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Acetylene and Ethylene Adsorption on a β-Mo2C(100) Surface: A Periodic DFT Study on the Role of C- and Mo-Terminations for Bonding and Hydrogenation Reactions

dc.creatorJimenez-Orozco C.spa
dc.creatorFlorez E.spa
dc.creatorMoreno A.spa
dc.creatorLiu P.spa
dc.creatorRodriguez J.A.spa
dc.date.accessioned2017-12-19T19:36:44Z
dc.date.available2017-12-19T19:36:44Z
dc.date.created2017
dc.identifier.issn19327447
dc.identifier.urihttp://hdl.handle.net/11407/4284
dc.description.abstractMo2C catalysts are widely used in hydrogenation reactions; however, the role of the C and Mo terminations in these catalysts is not clear. Understanding the binding of adsorbates is key for explaining the activity of Mo2C. The adsorption of acetylene and ethylene, probe molecules representing alkynes and olefins, respectively, was studied on a β-Mo2C(100) surface with C and Mo terminations using calculations based on periodic density functional theory. Moreover, the role of the C/Mo molar ratio was investigated to compare the catalytic potential of cubic (δ-MoC) and orthorhombic (β-Mo2C) surfaces. The geometry and electronic properties of the clean δ-MoC(001) and β-Mo2C(100) surfaces have a strong influence on the binding of unsaturated hydrocarbons. The adsorption of ethylene is weaker than that of acetylene on the surfaces of the cubic and orthorhombic systems; adsorption of the hydrocarbons was stronger on β-Mo2C(100) than on δ-MoC(001). The C termination in β-Mo2C(100) actively participates in both acetylene and ethylene adsorption and is not merely a spectator. The results of this work suggest that the β-Mo2C(100)-C surface could be the one responsible for the catalytic activity during the hydrogenation of unsaturated C≡C and C=C bonds, while the Mo-terminated surface could be poisoned or transformed by the strong adsorption of C and CHx fragments. (Chemical Equation Presented). © 2017 American Chemical Society.eng
dc.language.isoeng
dc.publisherAmerican Chemical Societyspa
dc.relation.isversionofhttps://www.scopus.com/inward/record.uri?eid=2-s2.0-85029514849&doi=10.1021%2facs.jpcc.7b05442&partnerID=40&md5=e98cf75bdd9602a6f351521524d6b1f5spa
dc.sourceScopusspa
dc.titleAcetylene and Ethylene Adsorption on a β-Mo2C(100) Surface: A Periodic DFT Study on the Role of C- and Mo-Terminations for Bonding and Hydrogenation Reactionsspa
dc.typeArticleeng
dc.rights.accessrightsinfo:eu-repo/semantics/restrictedAccess
dc.contributor.affiliationJimenez-Orozco, C., Química de Recursos Energéticos y Medio Ambiente, Instituto de Química, Facultad de Ciencias Exactas y Naturales, Universidad de Antioquia UdeA, Calle 70 No. 52-21, Medellín, Colombiaspa
dc.contributor.affiliationFlorez, E., Departamento de Facultad de Ciencias Básicas, Universidad de Medellín, Carrera 87 No 30-65, Medellín, Colombiaspa
dc.contributor.affiliationMoreno, A., Química de Recursos Energéticos y Medio Ambiente, Instituto de Química, Facultad de Ciencias Exactas y Naturales, Universidad de Antioquia UdeA, Calle 70 No. 52-21, Medellín, Colombiaspa
dc.contributor.affiliationLiu, P., Chemistry Department, Brookhaven National Laboratory, Upton, NY, United Statesspa
dc.contributor.affiliationRodriguez, J.A., Chemistry Department, Brookhaven National Laboratory, Upton, NY, United Statesspa
dc.identifier.doi10.1021/acs.jpcc.7b05442
dc.subject.keywordAcetyleneeng
dc.subject.keywordAdsorptioneng
dc.subject.keywordBinseng
dc.subject.keywordCatalyst activityeng
dc.subject.keywordCatalystseng
dc.subject.keywordChemical bondseng
dc.subject.keywordDensity functional theoryeng
dc.subject.keywordElectronic propertieseng
dc.subject.keywordEthyleneeng
dc.subject.keywordHydrocarbonseng
dc.subject.keywordLightingeng
dc.subject.keywordCatalytic potentialeng
dc.subject.keywordChemical equationseng
dc.subject.keywordEthylene adsorptioneng
dc.subject.keywordHydrogenation reactionseng
dc.subject.keywordMo-terminated surfaceeng
dc.subject.keywordOrthorhombic systemseng
dc.subject.keywordPeriodic density functional theoryeng
dc.subject.keywordUnsaturated hydrocarbonseng
dc.subject.keywordHydrogenationeng
dc.publisher.facultyFacultad de Ciencias Básicasspa
dc.abstractMo2C catalysts are widely used in hydrogenation reactions; however, the role of the C and Mo terminations in these catalysts is not clear. Understanding the binding of adsorbates is key for explaining the activity of Mo2C. The adsorption of acetylene and ethylene, probe molecules representing alkynes and olefins, respectively, was studied on a β-Mo2C(100) surface with C and Mo terminations using calculations based on periodic density functional theory. Moreover, the role of the C/Mo molar ratio was investigated to compare the catalytic potential of cubic (δ-MoC) and orthorhombic (β-Mo2C) surfaces. The geometry and electronic properties of the clean δ-MoC(001) and β-Mo2C(100) surfaces have a strong influence on the binding of unsaturated hydrocarbons. The adsorption of ethylene is weaker than that of acetylene on the surfaces of the cubic and orthorhombic systems; adsorption of the hydrocarbons was stronger on β-Mo2C(100) than on δ-MoC(001). The C termination in β-Mo2C(100) actively participates in both acetylene and ethylene adsorption and is not merely a spectator. The results of this work suggest that the β-Mo2C(100)-C surface could be the one responsible for the catalytic activity during the hydrogenation of unsaturated C≡C and C=C bonds, while the Mo-terminated surface could be poisoned or transformed by the strong adsorption of C and CHx fragments. (Chemical Equation Presented). © 2017 American Chemical Society.eng
dc.creator.affiliationQuímica de Recursos Energéticos y Medio Ambiente, Instituto de Química, Facultad de Ciencias Exactas y Naturales, Universidad de Antioquia UdeA, Calle 70 No. 52-21, Medellín, Colombiaspa
dc.creator.affiliationDepartamento de Facultad de Ciencias Básicas, Universidad de Medellín, Carrera 87 No 30-65, Medellín, Colombiaspa
dc.creator.affiliationChemistry Department, Brookhaven National Laboratory, Upton, NY, United Statesspa
dc.relation.ispartofesJournal of Physical Chemistry Cspa
dc.relation.ispartofesJournal of Physical Chemistry C Volume 121, Issue 36, 14 September 2017, Pages 19786-19795spa
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dc.identifier.reponamereponame:Repositorio Institucional Universidad de Medellínspa
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