Efficient Separation of Ethanol–Methanol and Ethanol–Water Mixtures Using ZIF‑8 Supported on a Hierarchical Porous Mixed-Oxide Substrate

This work reports a new approach for the synthesis of a zeolitic imidazolate framework (ZIF-8) composite. It employs the direct growth of the crystalline ZIF-8 on a mixed-metal oxide support TiO₂–SiO₂ (TSO), which mimics the porous structure of Populus nigra. Using the natural leaf as a template, the TSO support was prepared using a sol–gel method. The growth of the ZIF-8 layer on the TSO support was carried out by the seeds and second growth method. This method facilitates the homogeneous dispersion of ZIF-8 crystals at the surface of the TSO composite. The ZIF-8@TSO composite adsorbs methanol selectively, mainly due to the hierarchical porous structure of the mixed oxide support. As compared with the as-synthesized ZIF-8, a 50% methanol uptake is achieved in the ZIF-8@TSO composite, with only 25 wt % ZIF-8 loading. IAST simulations show that the ZIF-8@TSO composite has a preferential adsorption toward methanol when using an equimolar methanol–ethanol mixture. An opposite behavior is observed for the as-synthesized ZIF-8. The results show that combining MOFs and mixed-oxide supports with bioinspired structures opens opportunities for synthesizing new materials with unique and enhanced adsorption and separation properties.