Hydrolytically stable MOFs combining Ti(IV) ions and porphyrin ligands are expected to display outstanding photophysical properties, making them ideal photocatalysts for the overall water splitting reaction under solar light. We...

Solventless synthesis and processing of Metal Organic Frameworks (MOFs) is critical to implement these materials in applied technologies. Vapour phase synthesis of MOF thin films is particularly suitable for such...

Vapor Phase Infiltration (VPI), a technique derived from Atomic Layer Deposition (ALD) and based on sequential self-limiting chemistry is used to modify the stable microporous porphyrin-based Metal Organic Framework (MOF) MIL-173(Zr). VPI is an appealing approach to modify MOFs by inserting reactants with atomic precision. The microporous nature and chemical stability of MIL-173 enable post-synthesis modification by VPI without MOF degradation even with extremely reactive precursors such as trimethylaluminum (TMA) and diethylzinc (DEZ). VPI proceeds through the diffusion of gaseous organometallic reactants TMA and DEZ inside the microporous framework where they react with two kinds of chemical sites offered by the porphyrinic linker (phenolic functions and pyrrolic functions in the porphyrin core), without altering the crystallinity and permanent porosity of the MOF. 27 Al NMR, UV-vis absorption and IR spectroscopies are used to further characterize the modified material. Physisorption of both precursors is computationally simulated by Grand Canonical Monte Carlo methods and outlines the preferential adsorption sites. Impact of temperature, number of VPI cycles and pulse length are investigated and show that, Al and Zn are introduced in a saturating manner inside the MOF on both available reactive sites. Porosity prerequisite is outlined for VPI which is proven to be much more effective than classical solution-based methods as it is solventless, fast, prevents work-up steps and allows reactions not possible by classical solution approach.