Property–Activity Relations of Multifunctional Reactive Ensembles in Cation-Exchanged Zeolites: A Case Study of Methane Activation on Zn2+-Modified Zeolite BEA | Sciact - CRIS-system of Boreskov Institute of Catalysis

Property–Activity Relations of Multifunctional Reactive Ensembles in Cation-Exchanged Zeolites: A Case Study of Methane Activation on Zn2+-Modified Zeolite BEA Full article

Journal

PCCP: Physical Chemistry Chemical Physics
ISSN: 1463-9076 , E-ISSN: 1463-9084

Output data

Year: 2022, Volume: 24, Number: 11, Pages: 6492-6504 Pages count : 13 DOI: 10.1039/d1cp05854a

Tags

FRUSTRATED LEWIS PAIRS; HIGH-SILICA ZEOLITES; DIRECT CONVERSION; ACETIC-ACID; MECHANISTIC INSIGHT; PYRIDINE ADSORPTION; FTIR SPECTROSCOPY; MOLECULAR-SIEVES; PROBE MOLECULE; CH4 ACTIVATION

Authors

Kolganov Alexander A. ¹ , Gabrienko Anton A. ¹ , Chernyshov Ivan Yu. ² , Stepanov Alexander G. ¹ , Pidko Evgeny A. ^3,4

Affiliations

1	Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
2	TheoMAT Group, ChemBio Cluster, ITMO University, Lomonosova Street 9, Saint Petersburg, 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, The Netherlands
4	TsyfroCatLab Group, University of Tyumen, Volodarskogo St. 6, Tyumen 625003, Russia

Funding (3)

1	Ministry of Science and Higher Education of the Russian Federation	0239-2021-0003
2	Правительство Тюменской области	2.89-дон от 07.12.2020
3	Netherlands Organisation for Scientific Research

The reactivity theories and characterization studies for metal-containing zeolites are often focused on probing the metal sites. We present a detailed computational study of the reactivity of Zn-modified BEA zeolite towards C–H bond activation of the methane molecule as a model system that highlights the importance of representing the active site as the whole reactive ensemble integrating the extra-framework ZnEF2+ cations, framework oxygens (OF2−), and the confined space of the zeolite pores. We demonstrate that for our model system the relationship between the Lewis acidity, defined by the probe molecule adsorption energy, and the activation energy for methane C–H bond cleavage performs with a determination coefficient R2 = 0.55. This suggests that the acid properties of the localized extra-framework cations can be used only for a rough assessment of the reactivity of the cations in the metal-containing zeolites. In turn, studying the relationship between the activation energy and pyrrole adsorption energy revealed a correlation, with R2 = 0.80. This observation was accounted for by the similarity between the local geometries of the pyrrole adsorption complexes and the transition states for methane C–H bond cleavage. The inclusion of a simple descriptor for zeolite local confinement allows transferability of the obtained property–activity relations to other zeolite topologies. Our results demonstrate that the representation of the metal cationic species as a synergistically cooperating active site ensembles allows reliable detection of the relationship between the acid properties and reactivity of the metal cation in zeolite materials.

Kolganov A.A. , Gabrienko A.A. , Chernyshov I.Y. , Stepanov A.G. , Pidko E.A.
Property–Activity Relations of Multifunctional Reactive Ensembles in Cation-Exchanged Zeolites: A Case Study of Methane Activation on Zn2+-Modified Zeolite BEA
PCCP: Physical Chemistry Chemical Physics. 2022. V.24. N11. P.6492-6504. DOI: 10.1039/d1cp05854a WOS Scopus РИНЦ AN PMID OpenAlex

Submitted:	Dec 22, 2021
Accepted:	Feb 20, 2022
Published print:	Mar 7, 2022
Published online:	Mar 7, 2022

Web of science:	WOS:000765453800001
Scopus:	2-s2.0-85127138359
Elibrary:	48421192
Chemical Abstracts:	2022:606420
PMID:	35254352
OpenAlex:	W4221108202

DB	Citing
Web of science	7
Scopus	7
Elibrary	8
OpenAlex	8