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. 2022 Jun 10;12(6):601.
doi: 10.3390/membranes12060601.

Negatively Charged MOF-Based Composite Anion Exchange Membrane with High Cation Selectivity and Permeability

Xiaohuan Li  1 , Noor Ul Afsar  2 , Xiaopeng Chen  1 , Yifeng Wu  1 , Yu Chen  1 , Feng Shao  1 , Jiaxian Song  1 , Shuai Yao  1 , Ru Xia  1 , Jiasheng Qian  1 , Bin Wu  1 , Jibin Miao  1
Affiliations

Negatively Charged MOF-Based Composite Anion Exchange Membrane with High Cation Selectivity and Permeability

Xiaohuan Li et al. Membranes (Basel). .

Abstract

Every metal and metallurgical industry is associated with the generation of wastewater, influencing the living and non-living environment, which is alarming to environmentalists. The strict regulations about the dismissal of acid and metal into the environment and the increasing emphasis on the recycling/reuse of these effluents after proper remedy have focused the research community's curiosity in developing distinctive approaches for the recovery of acid and metals from industrial wastewaters. This study reports the synthesis of UiO-66-(COOH)2 using dual ligand in water as a green solvent. Then, the prepared MOF nanoparticles were introduced into the DMAM quaternized QPPO matrix through a straightforward blending approach. Four defect-free UiO-66-(COOH)2/QPPO MMMs were prepared with four different MOF structures. The BET characterization of UiO-66-(COOH)2 nanoparticles with a highly crystalline structure and sub-nanometer pore size (~7 Å) was confirmed by XRD. Because of the introduction of MOF nanoparticles with an electrostatic interaction and pore size screening effect, a separation coefficient (SHCl/FeCl2) of 565 and UHCl of 0.0089 m·h-1 for U-C(60)/QPPO were perceived when the loading dosage of the MOF content was 10 wt%. The obtained results showed that the prepared defect-free MOF membrane has broad prospects in acid recovery applications.

Keywords: UiO-66; acid recovery; cation separation; diffusive dialysis.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Preparation process of the UiO-66-(COOH)2 crystal and the synthesis of QPPO.
Figure 1
Figure 1
(a) XRD patterns of four different carboxyl groups of UiO-66-(COOH)2 nanoparticles and simulated UiO-66. (b) Zeta potential of four different carboxyl groups of UiO-66-(COOH)2 nanoparticles. (c) Zeta potential of UiO-66-(COOH)2 with different H4BTEC contents as a function of pH. (d) SEM and (e) TEM images of the U-C(50) nanoparticles.
Figure 2
Figure 2
(a) N2 adsorption isotherm and (b) pore size distribution of four different composition of ratio of ligand UiO-66-(COOH)2 nanoparticles.
Figure 3
Figure 3
(a) WU, (b) LER, and (c) IEC of UiO-66-(COOH)2/QPPO membranes with four kinds of MOF of different carboxyl group contents under different MOF fillers.
Figure 4
Figure 4
H+ dialysis coefficient (UHCl) and H+/Fe2+ separation factor (SHCl/FeCl2) of UiO-66-(COOH)2/QPPO with four kinds of MOF with different carboxyl group contents under different MOF loadings. (a) U-C(50)/QPPO, (b) U-C(60)/QPPO, (c) U-C(70)/QPPO, and (d) U-C(80)/QPPO.
Figure 5
Figure 5
SHCl/FeCl2 versus UHCl of the reported membranes under diffusion dialysis [35,36,37,38,39,40,41,42].
Figure 6
Figure 6
(a) XRD patterns of U-C(60)/QPPO with different MOF fillers. (b–e) SEM images of U-C(60)/QPPO with different filler loading. ((b). 5 wt%; (c). 7 wt%; (d). 10 wt%; (e). 20 wt%). U-C(60) in U-C(60)/QPPO was marked by red circle.
Figure 7
Figure 7
(a) H+ dialysis coefficient (UHCl) and H+/Fe2+ separation factor (SHCl/FeCl2) of U-C(60)/QPPO membranes with different pH values. (b) H+ dialysis coefficient (UHCl) and H+/Fe2+ separation factor (SHCl/FeCl2) of U-C(60)/QPPO membranes with different ionic strengths. (c) H+ dialysis coefficient (UHCl) and H+/Fe2+ separation factor (SHCl/FeCl2) of U-C(60)/QPPO membranes with different temperatures.
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