Is there a relationship between the M=O bond length (strength) of bulk mixed metal oxides and their catalytic activity?

Autores
Routray, Kamalakanta; Briand, Laura Estefania; Wachs, Israel E.
Año de publicación
2008
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
It is widely accepted in the catalysis literature that the bulk M=O bond of bulk mixed metal oxides controls catalytic activity. In the present study, for the first time, the bulk M=O bond lengths (strengths) and the surface catalytic activity of bulk metal vanadates and molybdates were quantitatively compared to allow examination of this long-standing hypothesis. The bulk M=O bond lengths were obtained from crystallographic studies and also determined by Raman spectroscopy. The surface catalytic activity was determined by CH3OH-temperature programmed surface reaction (TPSR) spectroscopy and steady-state methanol oxidation. The CH3OH-TPSR experiments provided the first-order rate constants for breaking of the C?H bond for the decomposition of the surface CH3O* intermediate to H2CO and the number of catalytic active sites Ns. The corresponding steady-state methanol oxidation studies provided the equilibrium adsorption constant Kads for breaking the methanol OH bond and the specific reaction rate (TOF). The findings clearly demonstrate the lack of correlations among krds, Kads, TOF, and the bulk M=O bond length (strength). This finding is not so surprising when one considers that the adsorption step involves breaking the methanol OH bond and the rate-determining step involves breaking the surface methoxy CH bond on surface MO sites, not bulk M=O bond-breaking.
Fil: Routray, Kamalakanta. Lehigh University. Chemical Engineering Department, Operando Molecular Spectroscopy and Catalysis Laboratory; Estados Unidos
Fil: Briand, Laura Estefania. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - la Plata. Centro de Investigación y Desarrollo En Ciencias Aplicadas "dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo En Ciencias Aplicadas; Argentina
Fil: Wachs, Israel E.. Lehigh University. Chemical Engineering Department, Operando Molecular Spectroscopy and Catalysis Laboratory; Estados Unidos
Materia
Catalists
Metal Oxide
Molybdates
Vanadates
Reaction
Methanol (Ch3oh)
Oxidation
Formaldehyde (H2co)
Spectroscopy
Raman
Tpsr
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/16649
Acceder
id CONICETDig_768104edb208f3c96ccdf3f797e77242
oai_identifier_str oai:ri.conicet.gov.ar:11336/16649
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Is there a relationship between the M=O bond length (strength) of bulk mixed metal oxides and their catalytic activity?Routray, KamalakantaBriand, Laura EstefaniaWachs, Israel E.CatalistsMetal OxideMolybdatesVanadatesReactionMethanol (Ch3oh)OxidationFormaldehyde (H2co)SpectroscopyRamanTpsrhttps://purl.org/becyt/ford/2.5https://purl.org/becyt/ford/2It is widely accepted in the catalysis literature that the bulk M=O bond of bulk mixed metal oxides controls catalytic activity. In the present study, for the first time, the bulk M=O bond lengths (strengths) and the surface catalytic activity of bulk metal vanadates and molybdates were quantitatively compared to allow examination of this long-standing hypothesis. The bulk M=O bond lengths were obtained from crystallographic studies and also determined by Raman spectroscopy. The surface catalytic activity was determined by CH3OH-temperature programmed surface reaction (TPSR) spectroscopy and steady-state methanol oxidation. The CH3OH-TPSR experiments provided the first-order rate constants for breaking of the C?H bond for the decomposition of the surface CH3O* intermediate to H2CO and the number of catalytic active sites Ns. The corresponding steady-state methanol oxidation studies provided the equilibrium adsorption constant Kads for breaking the methanol OH bond and the specific reaction rate (TOF). The findings clearly demonstrate the lack of correlations among krds, Kads, TOF, and the bulk M=O bond length (strength). This finding is not so surprising when one considers that the adsorption step involves breaking the methanol OH bond and the rate-determining step involves breaking the surface methoxy CH bond on surface MO sites, not bulk M=O bond-breaking.Fil: Routray, Kamalakanta. Lehigh University. Chemical Engineering Department, Operando Molecular Spectroscopy and Catalysis Laboratory; Estados UnidosFil: Briand, Laura Estefania. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - la Plata. Centro de Investigación y Desarrollo En Ciencias Aplicadas "dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo En Ciencias Aplicadas; ArgentinaFil: Wachs, Israel E.. Lehigh University. Chemical Engineering Department, Operando Molecular Spectroscopy and Catalysis Laboratory; Estados UnidosElsevier2008-03-10info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/16649Routray, Kamalakanta; Briand, Laura Estefania; Wachs, Israel E.; Is there a relationship between the M=O bond length (strength) of bulk mixed metal oxides and their catalytic activity?; Elsevier; Journal Of Catalysis; 256; 1; 10-3-2008; 145-1530021-9517enginfo:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0021951708001061info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jcat.2008.03.010info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:04:44Zoai:ri.conicet.gov.ar:11336/16649instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-03 10:04:45.071CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Is there a relationship between the M=O bond length (strength) of bulk mixed metal oxides and their catalytic activity?
title Is there a relationship between the M=O bond length (strength) of bulk mixed metal oxides and their catalytic activity?
spellingShingle Is there a relationship between the M=O bond length (strength) of bulk mixed metal oxides and their catalytic activity?
