Electrospinning Preparation and Photocatalytic Activity of H4SiW12O40/Ethylene Vinyl Alcohol Copolymer Nanofibrous Membrane†

doi:10.7503/cjcu20180500

Abstract

Abstract:

H₄SiW₁₂O₄₀(SiW₁₂)/ethylene vinyl alcohol(EVOH) copolymer composite nanofibrous membrane was prepared by electrospinning. Characterization with energy-dispersive X-ray spectroscopy(EDX) and Fourier transformation infrared spectroscopy(FTIR) indicated that SiW₁₂ was loaded into the EVOH nanofibrous membrane and its Keggin structure remained intact. The as-prepared SiW₁₂/EVOH composite nanofibrous membrane exhibited excellent photocatalytic activity in the degradation of methyl orange(MO) under xenon lamp irradiation. The degradation efficiency of MO reached 96.3% as the mass ratio of EVOH to SiW₁₂ was 2:1, which may be attributed to the synergistic effect of EVOH and SiW₁₂. More importantly, the composite nanofibrous membrane presented an excellent reusability. There was no significant decrease of photocatalytic activity of the catalyst after three cycles of reactions, which mainly because the hydrogen bonds between SiW₁₂ and EVOH could enhance the stability of SiW₁₂ in the membrane. In view of this, SiW₁₂/EVOH composite nanofibrous membranes exhibited the potential for practical applications to eliminate organic dyes from wastewater.

Key words: Electrospinning, Ethylene vinyl alcohol copolymer, H₄SiW₁₂O₄₀, Photocatalysis, Composite nanofibrous membrane

CLC Number:

O631

ZHANG Xinmu,CUI Xiangxu,YAOMA Kangyue,LI Tingting,ZHANG Zhiming. Electrospinning Preparation and Photocatalytic Activity of H₄SiW₁₂O₄₀/Ethylene Vinyl Alcohol Copolymer Nanofibrous Membrane^†[J]. Chemical Journal of Chinese Universities, 2019, 40(2): 372-378.

Figures/Tables 8

Fig.1 SEM images of SiW12/EVOH fibers with different mass ratios of EVOH to SiW12m(EVOH)/m(SiW12): (A) 1:0; (B) 4:1; (C) 3:1; (D) 2:1.Inset of (D) is corresponding EDX spectrum.

Fig.2 FTIR spectra of EVOH(a), SiW12(b) and SiW12/EVOH(c) nanofibrous membranes

Fig.3 Dynamic measurements of water permeation on the surface of EVOH and SiW12/EVOH nanofibrous membranes with different mass ratios of EVOH to SiW12m(EVOH)/m(SiW12): (A) 1:0; (B) 4:1; (C) 3:1; (D) 2:1.

Fig.4 Tensile strength of EVOH and SiW12/EVOH nanofibrous membranes with different mass ratios of EVOH to SiW12

Fig.5 UV-Vis spectra of MO vs. photoreaction time catalyzed by SiW12/EVOH nanofibrous membrane under xenon lamp irradiation(A) and the blank controlled experiments(B)

Fig.6 Photodegradation of MO over SiW12/EVOH nanofibrous membranes with different mass ratio of EVOH to SiW12(A) and effect of pH on photocatalytic activity of SiW12/EVOH nanofibrous membrane(B)(A) m(EVOH)/m(SiW12): a. 2:1; b. 3:1; c. 4:1. (B) pH: a. 1; b. 3; c. 5.

Table 1 Comparison of photocatalytic efficiency of different catalysts for the degradation of MO

Catalyst	Catalytic condition	MO degradation(%)	Ref.
Ag/TiO₂ film	[TiO₂]=120 mg/L, [AgNO₃]=10^-3 mol/L, initial	90	[25]
	pH=9.2, after 1 h illumination
Sulfate-modified titania(S $O 4 2 -$ /TiO₂ catalyst)	[Catalyst]=1.0 g/L, [S $O 4 2 -$ ]=25 mg/mL, 4 h	61	[26]
PSt-grafted ZnO nanoparticles	[Catalyst]=1.5 g/L, pH=7, 30 ℃, 5 h	83	[27]
ZnFe₂O₄/TiO₂ photocatalysts	[TiO₂]=5 g/L, [ZnFe₂O₄]=1.5%, 4 h	84	[28]
Natural rutile sample containing substituting	[Rutile]=1 g/L, [H₂O₂]=3.8 mmol/L, [V₂O₅]=	61	[29]
metal ions as V⁵⁺ and Fe³⁺	12.2 mg/mL, [FeO]=3.9 mg/mL, pH=3, 1 h
SiW₁₂/EVOH composite nanofibrous membrane	[H₄SiW₁₂O₄₀]=0.5 g/L, pH=1, 2.5 h	96.3	This work

Table 1 Comparison of photocatalytic efficiency of different catalysts for the degradation of MO

Catalyst	Catalytic condition	MO degradation(%)	Ref.
Ag/TiO₂ film	[TiO₂]=120 mg/L, [AgNO₃]=10^-3 mol/L, initial	90	[25]
	pH=9.2, after 1 h illumination
Sulfate-modified titania(S $O 4 2 -$ /TiO₂ catalyst)	[Catalyst]=1.0 g/L, [S $O 4 2 -$ ]=25 mg/mL, 4 h	61	[26]
PSt-grafted ZnO nanoparticles	[Catalyst]=1.5 g/L, pH=7, 30 ℃, 5 h	83	[27]
ZnFe₂O₄/TiO₂ photocatalysts	[TiO₂]=5 g/L, [ZnFe₂O₄]=1.5%, 4 h	84	[28]
Natural rutile sample containing substituting	[Rutile]=1 g/L, [H₂O₂]=3.8 mmol/L, [V₂O₅]=	61	[29]
metal ions as V⁵⁺ and Fe³⁺	12.2 mg/mL, [FeO]=3.9 mg/mL, pH=3, 1 h
SiW₁₂/EVOH composite nanofibrous membrane	[H₄SiW₁₂O₄₀]=0.5 g/L, pH=1, 2.5 h	96.3	This work

Fig.7 Photocatalytic activity of SiW12/EVOH nanofibrous membrane for MO degradation with three times of cycling useTimes of cycling use: (A) 1; (B) 2; (C) 3.

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Electrospinning Preparation and Photocatalytic Activity of H₄SiW₁₂O₄₀/Ethylene Vinyl Alcohol Copolymer Nanofibrous Membrane^†

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