纺织学报 ›› 2025, Vol. 46 ›› Issue (12): 57-65.doi: 10.13475/j.fzxb.20250401701

• 纤维材料 • 上一篇    下一篇

氨基功能化聚丙烯腈纳米纤维膜的制备及其对Cr(Ⅵ)的吸附性能

高俊1, 凌磊1, 陈缘1, 武丁胜1, 林韩蕾1, 李振宇2, 凤权1()   

  1. 1.安徽工程大学 安徽省先进纤维材料工程研究中心, 安徽 芜湖 241000
    2.沙特水务局, 沙特 利雅得 12213
  • 收稿日期:2025-04-09 修回日期:2025-09-10 出版日期:2025-12-15 发布日期:2026-02-06
  • 通讯作者: 凤权(1975—),男,教授,博士。主要研究方向为功能性纳米纤维膜的制备。E-mail:fengquan@ahpu.edu.cn。
  • 作者简介:高俊(1999—),男,硕士生。主要研究方向为功能性纳米纤维膜的制备。
  • 基金资助:
    安徽省自然科学联合基金项目(2308085UM03);安徽省重点研究开发项目(2022l07020006);安徽省先进纤维材料工程研究中心(2023AFMC05);芜湖市科技计划项目(2024cj46)

Preparation and Cr(Ⅵ) adsorption of amino-functionalized polyacrylonitrile nanofiber membrane

GAO Jun1, LING Lei1, CHEN Yuan1, WU Dingsheng1, LIN Hanlei1, LI Zhenyu2, FENG Quan1()   

  1. 1. Advanced Fiber Materials Engineering Research Center of Anhui Province, Anhui Polytechnic University,Wuhu, Anhui 241000, China
    2. Saudi Water Authority, Riyadh 12213, Saudi Arabia
  • Received:2025-04-09 Revised:2025-09-10 Published:2025-12-15 Online:2026-02-06

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摘要： 针对六价铬离子(Cr(Ⅵ))废水对生态环境和人体健康造成巨大危害的问题,开发高效、快速去除Cr(Ⅵ)离子或降低其毒性的吸附材料具有重大意义。通过静电纺丝法制备聚乙烯亚胺(PEI)/聚丙烯腈(PAN)纳米纤维膜,用于吸附和解毒含Cr(Ⅵ)废水。探究了PEI/PAN纳米纤维膜的形貌和结构特征,测试酸碱值、初始质量浓度、温度和时间与吸附性能的关系,并分析其吸附行为。结果表明:PEI/PAN纳米纤维膜直径均匀、表面光滑;接触角为20.03°,展现出优良的亲水性;在温度为318 K、pH值为3的条件下,PEI/PAN纳米纤维膜对500 mg/L的Cr(Ⅵ)溶液的吸附效果最佳,吸附量可达191.73 mg/g;吸附符合Langmuir吸附等温模型,表明其吸附类型为单分子层吸附;吸附热力学表明,吸附是一种自发的吸热反应,高温对吸附过程具有推动作用;吸附动力学的拟合更符合准二级动力学,表明化学吸附占主导;且重复使用5次后仍能达到首次使用效果的67.56%,具备较好的可重复使用性能。

关键词: 铬, 聚丙烯腈, 聚乙烯亚胺, 纳米纤维膜, 吸附性能, 静电纺丝, 废水处理

Abstract:

Objective To address the environmental and health hazards posed by hexavalent chromium (Cr(Ⅵ)) in industrial effluents, the development of an effective adsorbent capable of removing or detoxifying Cr(Ⅵ) ions is of critical importance. Current adsorbent materials exhibit limitations in removal efficiency and regeneration durability. This study focuses on synthesizing a polyvinylimine/polyacrylonitrile (PEI/PAN) composite nanofiber membrane via electrospinning technology to achieve high-performance adsorption and detoxification of Cr(Ⅵ) contaminated wastewater.

Method In this study, PEI/PAN composite nanofiber membrane was prepared by electrospinning, using polyacrylonitrile and polyvinyleneimine, for the removal of Cr(Ⅵ) in wastewater. The physical and chemical properties of nanofiber membranes were characterized by scanning electron microscope (SEM), X-ray diffrac-tion (XRD), Fourier transform IR (FT-IR) and water contact angle (WCA). In addition, the effects of acid-base value, temperature, initial concentration and time on Cr(Ⅵ) performance were analyzed by batch experiments. Finally, the adsorption behavior of nanofiber membranes was further studied according to adsorption isotherms, adsorption thermodynamics and adsorption dynamics.

