H4SiW12O40/乙烯-乙烯醇共聚物复合纳米纤维膜的制备及光催化性能

doi:10.7503/cjcu20180500

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (2): 372.doi: 10.7503/cjcu20180500

H₄SiW₁₂O₄₀/乙烯-乙烯醇共聚物复合纳米纤维膜的制备及光催化性能

张馨木, 崔向旭, 姚马康悦, 李婷婷, 张志明()

华北理工大学材料科学与工程学院, 唐山市功能高分子材料重点实验室, 唐山 063210

收稿日期:2018-07-14 出版日期:2019-02-10 发布日期:2018-11-16
作者简介:
联系人简介: 张志明, 男, 博士, 副教授, 主要从事聚合物基复合材料研究. E-mail: zhangzhiming1942@163.com
基金资助:
国家自然科学基金(批准号: 51172062、 51472074)、河北省自然科学基金(批准号: E2016209202)、河北省“百人计划”项目(批准号: E2012100005)、华北理工大学国家自然科学基金培育项目(批准号: GP201517)、华北理工大学2017年大学生创新创业训练计划项目(批准号: X2017194)和河北省高等学校科学技术研究项目(批准号: ZD2018053)资助

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

ZHANG Xinmu, CUI Xiangxu, YAOMA Kangyue, LI Tingting, ZHANG Zhiming^*()

College of Material Science and Engineering, Key Laboratory of Functional Polymer Materials of Tangshan, North China University of Science and Technology, Tangshan 063210, China

Received:2018-07-14 Online:2019-02-10 Published:2018-11-16
Contact: ZHANG Zhiming E-mail:zhangzhiming1942@163.com
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.51472074, 51172062), the Natural Science Foundation of Hebei Province of China(No.E2016209202), the Hundred Talents Program of Hebei Province of China(No.E2012100005), the Engagement Fund of North China University of Science and Technology(No.GP201517), the College Students’ Innovation and Entrepreneurship Training Program of North China University of Science and Technology of China(No.X2017194) and the Scientific Research Foundation for Colleges and Universities of Hebei Province of China(No.ZD2018053)

摘要/Abstract

摘要：

利用静电纺丝技术制备了H₄SiW₁₂O₄₀(SiW₁₂)/乙烯-乙烯醇共聚物(EVOH)复合纳米纤维膜. X射线能谱(EDX)和红外光谱(IR)表征结果表明, SiW₁₂负载到EVOH纤维膜中, 且其Keggin结构完好无损. SiW₁₂/EVOH复合纳米纤维膜在氙灯光源照射下对甲基橙(MO)表现出优异的光催化活性. 当EVOH与SiW₁₂的质量比为2:1时, MO降解率可达96.3%. 复合纳米纤维膜优异的光催化活性主要归于EVOH与SiW₁₂的协同相互作用. 复合纤维膜具有良好的可重复使用性, 循环使用3次后, 其光催化活性没有明显下降. 因此, SiW₁₂/EVOH复合纳米纤维膜在去除废水中有机染料方面具有广阔的应用前景.

关键词: 静电纺丝, 乙烯-乙烯醇共聚物, H₄SiW₁₂O₄₀, 光催化, 复合纳米纤维膜

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

中图分类号:

O631

TrendMD:

张馨木, 崔向旭, 姚马康悦, 李婷婷, 张志明. H₄SiW₁₂O₄₀/乙烯-乙烯醇共聚物复合纳米纤维膜的制备及光催化性能. 高等学校化学学报, 2019, 40(2): 372.

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

图/表 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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H₄SiW₁₂O₄₀/乙烯-乙烯醇共聚物复合纳米纤维膜的制备及光催化性能

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

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