纺织学报 ›› 2025, Vol. 46 ›› Issue (09): 57-65.doi: 10.13475/j.fzxb.20241105401

• 纤维材料 • 上一篇    下一篇

聚丙烯腈/聚吡咯纳米纤维膜的制备及其对铬离子的吸附性能

毛泽1, 高俊1, 凌磊1, 武丁胜1, 陶云1, 张春2, 李申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.江苏久吾高科技股份有限公司, 江苏 南京 211800
  • 收稿日期:2024-11-25 修回日期:2025-06-13 出版日期:2025-09-15 发布日期:2025-11-12
  • 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:毛泽(2000—),男,硕士生。主要研究方向为功能性纤维膜的制备。
  • 基金资助:
    安徽省自然科学基金项目(2208085QE139);安徽省重点研发项目(2022107020006);安徽省先进纤维材料工程研究中心项目(2023AFMC17)

Preparation and Cr6+ adsorption of polyacrylonitrile/polypyrrole nanofiber membrane

MAO Ze1, GAO Jun1, LING Lei1, WU Dingsheng1, TAO Yun1, ZHANG Chun2, LI Shen2, FENG Quan1()   

  1. 1. Advanced Fiber Materials Engineering Research Center, Anhui Polytechnic University, Wuhu, Anhui 241000, China
    2. Jiangsu JIUWU HI-TECH Co., Ltd., Nanjing, Jiangsu 211800, China
  • Received:2024-11-25 Revised:2025-06-13 Published:2025-09-15 Online:2025-11-12

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摘要： 针对六价铬离子(Cr6+)具有高毒性且难去除的问题,采用静电纺丝和原位氧化的方法制备聚丙烯腈/聚吡咯(PAN/PPy)纳米纤维膜。对PAN/PPy纳米纤维膜的形貌和结构进行表征,并探究其吸附性能和吸附行为。结果表明:PAN/PPy纳米纤维膜被成功制备,在温度为318 K、pH为2、Cr6+质量浓度为100 mg/L时,PAN/PPy纳米纤维膜达到最佳吸附容量(91.3 mg/g)。吸附等温线证实PAN/PPy纳米纤维膜对Cr6+吸附符合Langmuir吸附等温模型,说明PAN/PPy纳米纤维膜对Cr6+是单分子层吸附;吸附热力学结果表明,吸附过程是非自发的吸热反应;吸附动力学符合准二级动力学,属于化学吸附。PAN/PPy纳米纤维膜对Cr6+具有一定的还原能力,其中约41.3%的Cr6+被还原为Cr3+,且具有良好的可重复使用性能。

关键词: 铬, 聚丙烯腈, 聚吡咯, 纳米纤维膜, 吸附性能, 静电纺丝

Abstract:

Objective Heavy metal ions (Cr6+ as an example) are highly toxic and difficult to remove from wastewater, causing serious environmental problems. Many reported nanoparticle adsorbents show good effects, but are inconvenient for recycling and reuse, limiting the application of specific scenarios. Therefore, it is of great significance to develop adsorbents that could be reused as well as having good adsorption effect.

Method Polyacrylonitrile/polyaniline (PAN/PPy) nanofiber membrane were prepared by electrospinning and in-situ oxidation using polyacrylonitrile and pyrrole as raw materials. PAN/PPy nanofibers membrance were characterized by scanning electron microscope (SEM), X-ray diffractometer (XRD) and Fourier transform infrared (FT-IR)spectrometer. Tensile performance and hydrophilicity were evaluated using tensile testing equipment and water contact angle (WCA) measuring instrument, respectively. The influences of different factors (temperature, pH value and Cr6+ concentration) on the adsorption properties of PAN/PPy nanofiber membrane were investigated, and the adsorption isotherm, adsorption thermodynamics and adsorption kinetics of PAN/PPy nanofibers membrance were analyzed.

