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Insight into the direct conversion of methane to methanol on modified ZIF-204 from the perspective of DFT-based calculations

Direct oxidation of methane over oxo-doped ZIF-204, a bio-mimetic metal–organic framework, is investigated under first-principles calculations based on density functional theory. In the pristine ZIF-204, the tetrahedral methane molecule anchors to an open monocopper site via the so-called η(2) confi...

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Autores principales: Le, Thong Nguyen-Minh, Le, Thu Bao Nguyen, Nguyen, Phat Tan, Nguyen, Trang Thuy, Tran, Quang Ngoc, Nguyen, Toan The, Kawazoe, Yoshiyuki, Phan, Thang Bach, Nguyen, Duc Manh
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10214002/
https://www.ncbi.nlm.nih.gov/pubmed/37250213
http://dx.doi.org/10.1039/d3ra02650g
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author Le, Thong Nguyen-Minh
Le, Thu Bao Nguyen
Nguyen, Phat Tan
Nguyen, Trang Thuy
Tran, Quang Ngoc
Nguyen, Toan The
Kawazoe, Yoshiyuki
Phan, Thang Bach
Nguyen, Duc Manh
author_facet Le, Thong Nguyen-Minh
Le, Thu Bao Nguyen
Nguyen, Phat Tan
Nguyen, Trang Thuy
Tran, Quang Ngoc
Nguyen, Toan The
Kawazoe, Yoshiyuki
Phan, Thang Bach
Nguyen, Duc Manh
author_sort Le, Thong Nguyen-Minh
collection PubMed
description Direct oxidation of methane over oxo-doped ZIF-204, a bio-mimetic metal–organic framework, is investigated under first-principles calculations based on density functional theory. In the pristine ZIF-204, the tetrahedral methane molecule anchors to an open monocopper site via the so-called η(2) configuration with a physisorption energy of 0.24 eV. This weak binding arises from an electrostatic interaction between the negative charge of carbon in the methane molecule and the positive Cu(2+) cation in the framework. In the modified ZIF-204, the doped oxo species is stabilized at the axial position of a CuN(4)-base square pyramid at a distance of 2.06 Å. The dative covalent bond between Cu and oxo is responsible for the formation energy of 1.06 eV. With the presence of the oxo group, the presenting of electrons in the O_p(z) orbital accounts for the adsorption of methane via hydrogen bonding with an adsorption energy of 0.30 eV. The methane oxidation can occur via either a concerted direct oxo insertion mechanism or a hydrogen-atom abstraction radical rebound mechanism. Calculations on transition-state barriers show that reactions via the concerted direct oxo insertion mechanism can happen without energy barriers. Concerning the hydrogen-atom abstraction radical rebound mechanism, the C–H bond dissociation of the CH(4) molecule is barrierless, but the C–O bond recombination to form the CH(3)OH molecule occurs through a low barrier of 0.16 eV. These predictions suggest the modified ZIF-204 is a promising catalyst for methane oxidization.
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spelling pubmed-102140022023-05-27 Insight into the direct conversion of methane to methanol on modified ZIF-204 from the perspective of DFT-based calculations Le, Thong Nguyen-Minh Le, Thu Bao Nguyen Nguyen, Phat Tan Nguyen, Trang Thuy Tran, Quang Ngoc Nguyen, Toan The Kawazoe, Yoshiyuki Phan, Thang Bach Nguyen, Duc Manh RSC Adv Chemistry Direct oxidation of methane over oxo-doped ZIF-204, a bio-mimetic metal–organic framework, is investigated under first-principles calculations based on density functional theory. In the pristine ZIF-204, the tetrahedral methane molecule anchors to an open monocopper site via the so-called η(2) configuration with a physisorption energy of 0.24 eV. This weak binding arises from an electrostatic interaction between the negative charge of carbon in the methane molecule and the positive Cu(2+) cation in the framework. In the modified ZIF-204, the doped oxo species is stabilized at the axial position of a CuN(4)-base square pyramid at a distance of 2.06 Å. The dative covalent bond between Cu and oxo is responsible for the formation energy of 1.06 eV. With the presence of the oxo group, the presenting of electrons in the O_p(z) orbital accounts for the adsorption of methane via hydrogen bonding with an adsorption energy of 0.30 eV. The methane oxidation can occur via either a concerted direct oxo insertion mechanism or a hydrogen-atom abstraction radical rebound mechanism. Calculations on transition-state barriers show that reactions via the concerted direct oxo insertion mechanism can happen without energy barriers. Concerning the hydrogen-atom abstraction radical rebound mechanism, the C–H bond dissociation of the CH(4) molecule is barrierless, but the C–O bond recombination to form the CH(3)OH molecule occurs through a low barrier of 0.16 eV. These predictions suggest the modified ZIF-204 is a promising catalyst for methane oxidization. The Royal Society of Chemistry 2023-05-26 /pmc/articles/PMC10214002/ /pubmed/37250213 http://dx.doi.org/10.1039/d3ra02650g Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Le, Thong Nguyen-Minh
Le, Thu Bao Nguyen
Nguyen, Phat Tan
Nguyen, Trang Thuy
Tran, Quang Ngoc
Nguyen, Toan The
Kawazoe, Yoshiyuki
Phan, Thang Bach
Nguyen, Duc Manh
Insight into the direct conversion of methane to methanol on modified ZIF-204 from the perspective of DFT-based calculations
title Insight into the direct conversion of methane to methanol on modified ZIF-204 from the perspective of DFT-based calculations
title_full Insight into the direct conversion of methane to methanol on modified ZIF-204 from the perspective of DFT-based calculations
title_fullStr Insight into the direct conversion of methane to methanol on modified ZIF-204 from the perspective of DFT-based calculations
title_full_unstemmed Insight into the direct conversion of methane to methanol on modified ZIF-204 from the perspective of DFT-based calculations
title_short Insight into the direct conversion of methane to methanol on modified ZIF-204 from the perspective of DFT-based calculations
title_sort insight into the direct conversion of methane to methanol on modified zif-204 from the perspective of dft-based calculations
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10214002/
https://www.ncbi.nlm.nih.gov/pubmed/37250213
http://dx.doi.org/10.1039/d3ra02650g
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