Thermal decarboxylation for the generation of hierarchical porosity in isostructural metal–organic frameworks containing open metal sites

Abstract

The effect of metal-cluster redox identity on the thermal decarboxylation of a series of isostructural metal–organic frameworks (MOFs) with tetracarboxylate-based ligands and trinuclear μ₃-oxo clusters was investigated. The PCN-250 series of MOFs can consist of various metal combinations (Fe₃, Fe/Ni, Fe/Mn, Fe/Co, Fe/Zn, Al₃, In₃, and Sc₃). The Fe-based system can undergo a thermally induced reductive decarboxylation, producing a mixed valence cluster with decarboxylated ligand fragments subsequently eliminated to form uniform mesopores. We have extended the analysis to alternative monometallic and bimetallic PCN-250 systems to observe the cluster's effect on the decarboxylation process. Our results suggest that the propensity to undergo decarboxylation is directly related to the cluster redox accessibility, with poorly reducible metals, such as Al, In, and Sc, unable to thermally reduce at the readily accessible temperatures of the Fe-containing system. In contrast, the mixed-metal variants are all reducible. We report improvements in gas adsorption behavior, significantly the uniform increase in the heat of adsorption going from the microporous to hierarchically induced decarboxylated samples. This, along with Fe oxidation state changes from ⁵⁷Fe Mössbauer spectroscopy, suggests that reduction occurs at the clusters and is essential for mesopore formation. These results provide insight into the thermal behavior of redox-active MOFs and suggest a potential future avenue for generating mesoporosity using controlled cluster redox chemistry.