Estudo teórico da interação metal−suporte em aglomerados de paládio depositados sobre as superfícies (110D) e (110C) da γ-alumina
Autor(a) principal: | |
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Data de Publicação: | 2021 |
Outros Autores: | |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Biblioteca Digital de Teses e Dissertações da UERJ |
Texto Completo: | http://www.bdtd.uerj.br/handle/1/18973 |
Resumo: | The metal−support interaction (MSI) existing in heterogeneous catalysts influences the structure−performance relationship of these materials. Concomitantly with the metal-metal interaction (MMI), the MSI hinders or favors the anchoring of adsorbate species on the catalyst and control the morphology and growth of the metal particle. γ-alumina (γ-Al2O3), an oxide widely used as support, presents a structural arrangement still not well-defined experimentally, being the main discussions regarding the crystal lattice and the distribution of octahedral (Alo) and tetrahedral (Alt) aluminum cations along with the bulk and surface. Quantum-mechanical calculations by Density Functional Theory (DFT) were performed to study the MSI effect in models proposed to represent γ-alumina (spinel-like)-supported palladium catalysts. Two approaches were adopted in this work: I – Analysis of the influence of different surfaces exposed by γ-alumina ((110D) and (110C)) on MSI in Pd4/γ-alumina models, facing the interaction with a fifth palladium atom and with one NO molecule and II – Study of the sequential growth (atom to atom) of a Pdn cluster (n = 1−7) on the (110D) surface of γ-alumina. The main results show that the magnitude of the MSI is twice as high when the (110C) surface is exposed. Distinct arrangements for Pd4 are produced on (110) terminations: boat (110D) and butterfly (110C). Natural Bond Orbital (NBO) calculations show that an electronic MSI (EMSI) is promoted at Pd/(110) interfaces, with Pd4→γ-alumina backdonation being the preferential direction. The EMSI effect modifies the intensity of the MMI, making the butterfly arrangement more cohesive than the boat. The MSI and the MMI act synergistically, decreasing the bonding energy of individual palladium atoms at most sites, mainly on the (110D) surface. Energy Decomposition Analysis (EDA) shows that the nature of the Pd−Al interaction depends on the coordination environment of the cation and the exposed surface of the γ-alumina, while Pd−O is mostly electrostatic. The most acidic sites on surfaces are Alo at (110D) and Alt at (110C). Palladium atoms bonded to oxygen anions also behave as acid centers, attracting adsorbates preferentially. The MSI/MMI effects make the nucleation of a fifth palladium atom more favored on Pd4/(110D), indicating lesser stability of this system face to Pd4/(110C). On the other hand, NO anchors preferentially in bridge − mode that most favors N−O bond break − on (110D) termination only. MSI and MMI effects are competitive along with the growth of Pdn on γ-alumina. From n=6, the MMI starts to command the process, suggesting an energetic favoring of sintering from this point on. |
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Cruz, Maurício Tavares de Macedohttp://lattes.cnpq.br/1753494541981720Carneiro, José Walkimar de Mesquitahttp://lattes.cnpq.br/0365017664358426Baptista, Leonardohttp://lattes.cnpq.br/2182432135517042Ferreira, Glaucio Bragahttp://lattes.cnpq.br/2670586422627997Lage, Mateus Ribeirohttp://lattes.cnpq.br/7180752938220497Delarmelina, Maiconhttp://lattes.cnpq.br/7778812717476251http://lattes.cnpq.br/4563992882646426Prates, Letícia Maialeticiamaiapr@gmail.com2023-01-27T12:56:35Z2021-12-14PRATES, Letícia Maia. Estudo teórico da interação metal−suporte em aglomerados de paládio depositados sobre as superfícies (110D) e (110C) da γ-alumina. 2021. 