Isobutane Activation and Transformation on In-Modified ZSM-5 Zeolites: Insights from Solid-State NMR, FTIR Spectroscopy, and DFT Calculations | Sciact - CRIS-система Института катализа

Isobutane Activation and Transformation on In-Modified ZSM-5 Zeolites: Insights from Solid-State NMR, FTIR Spectroscopy, and DFT Calculations Научная публикация

Журнал

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

Вых. Данные

Год: 2024, Том: 128, Номер: 39, Страницы: 16532-16550 Страниц : 19 DOI: 10.1021/acs.jpcc.4c05632

Ключевые слова

BUTYL ALCOHOL DEHYDRATION; H/D HYDROGEN-EXCHANGE; C-13 CHEMICAL-SHIFTS; METHANE ACTIVATION; H-ZSM-5 ZEOLITE; CATALYTIC-ACTIVITY; ACTIVE-SITES; VIBRATIONAL-SPECTRA; SELECTIVE REDUCTION; NOX REDUCTION

Авторы

Lashchinskaya Zoya N. ¹ , Gabrienko Anton A. ¹ , Arzumanov Sergei S. ¹ , Toktarev Alexander V. ¹ , Prosvirin Igor P. ¹ , Stepanov Alexander G. ¹

Организации

1	Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia

Информация о финансировании (2)

1	Российский научный фонд	22-13-00029
2	Министерство науки и высшего образования Российской Федерации (с 15 мая 2018)	FWUR-2024-0032

With respect to the potential application of indium-modified zeolites for light alkane conversion to simple aromatic hydrocarbons and their oxidation to carboxylic acids, the pathways of isobutane transformation on the In/H-ZSM-5 zeolite have been investigated by a combination of solid-state NMR spectroscopy, FTIR spectroscopy, and density functional theory (DFT) calculations. It is found that isobutane undergoes activation on InO+ sites of In/H-ZSM-5 zeolites via the “alkyl” pathway to yield isobutylindium species, which precedes the formation of isobutene at 296 K. Analysis of isobutene transformation on In/H-ZSM-5 shows the formation of allyl-like intermediates, alkoxy species, and cyclopentenyl cations from the alkene. This implies that oligomerization and aromatization of isobutene formed from the alkane occurred with the involvement of both InO+ sites and Brønsted acid sites (BASs) at 473–573 K. At higher temperatures (T ≥ 623 K), C2–C4 surface carboxylic species have been found as the products of isobutane oxidation. It is inferred that the direct oxidation of isobutane molecules to carboxylate species does not occur, contrary to the earlier found cases with propane and n-butane transformation on In-modified zeolites. Additionally, DFT calculations have been used to analyze the localization of indium species in the ZSM-5 zeolite, the energies of isobutane and isobutene adsorption on differently located active sites (InO+ and BAS), and the mechanisms of C–H bond activation in the alkane.

Lashchinskaya Z.N. , Gabrienko A.A. , Arzumanov S.S. , Toktarev A.V. , Prosvirin I.P. , Stepanov A.G.
Isobutane Activation and Transformation on In-Modified ZSM-5 Zeolites: Insights from Solid-State NMR, FTIR Spectroscopy, and DFT Calculations
The Journal of Physical Chemistry C. 2024. V.128. N39. P.16532-16550. DOI: 10.1021/acs.jpcc.4c05632 WOS Scopus OpenAlex

Поступила в редакцию:	21 авг. 2024 г.
Принята к публикации:	17 сент. 2024 г.
Опубликована online:	24 сент. 2024 г.
Опубликована в печати:	3 окт. 2024 г.

Web of science:	WOS:001320777900001
Scopus:	2-s2.0-85205749056
OpenAlex:	W4402765040

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