Cu-BTC/PVDF杂化膜的原位掺杂制备及增强的染料吸附性能

doi:10.7503/cjcu20170727

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (7): 1384.doi: 10.7503/cjcu20170727

• 研究论文: 无机化学 • 上一篇下一篇

Cu-BTC/PVDF杂化膜的原位掺杂制备及增强的染料吸附性能

于承鑫, 刘洋洋, 张霞()

东北大学理学院化学系, 沈阳 110819

收稿日期:2017-11-13 出版日期:2018-07-10 发布日期:2018-04-18
作者简介:联系人简介: 张霞, 女, 博士, 教授, 主要从事有机-无机杂化膜的制备与性能研究. E-mail: xzhang@mail.neu.edu.cn
基金资助:
国家自然科学基金(批准号: 21501023)和国家级大学生创新创业训练计划项目(批准号: 201710145015)资助.

Preparation of Cu-BTC/PVDF Hybrid Membranes Using in situ Doping Method and Their Enhanced Dye Adsorption Properties^†

YU Chengxin, LIU Yangyang, ZHANG Xia^*()

Department of Chemistry, College of Sciences, Northeastern University, Shenyang 110819, China

Received:2017-11-13 Online:2018-07-10 Published:2018-04-18
Contact: ZHANG Xia E-mail:xzhang@mail.neu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.21501023) and the National Training Program of Innovation and Entrepreneurship for Undergraduates, China(No.201710145015)

摘要/Abstract

摘要：

将Cu-BTC颗粒与聚偏氟乙烯(PVDF)溶液共混, 原位掺杂制备了Cu-BTC/PVDF杂化膜, 利用扫描电子显微镜(SEM)、 X射线衍射仪、热重分析仪和傅里叶变换红外光谱仪等对杂化膜的结构进行了表征, 并对杂化膜的亲/疏水性质、膜孔隙率以及膜水通量进行了测定, 探讨了Cu-BTC的掺杂量对杂化膜结构和性质的影响. 结果表明, Cu-BTC的存在使PVDF薄膜的成核机理发生改变, 降低了PVDF膜孔尺寸, 提高了膜表面亲水性和水通量. 在对刚果红(CR)的吸附实验中, Cu-BTC/PVDF杂化膜表现出显著增强的吸附活性, 且随着Cu-BTC掺杂量的增加, Cu-BTC/PVDF对CR的吸附性能逐渐增强. 吸附热动力学拟合结果表明, 吸附过程以Langmuir单分子层吸附和化学吸附为主要特征.

关键词: MOF膜, 染料吸附, Cu-BTC/聚偏氟乙烯杂化膜, 刚果红

Abstract:

Cu-BTC/PVDF Hybrid membranes were fabricated through blending the Cu-BTC particles and poly(vinylidenefluoride)(PVDF) casting solution and the followed lyotropic phase transition process. Scanning electron microscopy(SEM), X-ray diffraction(XRD), thermogravimetric analysis(TG) and Fourier transform infrared spectroscopy(FTIR) were used to characterize these hybrid membranes, and the hydrophilic/hydrophobic properties, membrane porosity and membrane water flux were also measured. The effects of doping amount of Cu-BTC on the structure and properties of the hybrid membranes were discussed in detail. The results showed that in the presence of Cu-BTC particles, the nucleation mechanism of PVDF was changed to heterogeneous nucleation, and as a result, the pore size of PVDF membranes was reduced, the hydrophilicity and water flux of the hybrid membranes were improved evidently compared with pristine PVDF films. In the adsorption experiments of Congo red(CR), all the Cu-BTC/PVDF hybrid membranes presented significant enhanced adsorption activity, and with the increase of the doping amount of Cu-BTC, the adsorption properties of Cu-BTC/PVDF hybrid membranes were enhanced gradually. The adsorption thermal dynamics analyses indicated that the adsorption process is mainly characterized by Langmuir monolayer adsorption and chemical adsorption.

