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Theoretical Exploration of the Mechanisms for Methane-to-Methanol Conversion Using Bare and ZSM-5-Supported Pd4Clusters

Authors :
Dutta, Priyanka
Biswakarma, Nishant
Dowerah, Dikshita
Neog, Shilpa
Phonglo, Ambalika
Sarma, Plaban Jyoti
Gour, Nand Kishor
Deka, Ramesh Chandra
Source :
The Journal of Physical Chemistry - Part C; December 2024, Vol. 128 Issue: 50 p21263-21279, 17p
Publication Year :
2024

Abstract

This paper presents a comprehensive mechanistic investigation into the partial oxidation of methane to methanol on bare and ZSM-5-supported Pd4clusters utilizing N2O as an oxidant. The study employs density functional theory (DFT) with ONIOM2 (QM: MM) (B3PW91/LANL2DZ/6-31G(d,p):UFF) with dispersion correction calculations to explore potential energy surfaces (PESs) associated with the methane-to-methanol conversion process in a ZSM-5-supported Pd4cluster. Two spin multiplicities (SM = 1, 3) were considered for the overall reaction pathway. The investigation reveals that C–H activation of methane takes place subsequent to the formation of Pd4O from the N2O decomposition step, which ultimately leads to methanol formation. The study indicates that in terms of activation barrier, the N–O and C–H activation steps exhibit a lower energy barrier in the singlet state, while the recombination step of CH3and OH moieties is preferable in the triplet spin state. However, the reaction process does not involve any spin crossover, as the triplet spin state consistently maintains the lowest energy pathway throughout the reaction. From the overall analysis of the reaction mechanisms for methane to methanol, it is evident that zeolite support and spin multiplicity play a significant role in lowering the activation barriers.

Details

Language :
English
ISSN :
19327447 and 19327455
Volume :
128
Issue :
50
Database :
Supplemental Index
Journal :
The Journal of Physical Chemistry - Part C
Publication Type :
Periodical
Accession number :
ejs68230889
Full Text :
https://doi.org/10.1021/acs.jpcc.4c05047