Controlling the molecular diffusion in MOFs with the acidity of monocarboxylate modulators

Abstract

The catalytic performance of metal–organic frameworks (MOFs) is related to their physicochemical properties, such as particle size, defect chemistry and porosity, which can be potentially controlled by coordination modulation. By combining PXRD, ¹HNMR, FT-IR, and N₂ uptake measurements we have gained insights into the control of different types of defects (missing linker or missing cluster consequence of the spatial distribution of missing linkers, and a combination of both) by the type of modulator employed. We show that the molar percent of defects, either as missing linkers or as a part of missing cluster defects, is related to the acidity of a modulator and its subsequent incorporation into the UiO-66 structure. Modulators with strong acidity and small size result in a considerable defect induction that causes an increase in the external surface area and mesopore volume, which is beneficial for the ring-opening of epoxides with amines, using UiO-66 defect-modulated MOFs as heterogeneous catalysts.