Highly Efficient Permeation and Separation of Gases with Metal-Organic Frameworks Confined in Polymeric Nanochannels.

This work demonstrates the confinement of porous metal-organic framework (HKUST-1) on the surface and walls of track-etched nanochannel in polyethylene terephthalate (np-PET) membrane using a liquid-phase epitaxy (LPE) technique. The composite membrane (HKUST-1/np-PET) exhibits defect-free MOF growth continuity, strong attachment of MOF to the support, and a high degree of flexibility. The high flexibility and the strong confinement of the MOF in composite membrane results from (i) the flexible np-PET support, (ii) coordination attachment between HKUST-1 and the support, and (iii) the growth of HKUST-1 crystal in nanoconfined geometries. The MOF has a preferred growth orientation with a window size of 3.5 Å, resulting in a clear cut-off of CO from natural gas and olefins. The experimental results and DFT calculations show that the restricted diffusion of gases only takes place through the nanoporous MOF confined in the np-PET substrate. This research thereby provides a new perspective to grow other porous MOFs in artificially prepared nanochannels for the realization of continuous, flexible, and defect-free membranes for various applications.