Which Species, Zn2+ Cations or ZnO Clusters, Are More Efficient for Olefin Aromatization? 13C Solid-State NMR Investigation of n-But-1-ene Transformation on Zn-Modified Zeolite | Sciact - CRIS-система Института катализа

Which Species, Zn2+ Cations or ZnO Clusters, Are More Efficient for Olefin Aromatization? 13C Solid-State NMR Investigation of n-But-1-ene Transformation on Zn-Modified Zeolite Научная публикация

Журнал

ACS Catalysis
ISSN: 2155-5435

Вых. Данные

Год: 2020, Том: 10, Номер: 23, Страницы: 14224-14233 Страниц : 10 DOI: 10.1021/acscatal.0c03647

Ключевые слова

BEA zeolite, zinc, n-butene, oligomerization, aromatization, solid-state NMR, DFT

Авторы

Lashchinskaya Zoya N. ^1,2 , Gabrienko Anton A. ^1,2 , Arzumanov Sergei S. ^1,2 , Kolganov Alexander A. ¹ , Toktarev Alexander V. ¹ , Freude Dieter ³ , Haase Jürgen ³ , Stepanov Alexander G. ^1,2

Организации

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	Fakultät für Physik und Geowissenschaften, Universität Leipzig, 04103 Leipzig, Germany

Информация о финансировании (2)

1	Российский научный фонд German Research Foundation	19-43-04101
2	German Research Foundation	HA 1893/22-1

The analysis of n-but-1-ene transformation on Zn-modified zeolite H-BEA, containing zinc exclusively in the form of either Zn2+ cations (Zn2+/H-BEA sample) or small clusters of ZnO (ZnO/H-BEA sample), has been performed with 13C solid-state nuclear magnetic resonance (NMR) at 296–673 K. The number of intermediates, including π-complex of n-but-2-ene, methylallylzinc, and delocalized carbanionic species formed by the interaction of oligomeric polyenes with Zn sites, have been identified for both zeolite samples. Methyl-substituted cyclopentenyl cation and cyclohexadienyl cation are additionally identified for the reaction on ZnO/H-BEA. It is inferred that the aromatization of the olefin occurs basically with the involvement of Zn2+ sites on Zn2+/H-BEA. For ZnO/H-BEA, besides aromatization with the assistance of ZnO species, conjunct polymerization process with the involvement of Brønsted acid sites (BAS) contributes notably to the olefin aromatization. The latter process affords also some quantity of C1–C4 alkanes. It is concluded that the stronger interaction of the olefin (confirmed by density functional theory (DFT) calculations) and oligomeric polyenes with Zn2+ cations than with ZnO species and different quantities of BAS for two zeolite samples provide peculiar performances of Zn2+/H-BEA and ZnO/H-BEA zeolites for the olefin aromatization. Based on careful analysis of the obtained spectroscopic results, it is suggested that Zn-modified zeolite containing Zn2+ cationic species and some quantity of BAS should exhibit higher efficiency as the catalyst for small olefin and alkane aromatization compared to the zeolite with ZnO species and high concentration of BAS.

Lashchinskaya Z.N. , Gabrienko A.A. , Arzumanov S.S. , Kolganov A.A. , Toktarev A.V. , Freude D. , Haase J. , Stepanov A.G.
Which Species, Zn2+ Cations or ZnO Clusters, Are More Efficient for Olefin Aromatization? 13C Solid-State NMR Investigation of n-But-1-ene Transformation on Zn-Modified Zeolite
ACS Catalysis. 2020. V.10. N23. P.14224-14233. DOI: 10.1021/acscatal.0c03647 WOS Scopus РИНЦ CAPlus OpenAlex

Поступила в редакцию:	20 авг. 2020 г.
Принята к публикации:	23 окт. 2020 г.
Опубликована online:	20 нояб. 2020 г.
Опубликована в печати:	4 дек. 2020 г.

Web of science:	WOS:000598140200040
Scopus:	2-s2.0-85097763936
РИНЦ:	45078672
Chemical Abstracts:	2020:2403410
OpenAlex:	W3109047774

БД	Цитирований
Scopus	35
Web of science	32
РИНЦ	32
OpenAlex	33