Electronic Structure of the [Cu3(μ-O)3]2+ Cluster in Mordenite Zeolite and Its Effects on the Methane to Methanol Oxidation

Konstantinos D. Vogiatzis, Guanna Li, Emiel J.M. Hensen, Laura Gagliardi, Evgeny A. Pidko

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

Identifying Cu-exchanged zeolites able to activate C-H bonds and selectively convert methane to methanol is a challenge in the field of biomimetic heterogeneous catalysis. Recent experiments point to the importance of trinuclear [Cu3(μ-O)3]2+ complexes inside the micropores of mordenite (MOR) zeolite for selective oxo-functionalization of methane. The electronic structures of these species, namely, the oxidation state of Cu ions and the reactive character of the oxygen centers, are not yet fully understood. In this study, we performed a detailed analysis of the electronic structure of the [Cu3(μ-O)3]2+ site using multiconfigurational wave-function-based methods and density functional theory. The calculations reveal that all Cu sites in the cluster are predominantly present in the Cu(II) formal oxidation state with a minor contribution from Cu(III), whereas two out of three oxygen anions possess a radical character. These electronic properties, along with the high accessibility of the out-of-plane oxygen center, make this oxygen the preferred site for the homolytic C-H activation of methane by [Cu3(μ-O)3]2+. These new insights aid in the construction of a theoretical framework for the design of novel catalysts for oxyfunctionalization of natural gas and suggest further spectroscopic examination.

Original languageEnglish (US)
Pages (from-to)22295-22302
Number of pages8
JournalJournal of Physical Chemistry C
Volume121
Issue number40
DOIs
StatePublished - Oct 12 2017

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Zeolites
Methane
Electronic structure
Methanol
methane
methyl alcohol
Oxygen
electronic structure
Oxidation
oxidation
oxygen
biomimetics
natural gas
Biomimetics
Wave functions
zeolites
Electronic properties
Catalysis
catalysis
Density functional theory

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Electronic Structure of the [Cu3(μ-O)3]2+ Cluster in Mordenite Zeolite and Its Effects on the Methane to Methanol Oxidation. / Vogiatzis, Konstantinos D.; Li, Guanna; Hensen, Emiel J.M.; Gagliardi, Laura; Pidko, Evgeny A.

In: Journal of Physical Chemistry C, Vol. 121, No. 40, 12.10.2017, p. 22295-22302.

Research output: Contribution to journalArticle

Vogiatzis, Konstantinos D. ; Li, Guanna ; Hensen, Emiel J.M. ; Gagliardi, Laura ; Pidko, Evgeny A. / Electronic Structure of the [Cu3(μ-O)3]2+ Cluster in Mordenite Zeolite and Its Effects on the Methane to Methanol Oxidation. In: Journal of Physical Chemistry C. 2017 ; Vol. 121, No. 40. pp. 22295-22302.
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