitrile-co-styrene; PAN—Polyacrylonitrile; MMT-CA-NFM—Montmorillonite-impregnated cellulose acetate nanofiber membranes; CNF—Carbon nanofiber; PAFs—Porous aromatic frameworks; FM—Fiber membrane; MWCNTs-LCEFMs—Laccase-carrying electrospun fibrous membranes; PEI—Polyethyleneimine; ABN/TPU-NFM—ABN impregnated electrospun thermoplastic polyurethane nanofibrous membrane; DR-EDTA/PAN—Diazoresin-ethylene diamine tetraacetic acid/polyacrylonitrile; CS-REC—Chitosan-rectorite; EDA—Ethylenediamine; Ppy—Polypyrrole; ZCNs—Zirconia embedded in carbon nanowires; CHT—Chitin; APTES—Aminopropyltriethoxysilane; CNS—Carbonaceous nanospheres; PAA-S HNFs—Polyacrylic acid−silica hydrogel nanofibers; MB—Methylene blue; CR—Congo red; MO—Methyl orange; RB—Rhodamine B; CV—Crystal violet; BV 14—Basic violet 14; TC—Tetracycline; CIP—Ciprofloxacin; SDZ—Sulfadiazine; PPCP—Pharmaceuticals and personal care product; IBPF—Ibuprofen; CLXN—Chloroxylenol; DEET—N,N-diethyl-meta-toluamide. -
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