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

doi:10.7503/cjcu20170727

Abstract

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

CLC Number:

O614.12
O647

TrendMD:

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

Figures/Tables 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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