Journal of Textile Research ›› 2025, Vol. 46 ›› Issue (02): 170-179.doi: 10.13475/j.fzxb.20240805101

• Dyeing and Finishing Engineering • Previous Articles     Next Articles

Preparation of covalent organic framework/viscose spunlaced nonwoven fabrics and adsorption properties for dyestuff

LI Fengchun1,2, SUN Hui1,2(), YU Bin1,2, XIE Youxiu1,2, ZHANG Dewei1,2   

  1. 1. College of Textile Science and Engineering (International Institute of Silk), Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, China
    2. Zhejiang Provincial Innovation Center of Advanced Textile Technology, Shaoxing, Zhejiang 312000, China
  • Received:2024-08-27 Revised:2024-11-03 Online:2025-02-15 Published:2025-03-04
  • Contact: SUN Hui E-mail:sunhui@zstu.edu.com

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Abstract:

Objective Viscose spunlaced nonwoven fabrics (VSN) are a kind of nonwoven material prepared by spunlacing regenerated cellulose fibers and have the advantages of high strength and abrasion resistance, good air permeability and water wettability, and environmental friendliness and recyclability. Due to a large specific surface area and abundant reactive groups on the macromolecular chain, VSN has the potential to be used in the wastewater treatment field. However, in the face of complex water pollution system, VSN itself is difficult to achieve the efficient adsorption of organic dyes in water. It is necessary for VSN to be functionally modified for high adsorption of organic dyestuffs. Covalent organic frameworks (COFs) possess the advantages of high porosity, low density, customizable structural design, precise pore size, ease of functionalization, and excellent chemical stability, and have great potential as adsorbents for pollutant removal in water. Therefore, the functional modification of VSN using COFs is expected not only to enhance the organic dyestuffs adsorption efficiency of VSN, but also realize the effective recovery and recycling of COFs.

Method VSN was first pretreated with dilute hydrochloric acid. Pyridine-COF was then synthesized on the surface of VSN by in-situ solvothermal method using 1, 3, 5-tris(4-aminophenyl)benzene (TAP) and 2, 6-pyridinedicarboxaldehyde (DFP) as raw materials, and acetic acid as catalyst, obtaining Pyridine-COF/VSN. The morphology and structure of Pyridine-COF/VSN were studied, and the adsorption properties of organic dyestuffs were analyzed. Furthermore, the adsorption mechanism was explored by the adsorption kinetics and thermodynamics.

Results After in-situ solvothermal synthesis, Pyridine-COF uniformly covered the surface of the viscose fibers, showing a complete and regular spherical structure with a particle size of about 400 nm. In the FT-IR spectra of Pyridine-COF/VSN, the characteristic peaks of C=N of COF appeared besides the characteristic peaks attributed to VSN. The XPS spectra of Pyridine-COF/VSN showed that three peaks attributed to C, O, and N elements. The nuclear energy level N1s of Pyridine-COF/VSN were fitted, two peaks at 399.15 eV and 399.6 eV attributed to pyridine N (Pyridine-N) and —C—N=C. These phenomena verified that Pyridine-COF has been fixed on the surface of VSN. Compared with VSN, Pyridine-COF/ VSN showed a significant improvement in the adsorption efficiency of RhB in water. Pyridine-COF/VSN had adsorption capacity for both cationic organic dyestuffs including methylene blue (MB) and rhodamine (RhB) and anionic organic dyestuffs including congo red (CR) and methyl orange (MO). When the adsorption temperature was 25 ℃ and the pH of adsorption solution was 7, the adsorption efficiency of Pyridine-COF/VSN for RhB reached maximum, and was 98.06%, and the adsorption equilibrium time was 120 min. Compared with the quasi-primary kinetic model, the quasi-secondary kinetic model could better fit the adsorption process of Pyridine-COF/VSN for RhB, indicating that the whole adsorption process was mainly controlled by the chemical adsorption mechanism. The result from adsorption thermodynamics indicated that the adsorption process of Pyridine-COF/VSN for RhB was endothermic and spontaneous process. After six cycles, the adsorption efficiency of Pyridine-COF/VSN for RhB was still 64.60%. Compared with VSN, the tensile strength of the fabricated Pyridine-COF/VSN decreased, but the elongation at break increased.

Conclusion Compared with VSN, Pyridine-COF has outstanding adsorption for organic dyestuffs in water, and good reusable performance. When the adsorption temperature was 25 ℃ and the pH of adsorption solution was 7, the adsorption efficiency of Pyridine-COF/VSN for RhB was 98.06%. After six cycles, the adsorption efficiency of Pyridine-COF/VSN for RhB still kept 64.60%. It is hoped that our studies can expand the application of VSN on water treatment, and may provide some theoretical references for the preparation of nonwoven materials with high adsorption property.

Key words: covalent organic framework, viscose spunlaced nonwoven material, adsorption property, adsorption mechanism, dyestuff wastewater, wastewater treatment

CLC Number: 

  • TS176

Fig.1

Pyridine-COF/VSN experimental procedure (a) and synthetic mechanism diagram of Pyridine-COF (b)"

Fig.2

SEM images(a) of VSN,pre-treated VSN and Pyridine-COF/VSN and mapping profiles(b) of Pyridine-COF/VSN"

Fig.3

FT-IR spectra of VSN,Pyridine-COF/VSN and Pyridine-COF"

Fig.4

XPS survey spectra of VSN and Pyridine-COF/VSN (a) and N 1s spectrum of Pyridine-COF/VSN (b)"

Fig.5

Adsorption efficiency of Pyridine-COF/VSN and VSN for RhB"

Fig.6

Adsorption efficiency of Pyridine-COF/VSN for four organic dyes"

Fig.7

Adsorption efficiency of Pyridine-COF/VSN at different initial concentrations of RhB solution"

Fig.8

Adsorption efficiency of Pyridine-COF/VSN for RhB at different pH values"

Fig.9

Adsorption efficiency of Pyridine-COF/VSN for RhB at different adsorption temperatures"

Fig.10

Adsorption kinetic fitting curve of Pyridine-COF/VSN for RhB.(a)Linear fitting curve of pseudo first-order; (b) Pseudo second-order adsorption kinetic models"

Fig.11

Adsorption thermodynamic fitting curve of Pyridine-COF/VSN for RhB"

Tab.1

Adsorption thermodynamic parameters of Pyridine-COF/VSN for RhB at different temperatures"

ΔHθ/
(kJ·mol-1)		 ΔSθ/
(J·mol-1·K-1)		 ΔGθ/(kJ·mol-1)
298 K 303 K 308 K 313 K
101.32 356.72 -4.98 -6.77 -8.55 -10.33

Tab.2

Repeated adsorption efficiency of Pyridine-COF/VSN for RhB"

循环次数 1 2 3 4 5 6
吸附效率/% 98.06 97.08 95.94 89.58 81.86 64.60

Fig.12

Stress-strain curves of VSN,pre-treated VSN and Pyridine-COF/VSN"

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