Results The SEM images showed that the fiber surface changed from smooth to rough with pyrrole growth. The (110) crystal system of PAN appeared at 2θ=17°, the amorphous peak of PPy appeared at 2θ=24°, the characteristic peak of C≡N appeared at 2 243 cm-1 in the FT-IR spectra, and the characteristic peak appeared at 811 and 920 cm-1 as the tensile vibration of C—H. The characteristic peaks at 1 487 and 1 558 cm-1 correspond to the tensile vibration of C=C, and the peaks at 1 685 and 1 315 cm-1 represent the vibration of C=N and C—N, respectively. SEM, XRD and FT-IR results demonstrated the successful preparation of PAN/PPy nanofibers membrane. PAN/PPy nanofiber membrane exhibited good mechanical properties (stress 4.3 MPa, strain 41.8%, elastic modulus 9.824 MPa) and hydrophilicity (water contact angle reduced from 132.3° to 40.4°). The adsorption results showed that the adsorption performance of PAN/PPy nanofiber membrane for Cr6+ increased with the rise of temperature, and decreased with the increase of pH value, because the protonated amino group decreased with the increase of pH value. Under the conditions of Cr6+ concentration of 100 mg/L, pH=2 and 318 K, the adsorption of PAN/PPy nanofiber membrane on Cr6+ reached 91.3 mg/g. The adsorption isotherm, adsorption thermodynamics and adsorption kinetics of PAN/PPy nanofibers membrane were fitted to analyze the adsorption behavior of Cr6+ by the experimental data. The results showed that the adsorption isotherm was consistent with the Langmuir model, indicating that it was monolayer adsorption.The adsorption thermodynamics showed that the adsorption of Cr6+ by PAN/PPy nanofiber membrane is a non-spontaneous endothermic reaction. The fitting of adsorption kinetics accorded with pseudo-second-order kinetics, indicating that chemisorption plays an dominant role in the adsorption process. XPS analysis results showed that about 41.3% of Cr6+ was reduced to Cr3+. The investigation also showed that after repeated use for five cycles, more than 60% adsorption was maintained compared to the adsorption result of the first use, suggesting good reusable performance.

Conclusion PAN/PPy nanofiber membrane was prepared by electrospinning and in situ oxidation for adsorption and reduction of Cr6+in wastewater. The PAN/PPy nanofiber membrane successfully prepared has good mechanical properties and hydrophilicity. Under the conditions of pH=2, 318 K and Cr6+ concentration of 100 mg/L, the optimal adsorption performance was 91.3 mg/g. The adsorption of Cr6+ by PAN/PPy nanofiber membrane is a single molecular layer adsorption, beloning to a non-spontaneous endothermic reaction, in which chemisorption plays an important role. PAN/PPy nanofiber membrane has good reducing properties and show satisfactory reusability.

Key words: chromium, polyacrylonitrile, polypyrrole, nanofiber membrane, adsorption performance, electrospinning

中图分类号: 

  • TQ340.64

图1

纳米纤维膜的SEM照片"

图2

PAN和PAN/PPy纳米纤维膜的XRD图谱"

图3

PAN和PAN/PPy纳米纤维膜的红外光谱"

表1

不同样品的力学性能和亲水性能"

样品
名称		 断裂
应力/MPa		 断裂
应变/%		 弹性模
量/MPa		 接触角/
(°)
PAN 33.1 55.7 1.7 132.3
PAN/PPy 4.3 41.8 9.8 40.4

表2

温度对不同样品的吸附性能影响"

样品
名称		 不同温度下吸附量/(mg·g-1)
298 K 308 K 318 K
PAN 21.5 29.4 29.8
PAN/PPy 41.7 44.2 46.0

图4

pH值对PAN/PPy纳米纤维膜的Cr6+吸附性能影响"

图5

吸附等温线"

表3

吸附等温模型参数"

温度/K Langmuir Freundlich
298 Qm=76.03 mg/g
KL=0.012 5 L/mg
R2=0.995		 KF=58.26 mg(1-n)·Ln/g
n=0.070 3
R2=0.925
308 Qm=84.89 mg/g
KL=0.011 8 L/mg
R2=0.995		 KF=61.87 mg(1-n)·Ln/g
n=0.080 0
R2=0.924
318 Qm=91.31 mg/g
KL=0.011 1 L/mg
R2=0.999		 KF=72.24 mg(1-n)·Ln/g
n=0.071 6
R2=0.849

图6

吸附热力学"

表4

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 1.050 6 0.013 2 10 852.83 588.586 4 -6.358 96
308 1.013 7 0.011 8 11 408.04
318 0.990 2 0.011 0 11 909.02

图7

吸附动力学"

表5

吸附动力学参数"

质量浓度/(mg·L-1) 准一级 准二级
50 Qe=55.47 mg/g
k1=0.003 96 min-1
R2=0.852		 Qe=60.20 mg/g
k2=0.003 96 g/(mg·min)
R2=0.999
70 Qe=69.93 mg/g
k1=0.004 54 min-1
R2=0.937		 Qe=74 mg/g
k2=0.003 96 g/(mg·min)
R2=0.999
100 Qe=82.10 mg/g
k1=0.004 74 min-1
R2=0.966		 Qe=114.10 mg/g
k2=0.003 96 g/(mg·min)
R2=0.999

图8

XPS图谱"

图9

PAN/PPy的重复使用性能"

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