Key words: MOF membrane, Dye adsorption, Cu-BTC/poly(vinylidenefluoride)(PVDF) hybrid membrane, Congo red

中图分类号:

O614.12
O647

TrendMD:

于承鑫, 刘洋洋, 张霞. Cu-BTC/PVDF杂化膜的原位掺杂制备及增强的染料吸附性能. 高等学校化学学报, 2018, 39(7): 1384.

YU Chengxin, LIU Yangyang, ZHANG Xia. Preparation of Cu-BTC/PVDF Hybrid Membranes Using in situ Doping Method and Their Enhanced Dye Adsorption Properties^†. Chem. J. Chinese Universities, 2018, 39(7): 1384.

图/表 11

Scheme 1 Preparation process for Cu-BTC/PVDF hybrid membranes

Fig.1 XRD patterns of pristine Cu-BTC(4%)/PVDF(a), Cu-BTC(2%)/PVDF(b), Cu-BTC(1%)/PVDF(c), PVDF(d) and Cu-BTC(e)

Fig.2 SEM images of pristine PVDF(A, B) and Cu-BTC(4%)/PVDF membranes(C, D)^ (A), (C) the top-section images; (B), (D) the cross-section images.

Fig.3 TG curves(A) and FTIR spectra(B) of pristine PVDF(a), Cu-BTC(1%)/PVDF(b), Cu-BTC(2%)/PVDF(c), Cu-BTC(4%)/PVDF(d) and Cu-BTC(e)

Fig.4 Water contact angle and pure water permeability(A) and porosity(B) of pristine PVDF and

Fig.5 Adsorption capacities of CR on Cu-BTC(4%)/PVDF hybrid membranes under different pH values(A) and at different contact time(B)

Fig.6 Fitting curves of adsorption kinetics using first-order model(A) and second-order model(B)

Table 1 Fitting parameters calculated using first-order and second-order kinetics models

c₀(CR)/ (mg∙L^-1)	q_t_{, max}/ (μg∙cm^-2)	Pseudo-first order			Pseudo-second order
c₀(CR)/ (mg∙L^-1)	q_t_{, max}/ (μg∙cm^-2)	q_e/(μg∙cm^-2)	k₁/min^-1	R²	q_e/(μg∙cm^-2)	k₂/(cm²∙μg^-1∙min^-1)	R²
1200	796.36	2.304	9.92×10^-3	0.890	934.58	8.75×10^-6	0.997

Fig.7 Adsorption isotherm of CR on Cu-BTC(x)/PVDF hybrid membranes(A), fitting curves of adsorption isotherm data using Frendlich model(B) and Langmuir model(C) and results of cyclic adsorption tests for CR adsorption on Cu-BTC(4%)/PVDF hybrid membranes(D)^a. PVDF; b. Cu-BTC(1%)/PVDF; c. Cu-BTC(2%)/PVDF; d. Cu-BTC(4%)/PVDF.

Table 2 Fitting parameters for the adsorption isotherm of CR on Cu-BTC(4%)/PVDF

Langmuir model				Frendlich model
q_m/(μg∙cm^-2)	K_L/(mL∙μg^-1)	R²		K_F/(μg^1-1/ⁿ∙mL^1/ⁿ∙cm^-2)	n	R²
1157.41	0.00283	0.994		20.78	1.799	0.977

Table 3 Maximum adsorption capacity of CR calculated using Langmuir model

Membrane	PVDF	Cu-BTC(1%)/PVDF	Cu-BTC(2%)/PVDF	Cu-BTC(4%)/PVDF
q_m/(μg∙cm^-2)	125.28	414.94	1153.40	1157.40

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Cu-BTC/PVDF杂化膜的原位掺杂制备及增强的染料吸附性能

Preparation of Cu-BTC/PVDF Hybrid Membranes Using in situ Doping Method and Their Enhanced Dye Adsorption Properties^†

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Cu-BTC/PVDF杂化膜的原位掺杂制备及增强的染料吸附性能

Preparation of Cu-BTC/PVDF Hybrid Membranes Using in situ Doping Method and Their Enhanced Dye Adsorption Properties†

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Preparation of Cu-BTC/PVDF Hybrid Membranes Using in situ Doping Method and Their Enhanced Dye Adsorption Properties^†