Print Email Facebook Twitter Unraveling the Nature of Extraframework Catalytic Ensembles in Zeolites Title Unraveling the Nature of Extraframework Catalytic Ensembles in Zeolites: Flexibility and Dynamics of the Copper-Oxo Trimers in Mordenite Author Khramenkova, E. (TU Delft ChemE/Inorganic Systems Engineering) Medvedev, Michael G. (Russian Academy of Sciences) Li, Guanna (Wageningen University & Research) Pidko, E.A. (TU Delft ChemE/Algemeen; TU Delft ChemE/Inorganic Systems Engineering) Date 2021 Abstract Extraframework cations define the chemical versatility of zeolite catalysts. Addressing their structural complexity and dynamic behavior represents one of the main fundamental challenges in the field. Herein, we present a computational approach for the identification and analysis of the accessible pool of intrazeolite extraframework complexes with a Cu/MOR catalyst as an industrially important model system. We employ ab initio molecular dynamics for capturing the ensemble of reactive isomers with the [Cu3O3]2+ stoichiometry confined in the mordenite channels. The high structural diversity of the generated isomers was ensured by concentrating the kinetic energy along the low-curvature directions of the potential energy surface (PES). Geometrically distinct [Cu3O3]2+ complexes were identified via a series of clustering procedures ensuring that one structure of each local minima is retained. The proposed procedure has resulted in a set of previously unknown peroxo-complexes, which are >50 kJ/mol more stable than the recently hypothesized chair-shaped structure. Our analysis demonstrates that the most stable peroxo-containing clusters can be formed under operando conditions from molecular oxygen and the Cu3O unit, similar to that in methane monooxygenase (MMO) enzymes. To reference this document use: http://resolver.tudelft.nl/uuid:277e1cd4-5a06-4ec3-806c-c5c633bfed12 DOI https://doi.org/10.1021/acs.jpclett.1c03288 ISSN 1948-7185 Source The Journal of Physical Chemistry Letters, 12 (44), 10906-10913 Part of collection Institutional Repository Document type journal article Rights © 2021 E. Khramenkova, Michael G. Medvedev, Guanna Li, E.A. Pidko Files PDF acs.jpclett.1c03288.pdf 4.07 MB Close viewer /islandora/object/uuid:277e1cd4-5a06-4ec3-806c-c5c633bfed12/datastream/OBJ/view