Реферат: 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.

Библиографическая ссылка: Khramenkova E.V. , Medvedev M.G. , Li G. , Pidko E.A.
Unraveling the Nature of Extraframework Catalytic Ensembles in Zeolites: Flexibility and Dynamics of the Copper-Oxo Trimers in Mordenite
Journal of Physical Chemistry Letters. 2021. V.12. N44. P.10906-10913. DOI: 10.1021/acs.jpclett.1c03288 WOS Scopus OpenAlex

Идентификаторы БД:

≡ Web of science:	WOS:000719783300028
≡ Scopus:	2-s2.0-85119048729
≡ OpenAlex:	W3210659873

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