Functional UiO-66 Series Membranes with High Perm Selectivity of Monovalent and Bivalent Anions for Electrodialysis Applications,Industrial & Engineering Chemistry Research

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Functional UiO-66 Series Membranes with High Perm Selectivity of Monovalent and Bivalent Anions for Electrodialysis Applications
Industrial & Engineering Chemistry Research ( IF 3.8 ) Pub Date : 2021-03-02 , DOI: 10.1021/acs.iecr.0c05992
Huimin Ruan ₁ , Nengxiu Pan ₁ , Chao Wang ₁ , Lu Yu ₁ , Junbin Liao ₁ , Jiangnan Shen ₁

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Metal–organic frameworks (MOFs) have a good separation potential due to their uniform pore size, easy functionalization, and adjustable structure. Therefore, we make use of this feature of MOFs for the separation of Cl^–/SO₄^2– systems with different charges and sizes. In this work, two kinds of UiO-66 membranes with different functional groups were synthesized and applied to the monovalent perm-selective separation of the Cl^–/SO₄^2– system in electrodialysis (ED). UiO-66-NH₂ membranes were used to investigate the influence of current density and initial solution concentration on perm selectivity. A layer of UiO-66-NH₂ was first grown on the anodic alumina oxide (AAO) disks. After that, short chains containing sulfonic acid groups were grafted onto the amino groups by the ring-opening reaction of 1,3-propanesulfonate. The structural stability of the MOF layer was confirmed by XRD analysis of the membrane surface after the ED test. Ion exchange capacity (IEC) and elemental mapping were used to confirm the comparison changes in the degree of sulfonation. It was found that UiO-66-NH₂ membranes exhibited a higher monovalent anion perm selectivity with a peak value of 36.23 (initial mixture solution of 0.05 M NaCl and 0.05 M Na₂SO₄) at lower current density (2.5 mA·cm^–2). The perm selectivity of UiO-66-SO₃H membranes increased with running time under 24 h of sulfonation time. In particular, with low IEC value of 0.10–0.16, it still showed a good performance on perm selectivity. Compared with published polymer ion exchange membranes (perm selectivity < 5) for ED, it has higher perm selectivity, more convenient functionalization, and resistance to organic solvents.

中文翻译：

功能性UiO-66系列膜具有高电导率的单价和二价阴离子选择性，可用于电渗析应用

金属有机骨架（MOF）具有均匀的孔径，易于功能化和可调节的结构，因此具有良好的分离潜力。因此，我们利用MOF的这一功能来分离具有不同电荷和大小的Cl ^– / SO ₄^{2 –}系统。在这项工作中，二种UIO-66膜具有不同官能团的合成和施加到Cl组成的单价选择性渗透分离^- / SO ₄^2-系统在电渗析（ED）。用UiO-66-NH ₂膜研究电流密度和初始溶液浓度对电导率选择性的影响。一层UiO-66-NH ₂首先在阳极氧化铝（AAO）盘上生长。之后，通过1，3-丙磺酸盐的开环反应将含有磺酸基的短链接枝到氨基上。通过ED试验后的膜表面的XRD分析，确认了MOF层的结构稳定性。离子交换容量（IEC）和元素映射用于确认磺化度的比较变化。发现在较低的电流密度（2.5 mA·cm ^–₂）下，UiO-66-NH ₂膜表现出更高的单价阴离子渗透选择性，峰值为36.23（0.05 M NaCl和0.05 M Na ₂ SO _4的初始混合溶液）。²）。UiO-66-SO ₃的渗透选择性在磺化时间为24 h时，H膜随运行时间的增加而增加。特别是，当IEC值为0.10-0.16时，它在渗透选择性方面仍然表现出良好的性能。与已发布的用于ED的聚合物离子交换膜（渗透率选择性<5）相比，它具有更高的渗透率选择性，更方便的功能化以及对有机溶剂的耐受性。

更新日期：2021-03-17

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