Routray, Kamalakanta
Catalists
Metal Oxide
Molybdates
Vanadates
Reaction
Methanol (Ch3oh)
Oxidation
Formaldehyde (H2co)
Spectroscopy
Raman
Tpsr
title_short Is there a relationship between the M=O bond length (strength) of bulk mixed metal oxides and their catalytic activity?
title_full Is there a relationship between the M=O bond length (strength) of bulk mixed metal oxides and their catalytic activity?
title_fullStr Is there a relationship between the M=O bond length (strength) of bulk mixed metal oxides and their catalytic activity?
title_full_unstemmed Is there a relationship between the M=O bond length (strength) of bulk mixed metal oxides and their catalytic activity?
title_sort Is there a relationship between the M=O bond length (strength) of bulk mixed metal oxides and their catalytic activity?
dc.creator.none.fl_str_mv Routray, Kamalakanta
Briand, Laura Estefania
Wachs, Israel E.
author Routray, Kamalakanta
author_facet Routray, Kamalakanta
Briand, Laura Estefania
Wachs, Israel E.
author_role author
author2 Briand, Laura Estefania
Wachs, Israel E.
author2_role author
author
dc.subject.none.fl_str_mv Catalists
Metal Oxide
Molybdates
Vanadates
Reaction
Methanol (Ch3oh)
Oxidation
Formaldehyde (H2co)
Spectroscopy
Raman
Tpsr
topic Catalists
Metal Oxide
Molybdates
Vanadates
Reaction
Methanol (Ch3oh)
Oxidation
Formaldehyde (H2co)
Spectroscopy
Raman
Tpsr
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.5
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv It is widely accepted in the catalysis literature that the bulk M=O bond of bulk mixed metal oxides controls catalytic activity. In the present study, for the first time, the bulk M=O bond lengths (strengths) and the surface catalytic activity of bulk metal vanadates and molybdates were quantitatively compared to allow examination of this long-standing hypothesis. The bulk M=O bond lengths were obtained from crystallographic studies and also determined by Raman spectroscopy. The surface catalytic activity was determined by CH3OH-temperature programmed surface reaction (TPSR) spectroscopy and steady-state methanol oxidation. The CH3OH-TPSR experiments provided the first-order rate constants for breaking of the C?H bond for the decomposition of the surface CH3O* intermediate to H2CO and the number of catalytic active sites Ns. The corresponding steady-state methanol oxidation studies provided the equilibrium adsorption constant Kads for breaking the methanol OH bond and the specific reaction rate (TOF). The findings clearly demonstrate the lack of correlations among krds, Kads, TOF, and the bulk M=O bond length (strength). This finding is not so surprising when one considers that the adsorption step involves breaking the methanol OH bond and the rate-determining step involves breaking the surface methoxy CH bond on surface MO sites, not bulk M=O bond-breaking.
Fil: Routray, Kamalakanta. Lehigh University. Chemical Engineering Department, Operando Molecular Spectroscopy and Catalysis Laboratory; Estados Unidos
Fil: Briand, Laura Estefania. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - la Plata. Centro de Investigación y Desarrollo En Ciencias Aplicadas "dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo En Ciencias Aplicadas; Argentina
Fil: Wachs, Israel E.. Lehigh University. Chemical Engineering Department, Operando Molecular Spectroscopy and Catalysis Laboratory; Estados Unidos
description It is widely accepted in the catalysis literature that the bulk M=O bond of bulk mixed metal oxides controls catalytic activity. In the present study, for the first time, the bulk M=O bond lengths (strengths) and the surface catalytic activity of bulk metal vanadates and molybdates were quantitatively compared to allow examination of this long-standing hypothesis. The bulk M=O bond lengths were obtained from crystallographic studies and also determined by Raman spectroscopy. The surface catalytic activity was determined by CH3OH-temperature programmed surface reaction (TPSR) spectroscopy and steady-state methanol oxidation. The CH3OH-TPSR experiments provided the first-order rate constants for breaking of the C?H bond for the decomposition of the surface CH3O* intermediate to H2CO and the number of catalytic active sites Ns. The corresponding steady-state methanol oxidation studies provided the equilibrium adsorption constant Kads for breaking the methanol OH bond and the specific reaction rate (TOF). The findings clearly demonstrate the lack of correlations among krds, Kads, TOF, and the bulk M=O bond length (strength). This finding is not so surprising when one considers that the adsorption step involves breaking the methanol OH bond and the rate-determining step involves breaking the surface methoxy CH bond on surface MO sites, not bulk M=O bond-breaking.
publishDate 2008
dc.date.none.fl_str_mv 2008-03-10
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/16649
Routray, Kamalakanta; Briand, Laura Estefania; Wachs, Israel E.; Is there a relationship between the M=O bond length (strength) of bulk mixed metal oxides and their catalytic activity?; Elsevier; Journal Of Catalysis; 256; 1; 10-3-2008; 145-153
0021-9517
url http://hdl.handle.net/11336/16649
identifier_str_mv Routray, Kamalakanta; Briand, Laura Estefania; Wachs, Israel E.; Is there a relationship between the M=O bond length (strength) of bulk mixed metal oxides and their catalytic activity?; Elsevier; Journal Of Catalysis; 256; 1; 10-3-2008; 145-153
0021-9517
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0021951708001061
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jcat.2008.03.010
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
_version_ 1842269873027153920
score 13.13397

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