Metal–Organic Framework UiO-66 Layer: A Highly Oriented Membrane with Good Selectivity and Hydrogen Permeance

The 3D metal-organic framework (MOF) structure UiO-66 [Zr6O4(OH)4(bdc)6], featuring triangular pores of approximately 6 Å, has been successfully prepared as a thin supported membrane layer with high crystallographic orientation on ceramic α-Al2O3 supports. The adhesion of the MOF layer to the ceramic support was investigated in different taxing conditions. Furthermore, by coating this UiO-66 membrane with a thin polyimide (Matrimid) top layer, we prepared a multilayer composite. Said membranes have been evaluated in the separation of hydrogen (H2) from different binary mixtures at room temperature. H2 as the smallest molecule (2.9 Å) should pass the UiO-66 membrane preferably since the kinetic diameters of all the other gases under study are larger. The gas mixture separation factors for the neat UiO-66 membrane were indeed found to be H2/CO2 = 5.1, H2/N2 = 4.7, H2/CH4 = 12.9, H2/C2H6 = 22.4, and H2/C3H8 = 28.5. The coating with Matrimid led to a sharp cutoff for gases with kinetic diameters greater than 3.7 Å, resulting in increased separation performance.