H/D Exchange of n-Butane on In-Modified Zeolite BEA Investigated by 1H Magic-Angle Spinning Nuclear Magnetic Resonance In Situ | Sciact - CRIS-system of Boreskov Institute of Catalysis

H/D Exchange of n-Butane on In-Modified Zeolite BEA Investigated by 1H Magic-Angle Spinning Nuclear Magnetic Resonance In Situ Full article

Journal

The Journal of Physical Chemistry C
ISSN: 1932-7447 , E-ISSN: 1932-7455

Output data

Year: 2023, Volume: 127, Number: 43, Pages: 21122–21131 Pages count : 10 DOI: 10.1021/acs.jpcc.3c05483

Authors

Arzumanov Sergei S. ¹ , Gabrienko Anton A. ¹ , Toktarev Alexander V. ¹ , Freude Dieter ² , Haase Jürgen ² , Stepanov Alexander G. ¹

Affiliations

1	Siberian Branch of the Russian Academy of Sciences, Boreskov Institute of Catalysis, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
2	Fakultät für Physik und Geowissenschaften, Universität Leipzig, Linnéstr. 5, Leipzig 04103, Germany

Funding (2)

1	Ministry of Science and Higher Education of the Russian Federation	0239-2021-0003
2	Russian Science Foundation	22-13-00029

To establish the effect of indium species introduced in the zeolite on protolytic activation of the alkane by zeolite Brønsted acid sites (BASs), the kinetics of H/D hydrogen exchange between n-butane-d10 and the BAS of indium-modified zeolite H-BEA has been monitored by 1H magic-angle spinning nuclear magnetic resonance spectroscopy in situ at 455–573 K. Regioselectivity in the methyl groups of the alkane, high rate, and low activation energy (52–64 kJ mol–1) of the H/D exchange in the presence of either InO+ or In+ cations in the zeolite indicate that the mechanisms of protolytic activation and the H/D exchange for n-butane differ from that on pure acid-form zeolites. The promoting effect of InO+ cations on the reaction kinetics is more essential than that of In+ cations. It is proposed that InO+ sites located in the vicinity of BASs provide fast exchange with the methyl groups of the alkane in the initial period of the kinetics. The BASs that are remote from InO+ sites are involved in the H/D exchange with the alkane at the final period of the kinetics by protium transfer from the remote BAS to BAS vicinal to InO+ sites. The transfer is realized by the H/D exchange between the remote BAS and BAS vicinal to InO+ sites with the assistance of a minor quantity of molecular hydrogen (H2), evolved at n-butane dehydrogenation and working as the vehicle for this transfer.

Arzumanov S.S. , Gabrienko A.A. , Toktarev A.V. , Freude D. , Haase J. , Stepanov A.G.
H/D Exchange of n-Butane on In-Modified Zeolite BEA Investigated by 1H Magic-Angle Spinning Nuclear Magnetic Resonance In Situ
The Journal of Physical Chemistry C. 2023. V.127. N43. P.21122–21131. DOI: 10.1021/acs.jpcc.3c05483 WOS Scopus РИНЦ AN OpenAlex

Submitted:	Aug 14, 2023
Accepted:	Oct 9, 2023
Published online:	Oct 25, 2023
Published print:	Nov 2, 2023

Web of science:	WOS:001096387600001
Scopus:	2-s2.0-85177876848
Elibrary:	55290109
Chemical Abstracts:	2023:2192798
OpenAlex:	W4387935267

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