MIL-101 promotes aerobic oxidation in n-dodecane of dibenzothiophene (DBT) and its methyl-substituted derivatives to their corresponding sulfones with complete selectivity, without observation of the sulfoxide. DBT sulfones can be completely separated from n-dodecane by water extraction. MIL-101(Cr) without the need of pre-activation was found to be more convenient than the also-active MIL-101(Fe) analog. The reaction exhibits an induction period due to the diffusion inside the pore system of the solvent or oxygen and it is not observed if the MIL-101 sample is first in contact with the solvent at the reaction temperature for a sufficiently long time. MIL-101 is reusable for at least five times without any sign of deactivation according to the time-conversion plots. Evidence by electron paramagnetic resonance spectroscopy detecting the hydroperoxide radical adduct with a spin trapping agent and Raman spectroscopy detection of superoxide supports that the process is an auto-oxidation reaction initiated by MIL-101 following the expected radical chain mechanism inside the MIL-101 cages.

Assembly of different metal-organic frameworks (MOFs) into hybrid MOF-on-MOF heterostructures has been established as a promising approach to develop synergistic performances for a variety of applications. Here, we explore the performance of a MOF-on-MOF heterostructure by epitaxial growth of MIL-88B(Fe) onto UiO-66(Zr)-NH₂ nanoparticles. The face-selective design and appropriate energy band structure alignment of the selected MOF constituents have permitted its application as an active heterogeneous photocatalyst for solar-driven water splitting. The composite achieves apparent quantum yields for photocatalytic overall water splitting at 400 and 450 nm of about 0.9%, values that compare much favorably with previous analogous reports. Understanding of this high activity has been gained by spectroscopic and electrochemical characterization together with scanning transmission and transmission electron microscopy (STEM, TEM) measurements. This study exemplifies the possibility of developing a MOF-on-MOF heterostructure that operates under a Z-scheme mechanism and exhibits outstanding activity toward photocatalytic water splitting under solar light.

Stable mixed-metal Fe^III/Ni^II MIL-100 MOFs have been synthesized de novo and have been explored as superior heterogeneous catalysts in acid catalyzed reactions, presenting superior performances.