Spray Drying for Making Covalent Chemistry: Postsynthetic Modification of Metal-Organic Frameworks

Covalent postsynthetic modification (PSM) of metal-organic frameworks (MOFs) has attracted much attention due to the possibility of tailoring the properties of these porous materials. Schiff-base condensation between an amine and an aldehyde is one of the most common reactions in the PSM of MOFs. Here, we report the use of the spray drying technique to perform this class of organic reactions, either between discrete organic molecules or on the pore surfaces of MOFs, in a very fast (1-2 s) and continuous way. Using spray drying, we show the PSM of two MOFs, the amine-terminated UiO-66-NH₂ and the aldehyde-terminated ZIF-90, achieving conversion efficiencies up to 20 and 42%, respectively. Moreover, we demonstrate that it can also be used to postsynthetically cross-link the aldehyde groups of ZIF-90 using a diamine molecule with a conversion efficiency of 70%.