In recent years, Zr-based metal organic frameworks (MOFs) have revealed their potential for heterogeneous catalytic applications. The defect sites found in certain MOFs can act as catalysts or bonding sites for catalysts consisting of metal complexes. Computational studies can unravel the mechanisms of these catalyzed reactions and offer insights to improve the catalytic performance of these materials.<br/>We present a computational study using density functional theory on the mechanism of an aldol condensation reaction catalyzed by UiO-66 (a zirconium-oxide based MOF). Intriguing experimental data reveal a sizable difference in the activation energy when UiO-66, synthesized with no modulator, and UiO-66-mod, synthesized with a modulator, are used as catalysts. More strikingly, the rate determining step of the catalytic cycle changes with the different materials. We will discuss the mechanism of the reaction for these two materials, focusing on explaining this puzzling reactivity difference.<br/>     We will also present a computational study of  ethylene hydrogenation versus dimerization catalyzed by Ir decorated UiO-67 MOF. Ir single-site and tetranuclear Ir clusters have been installed on UiO-67, and show differing reactivities. We will discuss the mechanisms and the reactivity differences.<br/><br/>

Computational study of mechanisms in catalysis using metal organic frameworks

2019 Fall National Meeting

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