Journal of Textile Research ›› 2025, Vol. 46 ›› Issue (09): 57-65.doi: 10.13475/j.fzxb.20241105401

• Fiber Materials • Previous Articles     Next Articles

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 Online:2025-09-15 Published:2025-11-12
  • Contact: FENG Quan E-mail:fengquan@ahpu.edu.cn

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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

CLC Number: 

  • TQ340.64

Fig.1

SEM images of nanofibers membrane"

Fig.2

XRD patterns of PAN and PAN/PPy nanofiber membranes"

Fig.3

FT-IR specta of PAN and PAN/PPy nanofibes membranes"

Tab.1

Mechanical and hydrophilic properties of different samples"

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

Tab.2

Influence of temperature on adsorption of different samples"

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

Fig.4

Influences of pH value on Cr6+ adsorption properties of PAN/PPy nanofibers membrane"

Fig.5

Adsorption isotherms. (a) Influence of Cr6+ concentration on adsorpton of Cr6+ by PAN/PPy nanofiber membrane; (b) Nonlinear fitting curves of Langmuir model and Freundlich model; (c) Nonlinear fitting curves of two models at different temperatures"

Tab.3

Adsorption isotherm model parameters"

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

Fig.6

Adsorption thermodynamics"

Tab.4

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 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

Fig.7

Adsorption kinetics. (a) Pseudo-first-order; (b) Pseudo-second-order"

Tab.5

Adsorption kinetic parameter"

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

Fig.8

XPS specta of PAN/PPy nanofiber membrane. (a) XPS full spectra; (b) XPS fine spectra"

Fig.9

Reusable performance of PAN/PPy"

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