Methane Activation on Zn2+-Exchanged ZSM-5 Zeolites. The Effect of Molecular Oxygen Addition | Sciact - CRIS-система Института катализа

Methane Activation on Zn2+-Exchanged ZSM-5 Zeolites. The Effect of Molecular Oxygen Addition Научная публикация

Журнал

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

Вых. Данные

Год: 2015, Том: 119, Номер: 44, Страницы: 24910-24918 Страниц : 9 DOI: 10.1021/acs.jpcc.5b08759

Ключевые слова

HZSM-5 zeolites Magic angle spinning NMR Methane activation Modified zeolite Nonoxidative condition Oxygen-containing species Partial substitution Zeolite surfaces

Авторы

Gabrienko Anton A. ¹ , Arzumanov Sergei S. ^1,2 , Luzgin Mikhail V. ^1,2 , Stepanov Alexander G. ^1,2 , Parmon Valentin N. ¹

Организации

1	Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
2	Department of Natural Sciences, Novosibirsk State University, Pirogova Street 2, Novosibirsk 630090, Russia

Информация о финансировании (1)

Российский фонд фундаментальных исследований

14-03-00040

In relation to the reported methane activation on Zn-modified zeolite ZSM-5 at room temperature to afford the surface methoxy species by Xu et al. (Chem. Sci. 2012, 3, 2932), the activation of methane on Zn2+-exchanged H-ZSM-5 zeolite in the absence and the presence of molecular oxygen has been studied with 13C magic angle spinning (MAS) NMR spectroscopy. It has been established that the methane activation on zinc cationic sites under nonoxidative conditions occurs exclusively by an “alkyl” pathway to form the surface zinc-methyl species. The addition of the molecular oxygen (dioxygen) to methane adsorbed on the Zn2+-exchanged H-ZSM-5 zeolite results in the surface methoxy and other oxygen-containing species, such as formate, acetaldehyde, and acetic acid. The formation of the surface methoxy species occurs by the oxidation with molecular oxygen of zinc-methyl species primarily formed on the zeolite surface. The Zn2+/ZSM-5 zeolite with full substitution of Brønsted acid sites (BAS) by Zn2+ cations offers zinc-methyl species from methane at T ≥ 523 K, whereas Zn2+/H-ZSM-5 with partial substitution (60%) of BAS produces zinc-methyl at room temperature. BAS promotes the formation and decomposition (by the sample evacuation) of zinc-methyl species on Zn2+/H-ZSM-5 at room temperature. Zinc-methyl is readily oxidized by the dioxygen additive to offer methoxy species already at room temperature. Thus, it has been shown that pure methane forms only zinc-methyl species upon its interaction with zinc cationic sites of Zn2+-exchanged H-ZSM-5 zeolite, while the surface methoxide could be formed only by the interaction of zinc-methyl with dioxygen that might be contained in the reactive methane.

Gabrienko A.A. , Arzumanov S.S. , Luzgin M.V. , Stepanov A.G. , Parmon V.N.
Methane Activation on Zn2+-Exchanged ZSM-5 Zeolites. The Effect of Molecular Oxygen Addition
The Journal of Physical Chemistry C. 2015. V.119. N44. P.24910-24918. DOI: 10.1021/acs.jpcc.5b08759 WOS Scopus РИНЦ CAPlusCA OpenAlex

Поступила в редакцию:	8 сент. 2015 г.
Опубликована online:	26 окт. 2015 г.
Опубликована в печати:	5 нояб. 2015 г.

Web of science:	WOS:000364435200027
Scopus:	2-s2.0-84946781469
РИНЦ:	24969734
Chemical Abstracts:	2015:1649375
Chemical Abstracts (print):	163:553486
OpenAlex:	W2285384451

БД	Цитирований
Web of science	63
Scopus	73
РИНЦ	63
OpenAlex	73