Print Email Facebook Twitter Unraveling reaction networks behind the catalytic oxidation of methane with H2O2 over a mixed-metal MIL-53(Al,Fe) MOF catalyst Title Unraveling reaction networks behind the catalytic oxidation of methane with H2O2 over a mixed-metal MIL-53(Al,Fe) MOF catalyst Author Szécsényi, A. (TU Delft ChemE/Catalysis Engineering) Li, G. (TU Delft ChemE/Catalysis Engineering) Gascon, Jorge (King Abdullah University of Science and Technology) Pidko, E.A. (TU Delft ChemE/Inorganic Systems Engineering) Date 2018 Abstract Reaction paths underlying the catalytic oxidation of methane with H2O2 over an Fe containing MIL-53(Al) metal-organic framework were studied by periodic DFT calculations. Not only the activation of methane, but the full reaction network was considered, which includes the formation of the active site, the overoxidation of methane to CO2 and the decomposition of H2O2 to H2O and O2. Calculations indicate that the activation barrier for the initial activation of the Fe sites upon reaction with H2O2 is comparable to that of the subsequent C-H activation and also of the reaction steps involved in the undesirable overoxidation processes. The pronounced selectivity of the oxidation reaction over MIL-53(Al,Fe) towards the target mono-oxygenated CH3OH and CH3OOH products is attributed to the limited coordination freedom of the Fe species encapsulated in the extended octahedral [AlO6] structure-forming chains, which effectively prevents the direct overoxidation paths prior to product desorption from the active sites. Importantly, our computational analysis reveals that the active sites for the desired methane oxidation are able to much more efficiently promote the direct catalytic H2O2 decomposition reaction, rendering thus the current combination of the active site and the reactants undesirable for the prospective methane valorization process. To reference this document use: http://resolver.tudelft.nl/uuid:c7916952-8091-4eb9-a9d8-ca8e383eea00 DOI https://doi.org/10.1039/c8sc02376j ISSN 2041-6520 Source Chemical Science, 9 (33), 6765-6773 Part of collection Institutional Repository Document type journal article Rights © 2018 A. Szécsényi, G. Li, Jorge Gascon, E.A. Pidko Files PDF c8sc02376j.pdf 2.07 MB Close viewer /islandora/object/uuid:c7916952-8091-4eb9-a9d8-ca8e383eea00/datastream/OBJ/view