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n-Butane Transformation on In-Modified ZSM-5 Zeolite: A Case Study by 13C MAS NMR and FTIR Spectroscopy Full article

Journal The Journal of Physical Chemistry C
ISSN: 1932-7447 , E-ISSN: 1932-7455
Output data Year: 2023, Volume: 127, Number: 35, Pages: 17377–17388 Pages count : 12 DOI: 10.1021/acs.jpcc.3c04508
Tags Aromatic compounds, Fourier transform infrared spectroscopy, Hydrocarbons, Nuclear magnetic resonance spectroscopy, Zeolites
Authors Gabrienko Anton A. 1 , Arzumanov Sergei S. 1 , Lashchinskaya Zoya N. 1 , Toktarev Alexander V. 1 , Prosvirin Igor P. 1 , 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

Funding (1)

1 Russian Science Foundation 22-13-00029

Abstract: In-modified ZSM-5 zeolites are promising catalysts for light alkane dehydrogenation and aromatization. The mechanism of alkane activation and transformation on In-containing zeolites is still under discussion. In this work, n-butane transformation on H-ZSM-5 zeolite modified with InO+ sites has been investigated by 13C magic-angle spinning NMR and Fourier transform infrared (FTIR) spectroscopy at 296–673 K. It is established that n-butane conversion occurs by two parallel pathways: dehydrogenation to n-butene, followed by the formed alkene aromatization to simple aromatic hydrocarbons, and the direct oxidation of the alkane to C2–C6 carboxylate surface species. For the dehydrogenation pathway, n-butane activation has been established by FTIR spectroscopy to occur through C–H bond dissociation on the reactive In═O bond of the InO+ site. The oligomerization of the initially formed n-butene occurs by two pathways: (1) on InO+ sites via the formation of the n-butene π-complex and carbanionic allyl-like species as the intermediates; (2) with the involvement of Brønsted acid site (BAS). The formed oligomers convert to aromatics on the BAS with the formation of methyl-substituted cyclopentenyl cations as the intermediates. As for the oxidation pathway, the formation of the carboxylate surface species implies the dissociative adsorption of both the C–C and C–H bonds of the alkane on InO+ sites to give C2–C4 oxyindium-alkyl species. The latter are oxidized by InO+ to oxyindium-carboxylates, which can be further transformed to carboxylic acids by hydrolysis.
Cite: Gabrienko A.A. , Arzumanov S.S. , Lashchinskaya Z.N. , Toktarev A.V. , Prosvirin I.P. , Stepanov A.G.
n-Butane Transformation on In-Modified ZSM-5 Zeolite: A Case Study by 13C MAS NMR and FTIR Spectroscopy
The Journal of Physical Chemistry C. 2023. V.127. N35. P.17377–17388. DOI: 10.1021/acs.jpcc.3c04508 WOS Scopus РИНЦ AN OpenAlex
Dates:
Submitted: Jul 5, 2023
Accepted: Aug 14, 2023
Published online: Aug 24, 2023
Published print: Sep 7, 2023
Identifiers:
Web of science: WOS:001063612500001
Scopus: 2-s2.0-85170217145
Elibrary: 54954297
Chemical Abstracts: 2023:1749578
OpenAlex: W4386163487
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Scopus 6
Web of science 6
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