Aligned macrocycle pores in ultrathin films for accurate molecular sieving.
Aligned macrocycle pores in ultrathin films for accurate molecular sieving.
复制标题
超薄薄膜中的大环孔对齐，以精确的分子筛分。
DOI：
10.1038/s41586-022-05032-1
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发表时间：
2022-09
期刊：
影响因子：
64.8
通讯作者：
Livingston, Andrew G.
中科院分区：
文献类型：
--
作者：
Jiang, Zhiwei;Dong, Ruijiao;Evans, Austin M.;Biere, Niklas;Ebrahim, Mahmood A.;Li, Siyao;Anselmetti, Dario;Dichtel, William R.;Livingston, Andrew G.
聚合物膜广泛用于分离过程，包括脱盐、有机溶剂纳滤和原油分馏。然而，由于聚合物中定义不明确的空隙的分子波动，亚纳米孔的直接证据和操纵其尺寸的可行方法仍然具有挑战性。具有内腔的大环化合物可能会解决这一挑战。然而，具有不可区分的反应性的未官能化的大环倾向于在数百纳米厚的膜中无序堆积，阻碍腔互连和通孔的形成。在这里，我们合成了具有不同反应性的选择性官能化大环化合物，这些反应性优先排列以在纳米薄膜上形成明确的孔。通过将纳米膜厚度降低到几纳米来增强有序结构。这种定向结构使得能够直接可视化纳米膜表面中的亚纳米大环孔，通过改变大环身份来调整尺寸以达到精确度。对齐的大环膜提供了两倍的甲醇渗透性和更高的选择性相比，无序的同行。用于高价值的分离，在这里以富集大麻二酚油为例，它们实现了比商业最先进膜快一个数量级的乙醇传输和高三倍的富集。这种方法提供了一个可行的策略，在聚合物膜中创建亚纳米通道，并展示了其精确的分子分离的潜力。选择性官能化的大环化合物合成的反应性，优先对齐，以创建良好定义的孔在整个纳米薄膜提供了一种策略，以创建亚纳米通道的聚合物膜，并展示了准确的分子分离的潜力。
Polymer membranes are widely used in separation processes including desalination, organic solvent nanofiltration and crude oil fractionation. Nevertheless, direct evidence of subnanometre pores and a feasible method of manipulating their size is still challenging because of the molecular fluctuations of poorly defined voids in polymers. Macrocycles with intrinsic cavities could potentially tackle this challenge. However, unfunctionalized macrocycles with indistinguishable reactivities tend towards disordered packing in films hundreds of nanometres thick, hindering cavity interconnection and formation of through-pores. Here, we synthesized selectively functionalized macrocycles with differentiated reactivities that preferentially aligned to create well-defined pores across an ultrathin nanofilm. The ordered structure was enhanced by reducing the nanofilm thickness down to several nanometres. This orientated architecture enabled direct visualization of subnanometre macrocycle pores in the nanofilm surfaces, with the size tailored to ångström precision by varying the macrocycle identity. Aligned macrocycle membranes provided twice the methanol permeance and higher selectivity compared to disordered counterparts. Used in high-value separations, exemplified here by enriching cannabidiol oil, they achieved one order of magnitude faster ethanol transport and threefold higher enrichment than commercial state-of-the-art membranes. This approach offers a feasible strategy for creating subnanometre channels in polymer membranes, and demonstrates their potential for accurate molecular separations. Selectively functionalized macrocycles were synthesized with reactivities that preferentially aligned to create well-defined pores across an ultrathin nanofilm offering a strategy to create subnanometre channels in polymer membranes, and demonstrating potential for accurate molecular separations.
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