Unraveling the Nature of Extraframework Catalytic Ensembles in Zeolites: Flexibility and Dynamics of the Copper-Oxo Trimers in Mordenite

Elena V. Khramenkova, Michael G. Medvedev, Guanna Li, Evgeny A. Pidko*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

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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.

Original languageEnglish
Pages (from-to)10906-10913
JournalJournal of Physical Chemistry Letters
DOIs
Publication statusPublished - 2021

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