Results The PEI/PAN composite nanofiber membrane exhibited a uniform fiber diameter and a smooth surface morphology, with an average diameter of 0.32 μm. The absorption peak at 2 243 cm-1 indicated the nitrile (C══N) stretching vibration, confirming the incorporation of PAN. The peaks at 3 450 cm-1 and 2 935 cm-1 correspond to N—H bending and C—H stretching vibrations, respectively, while the peak at 1 734 cm-1 is attributed to the carbonyl (O══COCH3) stretching vibration, indicating the presence of PEI within the composite. A characteristic broad diffraction peak was observed at 2θ=17°, corresponding to the (110) crystallographic plane of PAN, along with a newly emerged and relatively broadened diffraction peak within the 20°-25° angular range. Mechanical test results indicated fracture elongation of 22.4% and fracture strength of 11.3 MPa, demonstrating superior mechanical performance. The composite nanofiber membrane exhibited a static water contact angle of 20.03°, indicating pronounced hydrophilicity. Following an evaluation of various parameters on the adsorption efficacy of the PEI/PAN composite nanofiber membrane, the findings reveal that the optimal removal efficiency occurred with a 500 mg/L Cr(Ⅵ) solution, achieving an adsorption capacity of 191.73 mg/g at 318 K and pH 3. Analysis of the adsorption isotherm, thermodynamics, and kinetics of the PEI/PAN composite nanofiber membrane reveals that the adsorption behavior aligns closely with the Langmuir isotherm model, indicating predominantly monolayer chemisorption. Thermodynamic data suggest the process is spontaneous and endothermic, with elevated temperatures favoring adsorption efficiency. Kinetic fitting corresponds to pseudo-second-order dynamics, highlighting the significant role of chemical interactions. Additionally, the membrane maintains 67.56% of its adsorption capacity after five reuse cycles, demonstrating good reusability and stability.

Conclusion PEI/PAN composite nanofiber membrane with uniform diameter and smooth surface were prepared by electrospinning. The influence of acid and base value, initial solution concentration, temperature and time on the adsorption performance was analyzed. At 318 K and pH 3, the PEI/PAN composite nanofiber membrane showed the best adsorption effect on Cr(Ⅵ), corresponding to a concentration of 191.73 mg/g. Through adsorption isotherm, adsorption thermodynamics and adsorption dynamics way to explore the PEI/PAN composite nanofiber membrane of Cr(Ⅵ) adsorption mechanism, found that the material and Langmuir model and secondary adsorption dynamics model fit is good, the whole adsorption process of chemical adsorption, and is spontaneous exothermic reaction, mainly have electrostatic attraction and redox action.

Key words: chromium, polyacrylonitrile, polyvinylimine, nanofiber membrane, adsorption performance, electrospinning, wastewater treatment

中图分类号: 

  • TQ340.64

图1

PAN和PEI/PAN的扫描电镜照片"

图2

PAN和PEI/PAN的直径分布图"

图3

PAN和PEI/PAN的红外光谱"

图4

PAN和PEI/PAN的XRD图谱"

表1

PAN和PEI/PAN的力学性能"

样品名称 断裂强度/MPa 断裂伸长率/% 弹性模量/MPa
PAN 5.8 35.7 16.2
PEI/PAN 11.3 22.4 50.4

图5

PAN和PEI/PAN的静态接触角"

图6

pH值对吸附容量的影响"

图7

初始质量浓度对吸附容量的影响"

表2

温度对PAN和PEI/PAN吸附容量的影响"

样品名称 不同温度下的吸附容量Qe/(mg·g-1)
298 K 308 K 318 K
PAN 24.793 30.362 33.728
PEI/PAN 83.145 105.944 112.585

图8

吸附等温线模型"

表3

吸附等温线参数"

温度/
K		 Langmuir模型 Freundlich模型
Qm/
(mg·g-1)		 k1/
(L·mg-1)		 R2 k2/
(mg(1-n)·
Ln·g-1)		 n R2
298 154.807 0.052 0.999 47.963 0.208 0.857
308 207.580 0.045 0.997 61.884 0.191 0.977
318 190.139 0.129 0.999 101.607 0.111 0.972

图9

吸附热力学模型"

表4

吸附热力学参数"

温度/
K		 ln(Kd/
(L·mg-1))		 ΔG/
(kJ·mol-1)		 ΔH/
(kJ·mol-1)		 ΔS/
(J·(mol·K)-1)
298 0.434 3 -1.076 1
308 0.597 2 -1.529 1 21.534 4 75.550 3
318 0.983 6 -2.600 4

图10

吸附动力学模型"

表5

吸附动力学参数"

准一级动力学模型 准二级动力学模型
Qe/
(mg·g-1)		 k3/
min-1		 R2 Qe/
(mg·g-1)		 k4/
(g·(mg·min)-1)		 R2
83.35 0.006 81 0.974 86.32 0.010 99 0.999

图11

PEI/PAN吸附前后的XPS谱图"

图12

PEI/PAN的循环使用性能"

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