264 f. Tese (Doutorado em Química) - Instituto de Química, Universidade do Estado do Rio de Janeiro, Rio de Janeiro, 2021.http://www.bdtd.uerj.br/handle/1/18973The metal−support interaction (MSI) existing in heterogeneous catalysts influences the structure−performance relationship of these materials. Concomitantly with the metal-metal interaction (MMI), the MSI hinders or favors the anchoring of adsorbate species on the catalyst and control the morphology and growth of the metal particle. γ-alumina (γ-Al2O3), an oxide widely used as support, presents a structural arrangement still not well-defined experimentally, being the main discussions regarding the crystal lattice and the distribution of octahedral (Alo) and tetrahedral (Alt) aluminum cations along with the bulk and surface. Quantum-mechanical calculations by Density Functional Theory (DFT) were performed to study the MSI effect in models proposed to represent γ-alumina (spinel-like)-supported palladium catalysts. Two approaches were adopted in this work: I – Analysis of the influence of different surfaces exposed by γ-alumina ((110D) and (110C)) on MSI in Pd4/γ-alumina models, facing the interaction with a fifth palladium atom and with one NO molecule and II – Study of the sequential growth (atom to atom) of a Pdn cluster (n = 1−7) on the (110D) surface of γ-alumina. The main results show that the magnitude of the MSI is twice as high when the (110C) surface is exposed. Distinct arrangements for Pd4 are produced on (110) terminations: boat (110D) and butterfly (110C). Natural Bond Orbital (NBO) calculations show that an electronic MSI (EMSI) is promoted at Pd/(110) interfaces, with Pd4→γ-alumina backdonation being the preferential direction. The EMSI effect modifies the intensity of the MMI, making the butterfly arrangement more cohesive than the boat. The MSI and the MMI act synergistically, decreasing the bonding energy of individual palladium atoms at most sites, mainly on the (110D) surface. Energy Decomposition Analysis (EDA) shows that the nature of the Pd−Al interaction depends on the coordination environment of the cation and the exposed surface of the γ-alumina, while Pd−O is mostly electrostatic. The most acidic sites on surfaces are Alo at (110D) and Alt at (110C). Palladium atoms bonded to oxygen anions also behave as acid centers, attracting adsorbates preferentially. The MSI/MMI effects make the nucleation of a fifth palladium atom more favored on Pd4/(110D), indicating lesser stability of this system face to Pd4/(110C). On the other hand, NO anchors preferentially in bridge − mode that most favors N−O bond break − on (110D) termination only. MSI and MMI effects are competitive along with the growth of Pdn on γ-alumina. From n=6, the MMI starts to command the process, suggesting an energetic favoring of sintering from this point on.A interação metal–suporte (MSI) existente em catalisadores heterogêneos influencia a relação estrutura-performance destes materiais. Concomitantemente à interação metal−metal (MMI), a MSI dificulta ou favorece o ancoramento de espécies adsorvato no catalisador e controla a morfologia e o crescimento da partícula metálica. A γ-alumina (γ-Al2O3), um óxido amplamente empregado como suporte, apresenta um arranjo estrutural ainda não bem definido experimentalmente, sendo as principais discussões quanto à rede cristalina e distribuição dos cátions alumínio octaédricos (Alo) e tetraédricos (Alt) ao longo do bulk e da superfície. Cálculos mecânico-quânticos por Teoria do Funcional de Densidade (DFT) foram realizados para o estudo do efeito MSI em modelos propostos para representar catalisadores de paládio suportado em γ-alumina com arranjo espinélio. Duas abordagens foram adotadas neste trabalho: I – Análise da influência das diferentes superfícies expostas pela γ-alumina ((110D) e (110C)) na MSI em modelos Pd4/γ-alumina, frente à interação com um quinto átomo de paládio e com uma molécula NO e II – Estudo do crescimento sequencial (átomo a átomo) de um aglomerado Pdn (n = 1−7) sobre a superfície (110D) da γ-alumina. Os principais resultados apontam que a magnitude da MSI é duas vezes maior quando a superfície (110C) é exposta. Arranjos