Propylene Transformation on Zn-Modified Zeolite: Is There Any Difference in the Effect of Zn2+ Cations or ZnO Species on the Reaction Occurrence? | Sciact - CRIS-system of Boreskov Institute of Catalysis

Propylene Transformation on Zn-Modified Zeolite: Is There Any Difference in the Effect of Zn2+ Cations or ZnO Species on the Reaction Occurrence? Full article

Journal

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

Output data

Year: 2019, Volume: 123, Number: 45, Pages: 27573-27583 Pages count : 11 DOI: 10.1021/acs.jpcc.9b07672

Tags

SOLID-STATE NMR; MODIFIED ZSM-5 ZEOLITES; PROMOTED H-ZSM-5 CATALYSTS; POLYETHYLENE CHAIN GROWTH; 2 ALTERNATIVE MECHANISMS; BOND-SHIFT REACTION; IN-SITU NMR; METHANE ACTIVATION; AROMATIC-HYDROCARBONS; PROPANE AROMATIZATION

Authors

Gabrienko Anton A. ^1,2 , Arzumanov Sergei S. ^1,2 , Toktarev Alexander V. ¹ , Freude Dieter ³ , Haase Jürgen 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 Str. 2, Novosibirsk 630090, Russia
3	Fakultät für Physik und Geowissenschaften, Universität Leipzig, Linnéstr. 5, Leipzig, 04103, Germany

Funding (2)

1	Russian Science Foundation German Research Foundation	19-43-04101
2	German Research Foundation	HA 1893/22-1

The peculiar role of either Zn2+ cations or small ZnO clusters located inside the zeolite pores in propylene transformation to aromatic hydrocarbons on Zn2+ /H-ZSM-5 and ZnO/H-BEA zeolites has been analyzed. C-13 MAS NMR and FTIR spectroscopic investigation has revealed similar properties of different Zn-sites with respect to propylene oligomerization. Both Zn2+ cations and ZnO species are capable to convert propylene to higher C-6-C-9 olefins which represent the precursors of simple benzene-based aromatics. The mechanism of such oligomerization has been inferred to include the following stages: (a) adsorption of propylene on the Zn-sites in the form of a sr-complex; (b) transformation of the sr-complex of propylene to sigma-allylzinc surface species at elevated temperature; (c) formation of C6+ olefins; (d) transformation of oligomeric C6+ olefins to simple aromatic molecules (benzene, toluene, and xylenes). NMR evidences that Bronsted acid sites (BAS) of both zeolite samples are not involved in the oligomerization to a large extent although definitely contribute to oligomers formation. Involvement of BAS in propylene oligomerization on ZnO/H-BEA zeolite is higher because of their larger quantity in the sample. The oligomerization has been monitored to proceed mainly via allylzinc species owing to the olefin insertion into the reactive Zn-C bond. In such a way, selective formation of the C-6-C-9 olefins occurs which accounts for a particular set of aromatic products detected for propylene transformation on Zn-modified zeolites.

Gabrienko A.A. , Arzumanov S.S. , Toktarev A.V. , Freude D. , Haase J. , Stepanov A.G.
Propylene Transformation on Zn-Modified Zeolite: Is There Any Difference in the Effect of Zn2+ Cations or ZnO Species on the Reaction Occurrence?
The Journal of Physical Chemistry C. 2019. V.123. N45. P.27573-27583. DOI: 10.1021/acs.jpcc.9b07672 WOS Scopus РИНЦ ANCAN OpenAlex

Submitted:	Aug 12, 2019
Accepted:	Sep 26, 2019
Published online:	Oct 23, 2019
Published print:	Nov 14, 2019

Web of science:	WOS:000497260100031
Scopus:	2-s2.0-85074785118
Elibrary:	41700328
Chemical Abstracts:	2019:2020606
Chemical Abstracts (print):	171:496719
OpenAlex:	W2981709000

DB	Citing
Scopus	28
Web of science	28
Elibrary	25
OpenAlex	26