Specific Oriented Metal–Organic Framework Membranes and Their Facet-Tuned Separation Performance

Modulating the crystal morphology, or the exposed crystal facets, of metal-organic frameworks (MOFs) expands their potential applications in catalysis, adsorption, and separation. In this article, by immobilizing the citrate modulators on Au nanoparticles and subsequently being fixed on solid copper hydroxide nanostrands, a well-intergrown and oriented HKUST-1 cube crystal membrane was formed at room temperature. In contrast, in the absence of Au nanoparticles, well-intergrown and oriented cuboctahedron and octahedron membranes were formed in water/ethanol and ethanol, respectively. The gas separation performances of these HKUST-1 membranes were tuned via their exposed facets with defined pore sizes. The HKUST-1 cube membrane with exposed {001} facets demonstrated the highest permeance but lowest gas binary separation factors, while the octahedron membrane with exposed {111} facets presented the highest separation factors but lowest permeance, since the window size of {111} facets is 0.46 nm which is smaller than 0.9 nm of {001} facets. Separation of 0.38 nm CO2 from 0.55 nm SF6 was realized by the HKUST-1 octahedron membrane. As a proof of concept, this will open a new way to design MOF-related separation membranes by facet controlling.