The conversion of CO2 and CH4 to acetic acid over the Au-exchanged ZSM-5 catalyst: a density functional theory study

Panjan, Wasinee; Sirijaraensre, Jakkapan; Warakulwit, Chompunuch; Pantu, Piboon; Limtrakul, Jumras

doi:10.1039/c2cp42066j

Cited by 65 publications

(55 citation statements)

References 59 publications

(57 reference statements)

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“…To illustrate distinct catalytic performance on chemical fixation of CO 2 to propylene carbonate catalyzed by these constructed MOFs with different metal centers, molecular dynamic simulations were conducted . First, the C atom of CO 2 molecule is sp hybridized, which can form σ bond with O atom.…”

Section: Resultsmentioning

confidence: 99%

Bimetallic Metal‐Organic Frameworks: Probing the Lewis Acid Site for CO₂ Conversion

Zou

Zeng

et al. 2016

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A highly porous metal-organic framework (MOF) incorporating two kinds of second building units (SBUs), i.e., dimeric paddlewheel (Zn2 (COO)4 ) and tetrameric (Zn4 (O)(CO2 )6 ), is successfully assembled by the reaction of a tricarboxylate ligand with Zn(II) ion. Subsequently, single-crystal-to-single-crystal metal cation exchange using the constructed MOF is investigated, and the results show that Cu(II) and Co(II) ions can selectively be introduced into the MOF without compromising the crystallinity of the pristine framework. This metal cation-exchangeable MOF provides a useful platform for studying the metal effect on both gas adsorption and catalytic activity of the resulted MOFs. While the gas adsorption experiments reveal that Cu(II) and Co(II) exchanged samples exhibit comparable CO2 adsorption capability to the pristine Zn(II) -based MOF under the same conditions, catalytic investigations for the cycloaddition reaction of CO2 with epoxides into related carbonates demonstrate that Zn(II) -based MOF affords the highest catalytic activity as compared with Cu(II) and Co(II) exchanged ones. Molecular dynamic simulations are carried out to further confirm the catalytic performance of these constructed MOFs on chemical fixation of CO2 to carbonates. This research sheds light on how metal exchange can influence intrinsic properties of MOFs.

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Section: Resultsmentioning

confidence: 99%

Bimetallic Metal‐Organic Frameworks: Probing the Lewis Acid Site for CO₂ Conversion

Zou

Zeng

et al. 2016

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“…In a previous work, [11] we have shown that the adsorption of CO 2 over Au I -ZSM-5 is less favorable than that of methane in the acetic acid production and that methane activation is needed in the first step of the reaction. Without catalyst, the direct conversion of methane and carbon dioxide to carboxylic acid is kinetically very unfavorable with an E a of 83.8 kcal mol À1 , as calculated at the M06 L/ 6-31G(d,p) level, or 87.6 kcal mol À1 if calculated at the MP2/6-31G(d,p) level of theory.…”

Section: Càh Activation Of Ethanementioning

confidence: 98%

“…lite to produce acetic acid [11] has been demonstrated theoretically. However, this process requires high activation energy.…”

Section: Introductionmentioning

confidence: 97%

Conversion of CO₂ and C₂H₆ to Propanoic Acid over a Au‐Exchanged MCM‐22 Zeolite

2013

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Finding novel catalysts for the direct conversion of CO2 to fuels and chemicals is a primary goal in energy and environmental research. In this work, density functional theory (DFT) is used to study possible reaction mechanisms for the conversion of CO2 and C2H6 to propanoic acid over a gold-exchanged MCM-22 zeolite catalyst. The reaction begins with the activation of ethane to produce a gold ethyl hydride intermediate. Hydrogen transfers to the framework oxygen leads then to gold ethyl adsorbed on the Brønsted-acid site. The energy barriers for these steps of ethane activation are 9.3 and 16.3 kcal mol(-1), respectively. Two mechanisms of propanoic acid formation are investigated. In the first one, the insertion of CO2 into the Au-H bond of the first intermediate yields gold carboxyl ethyl as subsequent intermediate. This is then converted to propanoic acid by forming the relevant C-C bond. The activation energy of the rate-determining step of this pathway is 48.2 kcal mol(-1). In the second mechanism, CO2 interacts with gold ethyl adsorbed on the Brønsted-acid site. Propanoic acid is formed via protonation of CO2 by the Brønsted acid and the simultaneous formation of a bond between CO2 and the ethyl group. The activation energy there is 44.2 kcal mol(-1), favoring this second pathway at least at low temperatures. Gold-exchanged MCM-22 zeolite can therefore, at least in principle, be used as the catalyst for producing propanoic acid from CO2 and ethane.

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“…However,t he knowledge about CÀCcoupling between CH 4 and CO 2 is very limited owing to the difficulty to identify active species to simultaneously activate and couple these two substrates. [3,13] Recently,T rinh and co-workers predicted that boron-doped copper is apotential catalyst to activate methane to form the absorbed CH x (x = 2, 3) on the catalytic surface and selectively promote the C À Cc oupling reaction to produce ethylene. [12] Herein, we present the first example of diatomic species (CuB + )t hat can also couple CH 4 and CO 2 to form H 2 C = C = Ou nder thermal collision conditions.…”

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confidence: 99%

Coupling of Methane and Carbon Dioxide Mediated by Diatomic Copper Boride Cations

et al. 2018

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The conversion of CO2 and CH4 to acetic acid over the Au-exchanged ZSM-5 catalyst: a density functional theory study

Cited by 65 publications

References 59 publications

Bimetallic Metal‐Organic Frameworks: Probing the Lewis Acid Site for CO₂ Conversion

Bimetallic Metal‐Organic Frameworks: Probing the Lewis Acid Site for CO₂ Conversion

Conversion of CO₂ and C₂H₆ to Propanoic Acid over a Au‐Exchanged MCM‐22 Zeolite

Coupling of Methane and Carbon Dioxide Mediated by Diatomic Copper Boride Cations

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The conversion of CO2 and CH4 to acetic acid over the Au-exchanged ZSM-5 catalyst: a density functional theory study

Cited by 65 publications

References 59 publications

Bimetallic Metal‐Organic Frameworks: Probing the Lewis Acid Site for CO2 Conversion

Bimetallic Metal‐Organic Frameworks: Probing the Lewis Acid Site for CO2 Conversion

Conversion of CO2 and C2H6 to Propanoic Acid over a Au‐Exchanged MCM‐22 Zeolite

Coupling of Methane and Carbon Dioxide Mediated by Diatomic Copper Boride Cations

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Bimetallic Metal‐Organic Frameworks: Probing the Lewis Acid Site for CO₂ Conversion

Bimetallic Metal‐Organic Frameworks: Probing the Lewis Acid Site for CO₂ Conversion

Conversion of CO₂ and C₂H₆ to Propanoic Acid over a Au‐Exchanged MCM‐22 Zeolite