Isobutane Activation and Transformation on In-Modified ZSM-5 Zeolites: Insights from Solid-State NMR, FTIR Spectroscopy, and DFT Calculations Full article
| Journal |
The Journal of Physical Chemistry C
ISSN: 1932-7447 , E-ISSN: 1932-7455 |
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| Output data | Year: 2024, Volume: 128, Number: 39, Pages: 16532-16550 Pages count : 19 DOI: 10.1021/acs.jpcc.4c05632 | ||
| Tags | 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 | ||
| Authors |
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| Affiliations |
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Funding (2)
| 1 | Russian Science Foundation | 22-13-00029 |
| 2 | Ministry of Science and Higher Education of the Russian Federation | FWUR-2024-0032 |
Abstract:
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.
Cite:
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
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
Dates:
| Submitted: | Aug 21, 2024 |
| Accepted: | Sep 17, 2024 |
| Published online: | Sep 24, 2024 |
| Published print: | Oct 3, 2024 |
Identifiers:
| Web of science: | WOS:001320777900001 |
| Scopus: | 2-s2.0-85205749056 |
| OpenAlex: | W4402765040 |
Citing:
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