Methane Activation on In-Modified ZSM-5 Zeolite. H/D Hydrogen Exchange of the Alkane with Bronsted Acid Sites | Sciact - CRIS-system of Boreskov Institute of Catalysis

Methane Activation on In-Modified ZSM-5 Zeolite. H/D Hydrogen Exchange of the Alkane with Bronsted Acid Sites Full article

Journal

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

Output data

Year: 2014, Volume: 118, Number: 26, Pages: 14427-14432 Pages count : 6 DOI: 10.1021/jp5037316

Tags

Activation analysis; Activation energy; Hydrogen; Magic angle spinning; Nuclear magnetic resonance spectroscopy; Zeolites

Authors

Arzumanov Sergei S. ^1,2 , Moroz Ilya B. ² , Freude Dieter ³ , Haase Jurgen ³ , Stepanov Alexander G. ^1,2

Affiliations

1	Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
2	Faculty of Natural Sciences, Department of Physical Chemistry, Novosibirsk State University, Pirogova Street 2, Novosibirsk 630090, Russia
3	Universitat Leipzig, Fakulta t fur Physik und Geowissenschaften, Linnestrasse 5, 04103 Leipzig, Germany

Funding (1)

Russian Foundation for Basic Research

14-03-00040

In relation to clarifying the pathway of methane activation on In-modified zeolites, a comparative analysis of kinetics of hydrogen (H/D) exchange between methane-d4 and Brønsted acid sites (BAS) for both the pure acid form zeolite (H-ZSM-5) and In-modified zeolites (In+/H-ZSM-5 and InO+/H-ZSM-5) has been performed. Monitoring of the kinetics has been carried out with 1H magic-angle spinning NMR spectroscopy in situ within the temperature range of 453–568 K. While the rate of exchange on In+/H-ZSM-5 is 1 order of magnitude larger than that on H-ZSM-5, the exchange occurs on InO+/H-ZSM-5 by 2 orders of magnitude faster than that on H-ZSM-5. Significant increase of the rate and decrease of the activation energy (Ea = 74 ± 6 kJ mol–1) and the temperature threshold (453 K) for the reaction of the exchange on InO+/H-ZSM-5 compared to the rate, activation energy, and temperature threshold (543 K) for the reaction on In+/H-ZSM-5 (Ea = 127 ± 27 kJ mol–1) and H-ZSM-5 (Ea = 118 ± 9 kJ mol–1) have been rationalized in terms of involvement of both InO+ and BAS in activation of methane molecules on the zeolite. Some transient intermediate complex of methane with the zeolite InO+ species and BAS has been assumed to be formed within the zeolite pore. This complex is involved either in the reaction of H/D exchange with BAS of the zeolite or evolves further to offer indium methyl species.

Arzumanov S.S. , Moroz I.B. , Freude D. , Haase J. , Stepanov A.G.
Methane Activation on In-Modified ZSM-5 Zeolite. H/D Hydrogen Exchange of the Alkane with Bronsted Acid Sites
The Journal of Physical Chemistry C. 2014. V.118. N26. P.14427-14432. DOI: 10.1021/jp5037316 WOS Scopus РИНЦ ANCAN OpenAlex

Submitted:	Apr 16, 2014
Accepted:	Jun 5, 2014
Published online:	Jun 19, 2014
Published print:	Jul 3, 2014

Web of science:	WOS:000338693600039
Scopus:	2-s2.0-84903761055
Elibrary:	24064226
Chemical Abstracts:	2014:938835
Chemical Abstracts (print):	161:87993
OpenAlex:	W2314378242

DB	Citing
Web of science	24
Scopus	24
Elibrary	21
OpenAlex	24