Nature of the Surface Intermediates Formed from Methane on Cu-ZSM-5 Zeolite: A Combined Solid-State Nuclear Magnetic Resonance and Density Functional Theory Study | Sciact - CRIS-система Института катализа

Nature of the Surface Intermediates Formed from Methane on Cu-ZSM-5 Zeolite: A Combined Solid-State Nuclear Magnetic Resonance and Density Functional Theory Study Научная публикация

Журнал

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

Вых. Данные

Год: 2020, Том: 124, Номер: 11, Страницы: 6242-6252 Страниц : 11 DOI: 10.1021/acs.jpcc.0c00311

Ключевые слова

Chemical activation; Density functional theory; Methane; Methanol; Nuclear magnetic resonance spectroscopy; Zeolites

Авторы

Kolganov Alexander A. ¹ , Gabrienko Anton A. ^1,2 , Yashnik Svetlana A. ¹ , Pidko Evgeny A. ³ , Stepanov Alexander G. ¹

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	Inorganic Systems Engineering Group, Department of Chemical Engineering, Faculty of Applied Sciences, Delft University of Technology, Van der Maasweg 9, Delft, 2629 HZ, Netherlands

Информация о финансировании (2)

1	Федеральное агентство научных организаций России	0303-2016-0003
2	Российский научный фонд	18-73-00016

The intermediates formed upon the interaction of methane with Cu-modified ZSM-5 zeolites (Cu/H-ZSM-5) have been analyzed with solid-state NMR spectroscopy and DFT methods. Methane activation by Cu/H-ZSM-5 zeolites gives rise to three distinct surface methoxy-like species (-O-CH3) detected by 13C MAS NMR spectroscopy with specific chemical shifts in the range of 53-63 ppm. DFT calculations on representative cluster models of different sites potentially present in Cu/H-ZSM-5 have been used to assign these signals to (i) methanol adsorbed on two neighboring Cu sites (Cu-(HOCH3)-Cu, 62.6 ppm), (ii) methanol adsorbed on zeolite Brønsted acid sites (52.9 ppm), and (iii) lattice-bound methoxy groups (Si-O(CH3)-Al, 58.6). The formation of these methoxy-like intermediates depends on the Cu loading and, accordingly, the type of Cu species in the Cu/H-ZSM-5 zeolite. For the sample with low (0.1 wt %) Cu loading containing exclusively mononuclear isolated Cu species, only the intermediates ii and iii have been detected. The Cu-bound intermediate (i) is formed upon methane activation by multinuclear Cu sites featuring Cu-O-Cu bridging moieties present in the materials with relatively higher Cu loading (1.38 wt %). The presented results indicate that methane activation by Cu/H-ZSM-5 can be promoted by both mono- and multinuclear Cu species confined in the zeolite matrix. Copyright © 2020 American Chemical Society.

Kolganov A.A. , Gabrienko A.A. , Yashnik S.A. , Pidko E.A. , Stepanov A.G.
Nature of the Surface Intermediates Formed from Methane on Cu-ZSM-5 Zeolite: A Combined Solid-State Nuclear Magnetic Resonance and Density Functional Theory Study

The Journal of Physical Chemistry C. 2020. V.124. N11. P.6242-6252. DOI: 10.1021/acs.jpcc.0c00311 WOS Scopus РИНЦ CAPlus OpenAlex

Полный текст от издателя

Поступила в редакцию:	13 янв. 2020 г.
Принята к публикации:	17 февр. 2020 г.
Опубликована online:	26 февр. 2020 г.
Опубликована в печати:	19 мар. 2020 г.

Web of science:	WOS:000526396000038
Scopus:	2-s2.0-85081694425
РИНЦ:	43254052
Chemical Abstracts:	2020:385557
OpenAlex:	W3007294050

БД	Цитирований
Scopus	16
Web of science	41
РИНЦ	36
OpenAlex	41