Methane to Methanol Transformation on Cu2+/H‐ZSM‐5 Zeolite. Characterization of Copper State and Mechanism of the Reaction | Sciact - CRIS-system of Boreskov Institute of Catalysis

Methane to Methanol Transformation on Cu2+/H‐ZSM‐5 Zeolite. Characterization of Copper State and Mechanism of the Reaction Full article

Journal

Chemistry - A European Journal
ISSN: 0947-6539 , E-ISSN: 1521-3765

Output data

Year: 2025, Volume: 31, Number: 10, Article number : e202403167, Pages count : 14 DOI: 10.1002/chem.202403167

Tags

methane • methanol • C–H bond activation • Cu-modified ZSM-5 zeolite • spectroscopy and DFT

Authors

Gabrienko Anton A. ¹ , Kolganov Alexander A. ^1,2 , Yashnik Svetlana A. ¹ , Kriventsov Vladimir V. ³ , Stepanov Alexander G. ¹

Affiliations

1	Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
2	Inorganic Systems Engineering (ISE), Department of Chemical Engineering, Delft University of Technology, 2629 HZ Delft, The Netherlands
3	Synchrotron Radiation Facility SKIF, Boreskov Institute of Catalysis, Kol’tsovo 630559, Russia

Funding (2)

1	Ministry of Science and Higher Education of the Russian Federation	FWUR-2024-0032
2	Ministry of Science and Higher Education of the Russian Federation	FWUR-2024-0040

Cu-modified zeolites provide methane conversion to methanol with high selectivity under mild conditions. The activity of different possible Cu-sites for methane transformation is still under discussion. Herein, ZSM-5 zeolite has been loaded with Cu2+ cations (1.4 wt% Cu) as characterized by UV–vis DRS, EPR, EXAFS, and 1H MAS NMR. It is inferred that Cu2+ cations, attached to the cation-exchange Al–O––Si sites of the zeolite framework, can exist in the form of either isolated or paired Cu2+ sites. The transformation of methane to methanol on these sites has been verified by the observation of the methoxy species formation using 13C MAS NMR and FTIR spectroscopy. The related mechanisms have been analyzed by DFT calculations. It is obtained that Cu2+ sites enable heterolytic C–H bond dissociation via the “alkyl” pathway resulting in methylcopper species which however are not detected experimentally due to further rapid transformation to surface methoxy species. For the paired Cu2+ sites, such reaction occurs through methyl radical formation and recombination with Si–O––Al site. Based on the obtained data, it has been concluded that methane transformation to methanol on Cu2+ sites, having no extra-framework oxygen ligand, is possible in Cu-modified zeolites.

Gabrienko A.A. , Kolganov A.A. , Yashnik S.A. , Kriventsov V.V. , Stepanov A.G.
Methane to Methanol Transformation on Cu2+/H‐ZSM‐5 Zeolite. Characterization of Copper State and Mechanism of the Reaction
Chemistry - A European Journal. 2025. V.31. N10. e202403167 :1-14. DOI: 10.1002/chem.202403167 WOS Scopus AN OpenAlex

Published online:

Jan 8, 2025

Web of science:	WOS:001396820100001
Scopus:	2-s2.0-85214987995
Chemical Abstracts:	2025:155579
OpenAlex:	W4406228332

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