Journal of Textile Research ›› 2026, Vol. 47 ›› Issue (1): 54-62.doi: 10.13475/j.fzxb.20250603301

• Fiber Materials • Previous Articles     Next Articles

Preparation and Cr(Ⅵ) adsorption of polyacrylonitrile/covalent organic framework composite nanofiber membranes

LING Lei1, CHEN Kai1, GAO Jun1, WU Dingsheng1, WANG Dengbing2, ZHANG Chun3, FENG Quan1()   

  1. 1. College of Textiles and Garments, Anhui Polytechnic University, Wuhu, Anhui 241000, China
    2. School of Materials and Chemical Engineering, Wuhu University, Wuhu, Anhui 241000, China
    3. Jiangsu JIUWU HI-TECH Co., Ltd., Nanjing, Jiangsu 211800, China
  • Received:2025-06-17 Revised:2025-10-24 Online:2026-01-15 Published:2026-01-15
  • Contact: FENG Quan E-mail:fengquan@ahpu.edu.cn

RichHTML

7

PDF (PC)

29

Abstract:

Objective In view of the serious threat cauced by hexavalent chromium (Cr(Ⅵ)) pollution to the ecological environment and human health, current mainstream adsorbent materials still have significant limitations in terms of removal efficiency and recycling. Therefore, the development of highly efficient, stable, and highly selective adsorptive detoxification materials for the treatment of Cr(Ⅵ)-containing wastewater has important practical significance.

Method Polyacrylonitrile (PAN)/1,4-phenylenediamine (Pa) blended fibers were prepared by electrospinning, which were immersed in a solution of 1,3,5-benzenetricarboxaldehyde (Tp) to in situ grow covalent organic framework (COF), thus obtaining a composite membrane. The membrane was characterized by scanning electron microscopy (SEM), X-ray diffractometer (XRD), Fourier transform infrared spectrometer (FT-IR) and X-ray photoelectron spectrometer (XPS). Its adsorption performance was evaluated under conditions of different pH values, temperatures and Cr(Ⅵ) concentrations, and its adsorption isotherm, adsorption thermodynamics and adsorption kinetics were analyzed.

Results The surface of the raw electrospun PAN/Pa fibers was smooth and uniform. Following the in situ growth of the COF, a nanoscale dendritic COF morphology was successfully constructed on the fiber surface, forming a hierarchical porous network and significantly increasing roughness. XRD patterns showed the characteristic crystal planes of the COF, while FT-IR spectra displayed the distinct C≡N vibration of PAN and the key functional group vibrations (C=O, C—N, N—H) of the COF. The attenuation of amino-related FT-IR peaks after Cr(VI) adsorption indicated the direct participation of these groups in the adsorption process. The composite PAN/COF nanofiber membrane exhibited enhanced rigidity, with a tensile stress of 8.3 MPa, a strain of 8.8%, and an elastic modulus of 94.3 MPa, compared to the more ductile pure PAN/Pa membrane. Its hydrophilicity was also improved, evidenced by a decrease in the water contact angle from 65.18° to 49.65°. Adsorption performance for Cr(VI) was highly dependent on solution conditions; and capacity increased with temperature and decreased with rising pH. This pH dependence is attributed to the protonation of amino groups under acidic conditions, enhancing electrostatic attraction, while deprotonation occurs under alkaline conditions. A maximum adsorption capacity of 99.4 mg/g was achieved under the conditions of 318 K and pH=1. Analysis of the adsorption process revealed that the isotherm conformed to the Freundlich model, suggesting multilayer adsorption on a heterogeneous surface. Thermodynamic parameters confirmed the process was spontaneous and endothermic. Adsorption kinetics followed the pseudo-second-order model, and XPS analysis indicated that approximately 46.7% of the adsorbed Cr(VI) was reduced to less toxic Cr(III), jointly pointing to a dominant chemisorption mechanism. Furthermore, the membrane demonstrated promising reusability, maintaining over 80% of its initial adsorption efficiency after seven adsorption-desorption cycles.

