Mixed-matrix membranes comprising NH2-MIL-53(Al) and Matrimid or 6FDA-DAM have been investigated. The metal organic framework (MOF) loading has been varied between 5 and 20 wt%, while NH2-MIL-53(Al) with three different morphologies, nanoparticles, nanorods, and microneedles has been dispersed in Matrimid. The synthesized membranes have been tested in the separation of CO2 from CH4 in an equimolar mixture. At 3 bar and 298 K for 8 wt% MOF loading, incorporation of NH2-MIL-53(Al) nanoparticles leads to the largest improvement compared to nanorods and microneedles. The incorporation of the best performing filler, i.e., NH2-MIL-53(Al) nanoparticles, into the highly permeable 6FDA-DAM has a larger effect, and the CO2 permeability increases up to 85% with slightly lower selectivities for 20 wt% MOF loading. Specifically, these membranes have a permeability of 660 Barrer with a CO2/CH4 separation factor of 28, leading to a performance very close to the Robeson limit of 2008. Furthermore, a new non-destructive technique based on Raman spectroscopy mapping is introduced to assess the homogeneity of the filler dispersion in the polymer matrix. The MOF contribution can be calculated by modeling the spectra. The determined homogeneity of the MOF filler distribution in the polymer is confirmed by focused ion beam scanning electron microscopy analysis.@en

During the last decade, the synthesis and application of metal-organic framework (MOF) nanosheets has received growing interest, showing unique performances for different technological applications. Despite the potential of this type of nanolamellar materials, the synthetic routes developed so far are restricted to MOFs possessing layered structures, limiting further development in this field. Here, a bottom-up surfactant-assisted synthetic approach is presented for the fabrication of nanosheets of various nonlayered MOFs, broadening the scope of MOF nanosheets application. Surfactant-assisted preorganization of the metallic precursor prior to MOF synthesis enables the manufacture of nonlayered Al-containing MOF lamellae. These MOF nanosheets are shown to exhibit a superior performance over other crystal morphologies for both chemical sensing and gas separation. As revealed by electron microscopy and diffraction, this superior performance arises from the shorter diffusion pathway in the MOF nanosheets, whose 1D channels are oriented along the shortest particle dimension.@en