Abstract

Fine chemical synthesis requires catalytic systems that can provide high activity and selectivity while remaining recoverable and stable under practical reaction conditions. This thesis investigates metal-organic framework (MOF)-based materials as platforms to bridge homogeneous and heterogeneous catalysis in hydrogenation and tandem transformations.

Two strategies were explored. In the first part, a mixed-linker UiO-66 framework with picolylamine groups was used to immobilize ruthenium species for olefin and aldehyde hydrogenation. The resulting Ru-MOF catalysts exhibited high activity and selectivity in olefin hydrogenation, and demonstrated that the Ru precursor and local coordination environment strongly influenced catalytic performance.

In the second part, ZIF-67 was used as a sacrificial precursor to prepare Co@C600, a cobalt catalyst consisting of cobalt nanoparticles embedded in a nitrogen-doped carbon matrix. This material was applied in the tandem hydroformylation-acetalization of alkenes using syngas and alcohols. The catalyst enabled the one-pot formation of acetals without isolating the aldehyde intermediate or using noble metals or additional acid co-catalysts. Experimental results and DFT calculations, indicated that nitrogen in the carbon support adjusts aldehyde adsorption to a range more favorable for catalytic turnover.

This work shows that MOFs can contribute to heterogeneous catalysis either as structurally defined supports for immobilized metal sites or as precursors to robust carbon-supported catalysts. The results offer useful design insights for MOF-based catalysts in selective hydrogenation and tandem carbonylation, while also highlighting important challenges related to active-site evolution, reaction conditions, and catalyst stability.