Conclusion The PAN/COF composite nanofiber membrane was prepared by electrospinning and in situ growth method for the adsorption and reduction treatment of Cr(Ⅵ)-containing wastewater. Characterizations by SEM, XRD and FT-IR prove that the PAN/COF composite nanofiber membrane with good mechanical properties and hydrophilicity has been successfully prepared. The influences factors such as temperature, pH value, initial Cr(Ⅵ) concentration and contact time on the adsorption performance were studied. The results showed that at 318 K and pH=1, the maximum adsorption capacity of the membrane for 100 mg/L Cr(Ⅵ) could reach 99.4 mg/g. The study of the adsorption mechanism indicated that the adsorption process of Cr(Ⅵ) on the PAN/COF composite membrane conformed to the characteristics of multi-molecular layer adsorption, was a spontaneous endothermic reaction, and was dominated by chemical adsorption. In addition, the composite membrane has good reduction performance and reusability.

Key words: hexavalent chromium, polyacrylonitrile, covalent organic framework, electrospinning, nanofiber membrane, adsorption, wastewater treatment, heavy metal ion

CLC Number: 

  • TQ340.64

Fig.1

SEM images of nanofiber membranes"

Fig.2

XRD patterns of materials"

Fig.3

XPS total patterns (a) and FT-IR spectra (b) of materials"

Fig.4

Mechanical and hydrophilic properties of different samples. (a) Stress-strain curves; (b) Static contact angles"

Tab.1

Influence of temperature on adsorption performance of different samples"

样品名称 吸附量/(mg·g-1)
298 K 308 K 318 K
PAN/Pa 37.2 54.3 58.3
PAN/COF 52.1 76.0 99.4

Fig.5

Influence of pH value on Cr(Ⅵ) adsorption performance of PAN/COF composite nanofiber membrane"

Fig.6

Influence of Cr(Ⅵ) mass concentration on Cr(Ⅵ) adsorption performance of PAN/COF composite nanofiber membrane"

Fig.7

Adsorption isotherm. (a) Nonlinear isotherm at 298 K; (b) Nonlinear isotherm at 308 K; (c) Nonlinear isotherm at 318 K; (d) Langmuir adsorption isotherm; (e) Freundlich adsorption isotherm"

Tab.2

Adsorption isotherm parameters"

温度/K Langmuir模型 Freundlich模型
Qm/(mg·g-1) KL/(L·mg-1) R2 KF/(mg(1-n)·Ln·g-1) n R2
298 70.76 0.045 0.988 23.59 0.208 0.975
308 105.07 0.078 0.985 0.021 8 0.839 0.999
318 116.11 0.267 0.998 63.85 0.132 0.989

Fig.8

Adsorption thermodynamics. (a) Influence of temperature on Langmuir reaction rate constant; (b) Van't Hoff plot"

Tab.3

Adsorption thermodynamic parameters"

温度/K Qm/
(mg·g-1)		 KL/
(L·mg-1)		 ΔG/
(kJ·mol-1)		 ΔH/
(kJ·mol-1)		 ΔS/
(J·K-1)
298 70.76 0.045 2 7 672.19 70 347.39 209.25
308 105.07 0.077 8 6 539.07
318 116.11 0.267 4 3 487.27

Fig.9

Adsorption kinetics models. (a) Nonlinear fitting of pseudo first and pseudo second order dynamics; (b) Adsorption kinetic model of Pseudo-first-order; (c) Adsorption kinetic model of Pseudo-second-order"

Tab.4

Adsorption kinetic model parameters"

准一级 准二级
Qe=47.30 mg/g Qe=54.55 mg/g
k1=0.007 75 min-1 k2=0.017 56 g/(mg·min)
R2=0.959 R2=0.996

Fig.10

XPS spectra. (a) XPS total spectra; (b) Cr 2p fine spectra"

Fig.11

Reusable performance of PAN/COF composite nanofiber membrane"

