Department of Chemical Engineering, Monash University, Clayton, Victoria, 3800, Australia.
Institute for Frontier Materials, Deakin University, Geelong, Victoria, 3216, Australia.
Angew Chem Int Ed Engl. 2019 Nov 18;58(47):16928-16935. doi: 10.1002/anie.201910408. Epub 2019 Oct 15.
Homochiral metal-organic framework (MOF) membranes have been recently reported for chiral separations. However, only a few high-quality homochiral polycrystalline MOF membranes have been fabricated due to the difficulty in crystallization of a chiral MOF layer without defects on porous substrates. Alternatively, mixed matrix membranes (MMMs), which combine potential advantages of MOFs and polymers, have been widely demonstrated for gas separation and water purification. Here we report novel homochiral MOF-polymer MMMs for efficient chiral separation. Homochirality was successfully incorporated into achiral MIL-53-NH nanocrystals by post-synthetic modification with amino acids, such as l-histidine (l-His) and l-glutamic acid (l-Glu). The MIL-53-NH-l-His and MIL-53-NH-l-Glu nanocrystals were then embedded into polyethersulfone (PES) matrix to form homochiral MMMs, which exhibited excellent enantioselectivity for racemic 1-phenylethanol with the highest enantiomeric excess value up to 100 %. This work, as an example, demonstrates the feasibility of fabricating diverse large-scale homochiral MOF-based MMMs for chiral separation.
手性金属有机骨架(MOF)膜最近被报道可用于手性分离。然而,由于在多孔基底上无缺陷的手性 MOF 层的结晶难度,仅制备出了少数高质量的手性多晶 MOF 膜。另外,混合基质膜(MMM)结合了 MOF 和聚合物的潜在优势,已广泛应用于气体分离和水净化。在此,我们报道了用于高效手性分离的新型手性 MOF-聚合物 MMM。通过后合成修饰氨基酸,如 l-组氨酸(l-His)和 l-谷氨酸(l-Glu),在手性 MIL-53-NH 纳米晶体中成功引入了手性。然后将 MIL-53-NH-l-His 和 MIL-53-NH-l-Glu 纳米晶体嵌入聚醚砜(PES)基质中形成手性 MMM,其对外消旋 1-苯乙醇表现出优异的对映选择性,最高对映体过量值高达 100%。这项工作为例,证明了制备各种大规模手性 MOF 基 MMM 用于手性分离的可行性。