纺织学报 ›› 2026, Vol. 47 ›› Issue (1): 54-62.doi: 10.13475/j.fzxb.20250603301

• 纤维材料 • 上一篇    下一篇

聚丙烯腈/共价有机框架复合纳米纤维膜的制备及其对Cr(Ⅵ)的吸附性能

凌磊1, 陈凯1, 高俊1, 武丁胜1, 汪邓兵2, 张春3, 凤权1()   

  1. 1.安徽工程大学 纺织服装学院, 安徽 芜湖 241000
    2.芜湖学院 材料与化工学院, 安徽 芜湖 241000
    3.江苏久吾高科技股份有限公司, 江苏 南京 211800
  • 收稿日期:2025-06-17 修回日期:2025-10-24 出版日期:2026-01-15 发布日期:2026-01-15
  • 通讯作者: 凤权(1975—),男,教授,博士。主要研究方向为功能性纤维膜的制备。E-mail: fengquan@ahpu.edu.cn。
  • 作者简介:凌磊(2002—),男,硕士生。主要研究方向为功能性纤维膜的制备。
  • 基金资助:
    安徽省自然科学联合基金项目(2308085UM03);安徽省高校自然科学研究项目(2022AH050958);安徽省先进纤维材料工程研究中心项目(2023AFMC05);芜湖市科技计划项目(2024cj46)

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 Published:2026-01-15 Online:2026-01-15

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摘要：

针对六价铬离子(Cr(Ⅵ))具有强毒性与致癌性,传统处理方法存在效率低、二次污染等问题,采用静电纺丝与原位生长技术,制备了聚丙烯腈/共价有机框架(PAN/COF)复合纳米纤维膜,用于Cr(Ⅵ)吸附与还原。分析了PAN/COF复合纳米纤维膜的形貌与结构,并测试其在不同条件下与Cr(Ⅵ)吸附性能的关系。结果表明:通过扫描电子显微镜、X射线衍射仪、傅里叶变换红外光谱仪等手段证实COF成功负载于PAN纤维表面,形成多级多孔结构;吸附性能研究表明,在pH=1、温度318 K、Cr(Ⅵ)质量浓度100 mg/L条件下,复合膜最大吸附量达99.4 mg/g;吸附等温线符合Freundlich模型,表明为多分子层吸附;吸附热力学显示吸附是自发吸热过程;吸附动力学符合准二级模型,证实化学吸附为主要机制;X射线光电子能谱分析表明,46.7%的Cr(Ⅵ)被还原为Cr(Ⅲ),经过7次吸附-脱附循环后,该PAN/COF复合纳米纤维膜的吸附效率仍能稳定保持在80%以上,具备优异的结构稳定性与循环复用性能。

关键词: 六价铬, 聚丙烯腈, 共价有机框架, 静电纺丝, 纳米纤维膜, 吸附, 废水处理, 重金属离子

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

中图分类号: 

  • TQ340.64

图1

纳米纤维膜的SEM照片"

图2

各材料的XRD图谱"

图3

各材料的XPS总谱与红外光谱"

图4

不同样品的力学性能和亲水性能"

表1

温度对不同样品吸附性能的影响"

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

图5

pH值对PAN/COF复合纳米纤维膜的Cr(Ⅵ)吸附性能影响"

图6

Cr(Ⅵ)质量浓度对PAN/COF复合纳米纤维膜的Cr(Ⅵ)吸附性能影响"

图7

吸附等温线"

表2

吸附等温线参数"

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

图8

吸附热力学"

表3

吸附热力学参数"

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

图9

吸附动力学模型"

表4

吸附动力学模型参数"

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

图10

XPS谱图"

图11

PAN/COF复合纳米纤维膜的可重复使用性能"

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