[1] SINGH V, AHMED G, VEDIKA S, et al. Toxic heavy metal ions contamination in water and their sustainable reduction by eco-friendly methods: isotherms, thermodynamics and kinetics study[J]. Scientific Reports, 2024, 14: 7595.
doi: 10.1038/s41598-024-58061-3 pmid: 38556536
[2] DHOKPANDE S R, DESHMUKH S M, KHANDEKAR A, et al. A review outlook on methods for removal of heavy metal ions from wastewater[J]. Separation and Purification Technology, 2024, 350: 127868.
doi: 10.1016/j.seppur.2024.127868
[3] YASIN M U, HAIDER Z, MUNIR R, et al. The synergistic potential of biochar and nanoparticles in phytoremediation and enhancing cadmium tolerance in plants[J]. Chemosphere, 2024, 354: 141672.
doi: 10.1016/j.chemosphere.2024.141672
[4] SHARMA B, SINGH A, SHARMA A, et al. Synthesis and characterization of zinc selenide/graphene oxide (ZnSe/GO) nanocomposites for electrochemical detection of cadmium ions[J]. Applied Physics A, 2024, 130(5): 297.
doi: 10.1007/s00339-024-07472-0
[5] VITELLI V, GIAMBORINO A, BERTOLINI A, et al. Cadmium stress signaling pathways in plants: molecular responses and mechanisms[J]. Current Issues in Molecular Biology, 2024, 46(6): 6052-6068.
doi: 10.3390/cimb46060361 pmid: 38921032
[6] ZHAO X N, ZHANG Y, GUO Y Y, et al. Preparation of magnetic hydroxyapatite whisker and its adsorption capacity to cadmium ion[J]. Materials Today Communications, 2024, 38: 108116.
doi: 10.1016/j.mtcomm.2024.108116
[7] SHERAZ N, SHAH A, HALEEM A, et al. Comprehensive assessment of carbon-, biomaterial- and inorganic-based adsorbents for the removal of the most hazardous heavy metal ions from wastewater[J]. RSC Advances, 2024, 14(16): 11284-11310.
doi: 10.1039/d4ra00976b pmid: 38595713
[8] ELEK G, MÜLLER M. Ervin Bauer's concept of biological thermodynamics and its different evalua-tions[J]. BioSystems, 2024, 235: 105090.
doi: 10.1016/j.biosystems.2023.105090
[9] ALI ALATABE M J, GHORBANPOUR M. A performance comparison of photo-Fenton decolorization of methylene blue by using bentonite/iron composites prepared by liquid phase and solid phase ion exchange method[J]. Desalination and Water Treatment, 2024, 317: 100027.
doi: 10.1016/j.dwt.2024.100027
[10] HSU C Y, AJAJ Y, MAHMOUD Z H, et al. Adsorption of heavy metal ions use chitosan/graphene nanocomposites: a review study[J]. Results in Chemistry, 2024, 7: 101332.
doi: 10.1016/j.rechem.2024.101332
[11] 庄严, 黄赳, 朱晓芳, 等. 铁碳纤维纳米二氧化铈复合材料吸附As的性能与机理[J]. 中国环境科学, 2024, 44(10): 5596-5606.
ZHUANG Yan, HUANG Jiu, ZHU Xiaofang, et al. Arsenic adsorption performance and mechanism using the iron-carbon fiber and nano cerium dioxide incorporated composite adsorbent[J]. China Environmental Science, 2024, 44(10): 5596-5606.
[12] 王永政, 黄林涛, 宋付权. 石油沥青/聚丙烯腈静电纺碳纳米纤维的制备工艺优化及其性能[J]. 纺织学报, 2024, 45(8): 107-115.
WANG Yongzheng, HUANG Lintao, SONG Fuquan. Process optimization and properties of petroleum pitch/polyacrylonitrile electrospun carbon nanofibers[J]. Journal of Textile Research, 2024, 45(8): 107-115.
[13] GODIYA C B, REVADEKAR C, KIM J, et al. Amine-bilayer-functionalized cellulose-chitosan composite hydrogel for the efficient uptake of hazardous metal cations and catalysis in polluted water[J]. Journal of Hazardous Materials, 2022, 436: 129112.
doi: 10.1016/j.jhazmat.2022.129112
[14] ZHAO B X, GAO B, SHI H X, et al. In situ removal of Cr6+ with an intelligent adsorbent: microwave synthesis, interface adsorption, thermodynamics, mechanism and self-regeneration[J]. Journal of Environmental Chemical Engineering, 2024, 12(2): 112045.
