Department of Chemical and Biological Engineering, Monash University, Clayton, VIC, 3800, Australia.
College of Science, Wuhan University of Science and Technology, Wuhan, 430072, China.
Nat Commun. 2023 Jan 18;14(1):286. doi: 10.1038/s41467-023-35970-x.
Controllable fabrication of angstrom-size channels has been long desired to mimic biological ion channels for the fundamental study of ion transport. Here we report a strategy for fabricating angstrom-scale ion channels with one-dimensional (1D) to three-dimensional (3D) pore structures by the growth of metal-organic frameworks (MOFs) into nanochannels. The 1D MIL-53 channels of flexible pore sizes around 5.2 × 8.9 Å can transport cations rapidly, with one to two orders of magnitude higher conductivities and mobilities than MOF channels of hybrid pore configurations and sizes, including Al-TCPP with 1D ~8 Å channels connected by 2D ~6 Å interlayers, and 3D UiO-66 channels of ~6 Å windows and 9 - 12 Å cavities. Furthermore, the 3D MOF channels exhibit better ion sieving properties than those of 1D and 2D MOF channels. Theoretical simulations reveal that ion transport through 2D and 3D MOF channels should undergo multiple dehydration-rehydration processes, resulting in higher energy barriers than pure 1D channels. These findings offer a platform for studying ion transport properties at angstrom-scale confinement and provide guidelines for improving the efficiency of ionic separations and nanofluidics.
一直以来,人们都希望能够可控地制备出埃米级通道,以模拟生物离子通道,从而深入研究离子输运。在此,我们报告了一种通过将金属有机骨架(MOFs)生长到纳米通道中,从而制备出具有一维(1D)到三维(3D)孔结构的埃米级离子通道的策略。具有约 5.2×8.9Å 柔性孔径的 1D MIL-53 通道能够快速传输阳离子,其电导率和迁移率比具有混合孔径结构和尺寸的 MOF 通道高出一到两个数量级,包括通过二维(2D)6Å 夹层连接的具有 1D8Å 通道的 Al-TCPP,以及~6Å 窗口和 9-12Å 腔的 3D UiO-66 通道。此外,3D MOF 通道表现出比 1D 和 2D MOF 通道更好的离子筛分性能。理论模拟表明,离子通过 2D 和 3D MOF 通道的传输应经历多次去水合-再水合过程,导致能量势垒高于纯 1D 通道。这些发现为研究埃米级限域下的离子输运特性提供了一个平台,并为提高离子分离和纳流控效率提供了指导。