Gao Liang, Chan Kwong-Yu, Li Chi-Ying Vanessa, Xie Liangxu, Olorunyomi Joseph F
Department of Chemistry , The University of Hong Kong , Pokfulam Road , Hong Kong , Hong Kong.
Nano Lett. 2019 Aug 14;19(8):4990-4996. doi: 10.1021/acs.nanolett.9b01211. Epub 2019 Jul 31.
Conventional ion-exchange polymeric membranes have limited selectivity due to their nonuniform and unstable structures. The rigid, regular, high porosity of metal organic framework (MOF) generally provides MOF membrane with exclusion/sieving effect but lack of electrostatic screening. Here we report for the first time a nonbiological highly selective MOF membrane with polyelectrolyte threaded in the nanochannel of metal organic framework (polyelectrolyte∼MOF) and its selective transport of alkali metal cations. Poly(sodium vinyl sulfonated--acrylic acid)∼MIL-53(Al) is prepared on anodic aluminum oxide substrate via steps of MOF MIL-53(Al) growth followed by in situ polymerization. The poly(VS--AA)∼MIL-53(Al) membrane demonstrates highly specific selectivity in transport of alkali metal cations. Rate of ion transport correlates inversely with the hydrated diameter of the ion reaching a low limiting rate near 0.7 nm hydrated diameter. Charge exclusion is demonstrated with blockage of anion transport under a concentration gradient. The highly uniform porous nanostructure of MOF and ionic function of polyelectrolyte offers the MOF membrane with synergistic selectivity based on exclusion forces of the framework and Coulomb forces from fixed charges of polyelectrolytes in nanochannels.
传统的离子交换聚合物膜由于其结构不均匀和不稳定,选择性有限。金属有机框架(MOF)具有刚性、规则且高孔隙率的特点,通常赋予MOF膜筛分效应,但缺乏静电筛选功能。在此,我们首次报道了一种非生物的高选择性MOF膜,其中聚电解质贯穿于金属有机框架的纳米通道中(聚电解质MOF),以及其对碱金属阳离子的选择性传输。通过MOF MIL-53(Al)生长步骤,随后进行原位聚合,在阳极氧化铝基底上制备了聚(乙烯基磺酸钠-丙烯酸)MIL-53(Al)。聚(VS-AA)~MIL-53(Al)膜在碱金属阳离子传输方面表现出高度特异性的选择性。离子传输速率与离子的水合直径成反比,在水合直径接近0.7nm时达到低极限速率。在浓度梯度下阴离子传输受阻,证明了电荷排斥作用。MOF高度均匀的多孔纳米结构和聚电解质的离子功能,基于框架的排斥力和纳米通道中聚电解质固定电荷的库仑力,为MOF膜提供了协同选择性。