Defect Stabilized Gold Atoms on Graphene as Potential Catalysts for Ethylene Epoxidation: A First-principles Investigation

Handle URI:
http://hdl.handle.net/10754/583494
Title:
Defect Stabilized Gold Atoms on Graphene as Potential Catalysts for Ethylene Epoxidation: A First-principles Investigation
Authors:
Liu, Xin; Yang, Yang; Chu, Minmin; Duan, Ting; Meng, Changgong; Han, Yu ( 0000-0003-1462-1118 )
Abstract:
We performed a first-principles based investigation on the potential role of Au atoms stabilized by defects on graphene in ethylene epoxidation. We showed that the interactions between the Au atoms and vacancies on graphene not only make the Au atomic diffusion a 2.10 eV endothermic process, but also tune the energy level of Au-d states for the activation of O2 and ethylene and promote the formation and dissociation of the peroxametallacycle intermediate. The catalytic cycle of ethylene epoxidation is initiated with the formation of a peroxametallacycle intermediate by the coadsorbed ethylene and O2, through the dissociation of which an ethylene epoxide molecule and an adsorbed O atom are formed. Then, gaseous ethylene reacts with the remnant O atom directly for the formation of another ethylene epoxide molecule. The desorption of ethylene epoxide is facilitated by the subsequent adsorption of O2 or ethylene and a new reaction cycle initiates. The calculated energy barriers for the formation and dissociation of the peroxametallacycle intermediate and the regeneration of Au sites are 0.30, 0.84 and 0.18 eV, respectively, and are significantly lower than those for aldehyde formation. These findings suggest the potential high catalytic performance of these Au atoms for ethylene epoxidation.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; Advanced Membranes and Porous Materials Research Center
Citation:
Defect Stabilized Gold Atoms on Graphene as Potential Catalysts for Ethylene Epoxidation: A First-principles Investigation 2015 Catal. Sci. Technol.
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Catal. Sci. Technol.
Issue Date:
24-Nov-2015
DOI:
10.1039/C5CY01619C
Type:
Article
ISSN:
2044-4753; 2044-4761
Additional Links:
http://pubs.rsc.org/en/Content/ArticleLanding/2015/CY/C5CY01619C
Appears in Collections:
Articles; Advanced Membranes and Porous Materials Research Center; Physical Sciences and Engineering (PSE) Division

Full metadata record

DC FieldValue Language
dc.contributor.authorLiu, Xinen
dc.contributor.authorYang, Yangen
dc.contributor.authorChu, Minminen
dc.contributor.authorDuan, Tingen
dc.contributor.authorMeng, Changgongen
dc.contributor.authorHan, Yuen
dc.date.accessioned2015-12-09T12:52:01Zen
dc.date.available2015-12-09T12:52:01Zen
dc.date.issued2015-11-24en
dc.identifier.citationDefect Stabilized Gold Atoms on Graphene as Potential Catalysts for Ethylene Epoxidation: A First-principles Investigation 2015 Catal. Sci. Technol.en
dc.identifier.issn2044-4753en
dc.identifier.issn2044-4761en
dc.identifier.doi10.1039/C5CY01619Cen
dc.identifier.urihttp://hdl.handle.net/10754/583494en
dc.description.abstractWe performed a first-principles based investigation on the potential role of Au atoms stabilized by defects on graphene in ethylene epoxidation. We showed that the interactions between the Au atoms and vacancies on graphene not only make the Au atomic diffusion a 2.10 eV endothermic process, but also tune the energy level of Au-d states for the activation of O2 and ethylene and promote the formation and dissociation of the peroxametallacycle intermediate. The catalytic cycle of ethylene epoxidation is initiated with the formation of a peroxametallacycle intermediate by the coadsorbed ethylene and O2, through the dissociation of which an ethylene epoxide molecule and an adsorbed O atom are formed. Then, gaseous ethylene reacts with the remnant O atom directly for the formation of another ethylene epoxide molecule. The desorption of ethylene epoxide is facilitated by the subsequent adsorption of O2 or ethylene and a new reaction cycle initiates. The calculated energy barriers for the formation and dissociation of the peroxametallacycle intermediate and the regeneration of Au sites are 0.30, 0.84 and 0.18 eV, respectively, and are significantly lower than those for aldehyde formation. These findings suggest the potential high catalytic performance of these Au atoms for ethylene epoxidation.en
dc.language.isoenen
dc.publisherRoyal Society of Chemistry (RSC)en
dc.relation.urlhttp://pubs.rsc.org/en/Content/ArticleLanding/2015/CY/C5CY01619Cen
dc.rightsArchived with thanks to Catal. Sci. Technol.en
dc.titleDefect Stabilized Gold Atoms on Graphene as Potential Catalysts for Ethylene Epoxidation: A First-principles Investigationen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentAdvanced Membranes and Porous Materials Research Centeren
dc.identifier.journalCatal. Sci. Technol.en
dc.eprint.versionPost-printen
dc.contributor.institutionSchool of Chemistry, State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, PR Chinaen
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorHan, Yuen
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