Graduate School of Energy, Environment, Water and Sustainability, Korea Advanced Institute of Science and Technology, Daejeon 305-701, Republic of Korea.
Department of Chemistry, Korea Advanced Institute of Science and Technology, Daejeon 305-701, Republic of Korea.
Nat Commun. 2016 Nov 10;7:13377. doi: 10.1038/ncomms13377.
Molecular architecture in nanoscale spaces can lead to selective chemical interactions and separation of species with similar sizes and functionality. Substrate specific sorbent chemistry is well known through highly crystalline ordered structures such as zeolites, metal organic frameworks and widely available nanoporous carbons. Size and charge-dependent separation of aqueous molecular contaminants, on the contrary, have not been adequately developed. Here we report a charge-specific size-dependent separation of water-soluble molecules through an ultra-microporous polymeric network that features fluorines as the predominant surface functional groups. Treatment of similarly sized organic molecules with and without charges shows that fluorine interacts with charges favourably. Control experiments using similarly constructed frameworks with or without fluorines verify the fluorine-cation interactions. Lack of a σ-hole for fluorine atoms is suggested to be responsible for this distinct property, and future applications of this discovery, such as desalination and mixed matrix membranes, may be expected to follow.
纳米级空间中的分子结构可以导致具有相似大小和功能的物质发生选择性的化学相互作用和分离。通过沸石、金属有机骨架和广泛可用的纳米多孔碳等高度结晶有序结构,人们熟知基于底物的特异吸附剂化学。相反,对于带电荷和不带电荷的水相分子污染物的尺寸和电荷依赖性分离,尚未得到充分发展。在这里,我们通过超微孔聚合物网络报告了一种带电荷的、尺寸依赖性的水溶性分子分离方法,该网络的主要表面官能团为氟。对带电荷和不带电荷的类似大小的有机分子进行处理,结果表明氟与电荷相互作用有利。使用具有或不具有氟的类似结构的框架进行对照实验,验证了氟-阳离子相互作用。氟原子缺乏σ-hole 被认为是导致这种独特性质的原因,预计这一发现的未来应用,如脱盐和混合基质膜,将会出现。