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Mechanistic insights into the C–H activation of methane mediated by the unsupported and silica-supported VO(2)OH and CrOOH: a DFT study

The direct activation and conversion of methane has been a topic of interest in both academia and industry for several decades. Deep understanding of the corresponding mechanism and reactivity mediated by diverse catalytic clusters, as well as the supporting materials, is still highly desired. In th...

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Autores principales: Zhao, Shidong, Ma, Lishuang, Xi, Yanyan, Shang, Hongyan, Lin, Xufeng
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8695886/
https://www.ncbi.nlm.nih.gov/pubmed/35423641
http://dx.doi.org/10.1039/d0ra10785a
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author Zhao, Shidong
Ma, Lishuang
Xi, Yanyan
Shang, Hongyan
Lin, Xufeng
author_facet Zhao, Shidong
Ma, Lishuang
Xi, Yanyan
Shang, Hongyan
Lin, Xufeng
author_sort Zhao, Shidong
collection PubMed
description The direct activation and conversion of methane has been a topic of interest in both academia and industry for several decades. Deep understanding of the corresponding mechanism and reactivity mediated by diverse catalytic clusters, as well as the supporting materials, is still highly desired. In this work, the regulation mechanism of C–H bond activation of methane, mediated by the closed-shell VO(2)OH, the open-shell CrOOH, and their silica supported clusters, has been investigated by density functional theory (DFT) calculations. The hydrogen-atom transfer (HAT) reaction towards methane C–H bond activation is more feasible when mediated by the unsupported/silica-supported CrOOH clusters versus the VO(2)OH clusters, due to the intrinsic spin density located on the terminal O(t) atom. The proton-coupled electron transfer (PCET) pathways are regulated by both the nucleophilicity of the O(t) site and the electrophilicity of the metal center, which show no obvious difference in energy consumption among the four reactions examined. Moreover, the introduction of a silica support can lead to subtle influences on the intermolecular interaction between the CH(4) molecule and the catalyst cluster, as well as the thermodynamics of the methane C–H activation.
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spelling pubmed-86958862022-04-13 Mechanistic insights into the C–H activation of methane mediated by the unsupported and silica-supported VO(2)OH and CrOOH: a DFT study Zhao, Shidong Ma, Lishuang Xi, Yanyan Shang, Hongyan Lin, Xufeng RSC Adv Chemistry The direct activation and conversion of methane has been a topic of interest in both academia and industry for several decades. Deep understanding of the corresponding mechanism and reactivity mediated by diverse catalytic clusters, as well as the supporting materials, is still highly desired. In this work, the regulation mechanism of C–H bond activation of methane, mediated by the closed-shell VO(2)OH, the open-shell CrOOH, and their silica supported clusters, has been investigated by density functional theory (DFT) calculations. The hydrogen-atom transfer (HAT) reaction towards methane C–H bond activation is more feasible when mediated by the unsupported/silica-supported CrOOH clusters versus the VO(2)OH clusters, due to the intrinsic spin density located on the terminal O(t) atom. The proton-coupled electron transfer (PCET) pathways are regulated by both the nucleophilicity of the O(t) site and the electrophilicity of the metal center, which show no obvious difference in energy consumption among the four reactions examined. Moreover, the introduction of a silica support can lead to subtle influences on the intermolecular interaction between the CH(4) molecule and the catalyst cluster, as well as the thermodynamics of the methane C–H activation. The Royal Society of Chemistry 2021-03-17 /pmc/articles/PMC8695886/ /pubmed/35423641 http://dx.doi.org/10.1039/d0ra10785a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Zhao, Shidong
Ma, Lishuang
Xi, Yanyan
Shang, Hongyan
Lin, Xufeng
Mechanistic insights into the C–H activation of methane mediated by the unsupported and silica-supported VO(2)OH and CrOOH: a DFT study
title Mechanistic insights into the C–H activation of methane mediated by the unsupported and silica-supported VO(2)OH and CrOOH: a DFT study
title_full Mechanistic insights into the C–H activation of methane mediated by the unsupported and silica-supported VO(2)OH and CrOOH: a DFT study
title_fullStr Mechanistic insights into the C–H activation of methane mediated by the unsupported and silica-supported VO(2)OH and CrOOH: a DFT study
title_full_unstemmed Mechanistic insights into the C–H activation of methane mediated by the unsupported and silica-supported VO(2)OH and CrOOH: a DFT study
title_short Mechanistic insights into the C–H activation of methane mediated by the unsupported and silica-supported VO(2)OH and CrOOH: a DFT study
title_sort mechanistic insights into the c–h activation of methane mediated by the unsupported and silica-supported vo(2)oh and crooh: a dft study
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8695886/
https://www.ncbi.nlm.nih.gov/pubmed/35423641
http://dx.doi.org/10.1039/d0ra10785a
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