How Do Zn2+ Ions Promote Methane Activation on Zinc-Modified Zeolites? A Hybrid Quantum-Chemical Study Full article
| Journal |
Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X |
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| Output data | Year: 2025, Volume: 64, Number: 25, Pages: 12846–12859 Pages count : 14 DOI: 10.1021/acs.inorgchem.5c02133 | ||
| Tags | Adsorption; Enthalpy; Hydrocarbons; Hydrogen; Zeolites | ||
| Authors |
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| Affiliations |
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Funding (1)
| 1 | Ministry of Science and Higher Education of the Russian Federation | FWUR-2024-0032 |
Abstract:
It was earlier established that Zn2+ species loaded in zeolites promoted alkane C–H bond activation by Brønsted acid sites (BAS). It was found that the rate of H/D hydrogen exchange between alkane and zeolite BAS increased dramatically, and the activation barrier decreased for Zn2+-modified zeolite compared to H-form zeolite. However, it still remains unclear what the nature of the promoting effect of Zn2+ species on C–H bond activation is. In this work, the possible mechanisms of methane hydrogen exchange on the Zn2+/H-ZSM-5 zeolite have been analyzed by means of hybrid quantum chemical calculations (PBEh-3c/DLPNO-CCSD(T)). Four models representing various locations of Zn2+ ions in H-ZSM-5 differing in Al distribution and local geometry have been investigated. Zn2+ sites are found to be rather diverse in their adsorption properties and reactivity. The earlier accepted hypothesis of H/D hydrogen exchange promotion via the formation of a transient molecular complex of methane with Zn2+ sites has been disproven by the PBEh-3c/DLPNO-CCSD(T) calculations. Conversely, the two-step mechanism of hydrogen exchange in methane on Zn2+/H-ZSM-5 involving zinc-methyl species formation is concluded to be the most probable. Thus, the rationalization of how Zn2+ sites affect alkane C–H bond activation by BAS has been provided.
Cite:
Lashchinskaya Z.N.
, Gabrienko A.A.
, Stepanov A.G.
How Do Zn2+ Ions Promote Methane Activation on Zinc-Modified Zeolites? A Hybrid Quantum-Chemical Study
Inorganic Chemistry. 2025. V.64. N25. P.12846–12859. DOI: 10.1021/acs.inorgchem.5c02133 WOS Scopus AN PMID OpenAlex
How Do Zn2+ Ions Promote Methane Activation on Zinc-Modified Zeolites? A Hybrid Quantum-Chemical Study
Inorganic Chemistry. 2025. V.64. N25. P.12846–12859. DOI: 10.1021/acs.inorgchem.5c02133 WOS Scopus AN PMID OpenAlex
Dates:
| Submitted: | May 12, 2025 |
| Accepted: | Jun 12, 2025 |
| Published online: | Jun 17, 2025 |
| Published print: | Jun 30, 2025 |
Identifiers:
| Web of science: | WOS:001520189900001 |
| Scopus: | 2-s2.0-105008331576 |
| Chemical Abstracts: | 2025:1366704 |
| PMID: | 40526139 |
| OpenAlex: | W4411368994 |