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Nature of the Surface Intermediates Formed from Methane on Cu-ZSM-5 Zeolite: A Combined Solid-State Nuclear Magnetic Resonance and Density Functional Theory Study Full article

Journal The Journal of Physical Chemistry C
ISSN: 1932-7447 , E-ISSN: 1932-7455
Output data Year: 2020, Volume: 124, Number: 11, Pages: 6242-6252 Pages count : 11 DOI: 10.1021/acs.jpcc.0c00311
Tags Chemical activation; Density functional theory; Methane; Methanol; Nuclear magnetic resonance spectroscopy; Zeolites
Authors Kolganov Alexander A. 1 , Gabrienko Anton A. 1,2 , Yashnik Svetlana A. 1 , Pidko Evgeny A. 3 , Stepanov Alexander G. 1
Affiliations
1 Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Novosibirsk 630090, Russia
2 Faculty of Natural Sciences, Department of Physical Chemistry, Novosibirsk State University, Novosibirsk 630090, Russia
3 Inorganic Systems Engineering Group, Department of Chemical Engineering, Faculty of Applied Sciences, Delft University of Technology, Van der Maasweg 9, Delft, 2629 HZ, Netherlands

Funding (2)

1 Federal Agency for Scientific Organizations 0303-2016-0003
2 Russian Science Foundation 18-73-00016

Abstract: The intermediates formed upon the interaction of methane with Cu-modified ZSM-5 zeolites (Cu/H-ZSM-5) have been analyzed with solid-state NMR spectroscopy and DFT methods. Methane activation by Cu/H-ZSM-5 zeolites gives rise to three distinct surface methoxy-like species (-O-CH3) detected by 13C MAS NMR spectroscopy with specific chemical shifts in the range of 53-63 ppm. DFT calculations on representative cluster models of different sites potentially present in Cu/H-ZSM-5 have been used to assign these signals to (i) methanol adsorbed on two neighboring Cu sites (Cu-(HOCH3)-Cu, 62.6 ppm), (ii) methanol adsorbed on zeolite Brønsted acid sites (52.9 ppm), and (iii) lattice-bound methoxy groups (Si-O(CH3)-Al, 58.6). The formation of these methoxy-like intermediates depends on the Cu loading and, accordingly, the type of Cu species in the Cu/H-ZSM-5 zeolite. For the sample with low (0.1 wt %) Cu loading containing exclusively mononuclear isolated Cu species, only the intermediates ii and iii have been detected. The Cu-bound intermediate (i) is formed upon methane activation by multinuclear Cu sites featuring Cu-O-Cu bridging moieties present in the materials with relatively higher Cu loading (1.38 wt %). The presented results indicate that methane activation by Cu/H-ZSM-5 can be promoted by both mono- and multinuclear Cu species confined in the zeolite matrix. Copyright © 2020 American Chemical Society.
Cite: Kolganov A.A. , Gabrienko A.A. , Yashnik S.A. , Pidko E.A. , Stepanov A.G.
Nature of the Surface Intermediates Formed from Methane on Cu-ZSM-5 Zeolite: A Combined Solid-State Nuclear Magnetic Resonance and Density Functional Theory Study
The Journal of Physical Chemistry C. 2020. V.124. N11. P.6242-6252. DOI: 10.1021/acs.jpcc.0c00311 WOS Scopus РИНЦ AN OpenAlex
Files: Full text from publisher
Dates:
Submitted: Jan 13, 2020
Accepted: Feb 17, 2020
Published online: Feb 26, 2020
Published print: Mar 19, 2020
Identifiers:
Web of science: WOS:000526396000038
Scopus: 2-s2.0-85081694425
Elibrary: 43254052
Chemical Abstracts: 2020:385557
OpenAlex: W3007294050
Citing:
DB Citing
Scopus 16
Web of science 46
Elibrary 43
OpenAlex 46
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