doi: 10.1016/j.jece.2024.112045
[15] HUANG W T, XU Y P, CHEN N S, et al. Amino-modified hemp stem for high-capacity adsorption of Cr(VI) from aqueous solution[J]. Journal of Environmental Chemical Engineering, 2023, 11(6): 111441.
doi: 10.1016/j.jece.2023.111441
[16] TONG Z B, MA D K, WU J N, et al. TpPa-1/{0 1 0}-BiVO4 S-scheme heterojunction fabricated on specific crystal facets for highly efficient H2O2 artificial photosynthesis[J]. Chemical Engineering Journal, 2024, 496: 154262.
doi: 10.1016/j.cej.2024.154262
[17] SHARMA D S, PATEL A P, BARIYA S N, et al. Electrospun PbS/PAN-PANI carbon nanofibers decorated on carbon cloth as pseudo-electrochemical capacitor material[J]. ACS Applied Electronic Materials, 2024, 6(5): 3617-3629.
doi: 10.1021/acsaelm.4c00320
[18] LIAO G M, KANG J J, ZHANG H P, et al. Covalent and non-covalent interaction of myofibrillar protein and cyanidin-3-O-glucoside: focus on structure, binding sites and in vitro digestion properties[J]. Journal of the Science of Food and Agriculture, 2024, 104(2): 905-915.
doi: 10.1002/jsfa.v104.2
[19] SHEN H Z, CHEN L, ZHOU C L, et al. Immobilizing Fe0 nanoparticles on covalent organic framework towards enhancement of Cr(VI) removal by adsorption and reduction synergistic effect[J]. Separation and Purification Technology, 2022, 290: 120883.
doi: 10.1016/j.seppur.2022.120883
[20] ZHOU Z Y, HU X L, ZHOU P, et al. Self-powered TpPa/PAN membrane-based flexible hydrovoltaic sensor for real-time Congo red monitoring[J]. Sensors and Actuators B: Chemical, 2025, 432: 137507.
doi: 10.1016/j.snb.2025.137507
[21] FAN X L, SONG X, SUN J X, et al. Hydrophilic/hydrophobic heterojunctions for enhanced photocatalytic hydrogen evolution via gas release dynamics[J]. Journal of Colloid and Interface Science, 2025, 683: 531-541.
doi: 10.1016/j.jcis.2024.12.095 pmid: 39700562
[22] JIAO H P, BI R X, XU A H, et al. Efficient adsorption and advanced purification of metal ions induced by synergistic effect of amine and thione on covalent organic frameworks[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2024, 691: 133924.
doi: 10.1016/j.colsurfa.2024.133924
[23] AN Q, WANG L L, ZHAO G F, et al. Constructing cooperative interface via bi-functional COF for facilitating the sulfur conversion and Li+ dynamics[J]. Advanced Materials, 2024, 36(4): 2305818.
doi: 10.1002/adma.v36.4
[24] SONG Z Y, XU Y T, ZHANG M Y, et al. Efficient removal of Cr (VI) by Bifunction zinc porphyrin COF: coupling adsorption with photocatalysis, performance evaluation, and mechanism analysis[J]. Journal of Colloid and Interface Science, 2025, 677: 346-358.
doi: 10.1016/j.jcis.2024.07.140 pmid: 39096703
[25] ZHONG X, LU Z P, LIANG W, et al. The magnetic covalent organic framework as a platform for high-performance extraction of Cr(VI) and bisphenol A from aqueous solution[J]. Journal of Hazardous Materials, 2020, 393: 122353.
doi: 10.1016/j.jhazmat.2020.122353
[1] KONG Yanhui, ZHANG Linping, MAO Zhiping, XU Hong. Preparation and hemostatic properties of methacryloyl gelatin fiber membranes [J]. Journal of Textile Research, 2026, 47(1): 1-10.
[2] ZHAO Jingwen, YUAN Xiangnan, GAO Jing, WANG Lu. Preparation and properties of polyacrylonitrile-Prussian blue/lactic acid/ciprofloxacin photothermal responsive antibacterial dressings [J]. Journal of Textile Research, 2026, 47(1): 20-28.
