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O: Fachverband Oberflächenphysik
O 33: Poster: Supported Nanoclusters and Catalysis
O 33.8: Poster
Dienstag, 19. März 2024, 18:00–20:00, Poster C
Computational Modeling of Metal-Organic Frameworks as Heterogeneous Catalysts for Biomass Conversion — •Manuel A Ortuño1, Thanh-Hiep T. Le1, David Ferro-Costas1,2, and Antonio Fernandez-Ramos1,2 — 1Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CIQUS), Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain — 2Departamento de Química Física, Facultade de Química, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain
Metal-organic frameworks (MOFs) have emerged as promising heterogeneous catalysts due to well-defined structure, surface area, and tunable pore size. In particular, MOFs with Zr-based nodes are stable and therefore used as heterogeneous catalysts for a myriad of reactions.
Here we focus on UiO-66, formed by Zr-oxide nodes and 1,4-benzenedicarboxylate linkers, for the catalytic conversion of methyl levulinate into γ-valerolactone. We computed cluster and periodic models at DFT level to unravel the reaction mechanism. The simulations supported a defective node as active site, where the reaction takes place via three main steps: hydrogen transfer, nucleophilic attack, and elimination. Further studies suggested that the presence of Ce in the node might improve catalytic performance. Later, we found that both cluster and periodic models behave similarly, and the choice of density functional does not affect the rate-determining step but it does significantly change the Gibbs energy barriers.
Keywords: DFT; Metal-organic frameworks; Catalysis; Reaction mechanisms; Biomass conversion