Solvent-free powder synthesis and MOF-CVD thin films of the large-pore metal-organic framework MAF-6

A simple solvent- and catalyst-free method is presented for the synthesis of the large-pore metal-organic framework (MOF) MAF-6 (RHO-Zn(eIm)2) based on the reaction of ZnO with 2-ethylimidazole vapor at temperatures ≤ 100 °C. By translating this method to a chemical vapor deposition (CVD) protocol, crystalline films of a large-pore material could be deposited for the first time entirely from the vapor phase. A combination of PALS and Kr physisorption measurements confirmed the porosity of these MOF-CVD films and the size of the MAF-6 supercages (diam. ~2 nm), in close agreement with powder data and calculations. MAF-6 powders and films were further characterized by XRD, TGA, SEM, FTIR, PDF and EXAFS. The exceptional uptake capacity of MAF-6 in comparison to ZIF-8 is demonstrated by vapor-phase loading of a molecule larger than the ZIF-8 windows.