[3] WANG Shihao, XU Xiaoyu, ZHENG Ting, WANG Jinxing, YAO Degang, WANG Jun, YE Xiangyu, TIAN Hui, LI Ting, ZHU Feichao. Research applications and prospect of carbon fiber nonwovens [J]. Journal of Textile Research, 2026, 47(1): 240-249.
[4] LUO Jiajun, HE Yaoquan, ZHAO Zhenhong, LI Jindao, ZHAO Jing, HUANG Gang, WANG Xianfeng. Preparation and properties of styrene-ethylene-butene-styrene/fluorinated polyimide waterproof and moisture permeable fibrous membranes [J]. Journal of Textile Research, 2026, 47(1): 38-45.
[5] LIU Ke, WANG Yuxi, CHENG Pan, ZHU Liping, XIA Ming, MEI Tao, XIANG Yang, ZHOU Feng, GAO Fei, WANG Dong. Preparation of porous sulfonated hydrogenated styrene-butadiene block copolymer fiber membrane and its adsorption performance for lysozyme [J]. Journal of Textile Research, 2025, 46(12): 1-10.
[6] WANG Xiaohu, BAO Anna, WEI Jingwen, ZHAO Xiaoman, HAN Xiao, HONG Jianhan. One-step fabrication and application of cross-scale sensing yarns via synergistic electrospinning-electrospraying process [J]. Journal of Textile Research, 2025, 46(12): 101-109.
[7] LIU Jinyang, LI Chengcai, ZHU Hailin, GUO Yuhai, JIANG Xueliang. Preparation and oil-water separation performance of asymmetric structure polytetrafluoroethene empty tube fiber membrane [J]. Journal of Textile Research, 2025, 46(12): 11-18.
[8] CHEN Ming, ZHANG Hao, ZHANG Ziyuan, YANG Qingbiao, GAO Ji, FAN Cunwei, SUN Jie. Synthesis and dyeing properties of acid dyes containing bio-based moieties [J]. Journal of Textile Research, 2025, 46(12): 142-151.
[9] XIE Weiwei, ZHU Qingpeng, SONG Jiaojiao, CHEN Zhiming. Synthesis of magnetic immobilized laccase and its efficient degradation of dyes [J]. Journal of Textile Research, 2025, 46(12): 163-170.
[10] LI Zongjie, LI Tengfei, LU Yihan, KANG Weimin. Research progress in coupled electrospinning of multifunctional and multilevel structured nanofiber filtration materials [J]. Journal of Textile Research, 2025, 46(12): 19-28.
[11] JI Qiao, YU Qingyuan, ZHOU Aihui, MA Bomou, XU Jin, YUAN Jiugang. Research progress in application of bacterial cellulose composites [J]. Journal of Textile Research, 2025, 46(12): 243-250.
[12] LIU Qingqing, MAO Xiaohui, YAO Yan, SUN Ying, CHEN Yu, ZHANG Xiaozhe, ZHU Liping, WANG Xuefen. Recent advances in fibrous separation membranes for functional modification and applications [J]. Journal of Textile Research, 2025, 46(12): 39-48.
[13] GAO Jun, LING Lei, CHEN Yuan, WU Dingsheng, LIN Hanlei, LI Zhenyu, FENG Quan. Preparation and Cr(Ⅵ) adsorption of amino-functionalized polyacrylonitrile nanofiber membrane [J]. Journal of Textile Research, 2025, 46(12): 57-65.
[14] ZHANG Huijie, LI Dengyu, ZHOU Xuan, LI Xiuyan, WANG Bin, XU Quan. Preparation and properties of sulfonated poly(ether ether ketone) Fe-Cr redox flow battery membranes [J]. Journal of Textile Research, 2025, 46(12): 83-91.
[15] HU Xinyang, WANG Hongzhi. Preparation of poly(vinylidene fluoride-trifluoride-trifluoroethylene)copolymer-based triboeletric nanogenerator and enhancement of its output power [J]. Journal of Textile Research, 2025, 46(12): 92-100.
Viewed
Full text


Abstract

Cited
  Shared   
  Discussed   
No Suggested Reading articles found!
京ICP备14006648号
Copyright 2021 © Editorial office of Journal of Textile Research
Supported by Beijing Magtech Co.Ltd