Solvent-assisted linker exchange enabled preparation of cerium-based metal–organic frameworks constructed from redox active linkers

Abstract

Cerium-based MOFs have shown much potential in fields such as catalysis and gas separation. However, hexanuclear Ce(IV) node MOFs are challenging to form in the presence of redox active species due to the ease of formation of Ce³⁺ in solution. Here, a facile solvent-assisted linker exchange procedure was developed to functionalize Ce-UiO-66 with amine and hydroxyl groups to produce MOFs that were unachievable via de novo methods. The resulting functionalized MOFs showed enhanced catalytic activity when testing the hydrolysis of the nerve agent simulant, dimethyl 4-nitrophenyl phosphate. By using an amine functionalized analogue of Ce-UiO-66, the hydrolysis rate was nearly doubled. With this study, we demonstrated that solvent-assisted linker exchange (SALE) is an effective tool to incorporate redox active linkers in Ce based MOFs that are otherwise unattainable de novo.