distintos para Pd4 são formados sobre as terminações (110): boat (110D) e butterfly (110C). Cálculos dos Orbitais Naturais de Ligação (NBO) mostram que uma MSI eletrônica (EMSI) é promovida nas interfaces Pd/(110), sendo a retrodoação Pd4→γ-alumina o sentido preferencial. O efeito EMSI modifica a intensidade da MMI, tornando o arranjo butterfly mais coeso que o boat. A MSI e a MMI atuam de forma sinérgica, diminuindo a energia de ligação dos átomos de paládio individualmente na maioria dos sítios, principalmente na superfície (110D). A Análise de Decomposição de Energia (EDA) mostra que a natureza da interação Pd−Al depende do ambiente de coordenação do cátion e da superfície exposta da γalumina, enquanto Pd−O é majoritariamente eletrostática. Os sítios mais ácidos nas superfícies são Alo em (110D) e Alt em (110C). Átomos de paládio ligados a ânions oxigênio também se comportam como centros ácidos, atraindo adsorvatos preferencialmente. Os efeitos MSI/MMI tornam a nucleação de um quinto átomo de paládio mais favorecida em Pd4/(110D), indicando menor estabilidade deste sistema frente à Pd4/(110C). Por outro lado, NO ancora preferencialmente bridge, o modo que mais favorece a quebra da ligação N−O, apenas sobre a terminação (110D). A MSI e a MMI mostram-se como efeitos competitivos ao longo do crescimento de Pdn sobre a γ-alumina. A partir de n=6, a MMI passa a comandar o processo, sugerindo um favorecimento energético da sinterização deste ponto em diante.Submitted by Ana Rachel CTC/Q (ana.teles@uerj.br) on 2023-01-27T12:56:35Z No. of bitstreams: 1 Tese - Letícia Maia Prates - 2021 - Completa.pdf: 73502498 bytes, checksum: 8d5469c16ff7c18b5b006871aac0d3b3 (MD5)Made available in DSpace on 2023-01-27T12:56:35Z (GMT). No. of bitstreams: 1 Tese - Letícia Maia Prates - 2021 - Completa.pdf: 73502498 bytes, checksum: 8d5469c16ff7c18b5b006871aac0d3b3 (MD5) Previous issue date: 2021-12-14Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPESapplication/pdfporUniversidade do Estado do Rio de JaneiroPrograma de Pós-Graduação em QuímicaUERJBrasilCentro de Tecnologia e Ciências::Instituto de QuímicaMetal–support interactionPalladium clustersPaládioAluminaInteração metal-suporteγ-aluminaAglomerados de paládioDFTNBOCIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA INORGANICAEstudo teórico da interação metal−suporte em aglomerados de paládio depositados sobre as superfícies (110D) e (110C) da γ-aluminaTheoretical study of the metal–support interaction in palladium clusters deposited on (110D) and (110C) surfaces of γ-aluminainfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisinfo:eu-repo/semantics/openAccessreponame:Biblioteca Digital de Teses e Dissertações da UERJinstname:Universidade do Estado do Rio de Janeiro (UERJ)instacron:UERJORIGINALTese - Letícia Maia Prates - 2021 - Completa.pdfTese - Letícia Maia Prates - 2021 - Completa.pdfapplication/pdf73502498http://www.bdtd.uerj.br/bitstream/1/18973/2/Tese+-+Let%C3%ADcia+Maia+Prates+-+2021+-+Completa.pdf8d5469c16ff7c18b5b006871aac0d3b3MD52LICENSElicense.txtlicense.txttext/plain; charset=utf-82123http://www.bdtd.uerj.br/bitstream/1/18973/1/license.txte5502652da718045d7fcd832b79fca29MD511/189732024-02-27 14:47:35.25oai:www.bdtd.uerj.br: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Biblioteca Digital de Teses e Dissertaçõeshttp://www.bdtd.uerj.br/PUBhttps://www.bdtd.uerj.br:8443/oai/requestbdtd.suporte@uerj.bropendoar:29032024-02-27T17:47:35Biblioteca Digital de Teses e Dissertações da UERJ - Universidade do Estado do Rio de Janeiro (UERJ)false |
dc.title.por.fl_str_mv |
Estudo teórico da interação metal−suporte em aglomerados de paládio depositados sobre as superfícies (110D) e (110C) da γ-alumina |
dc.title.alternative.eng.fl_str_mv |
Theoretical study of the metal–support interaction in palladium clusters deposited on (110D) and (110C) surfaces of γ-alumina |
title |
Estudo teórico da interação metal−suporte em aglomerados de paládio depositados sobre as superfícies (110D) e (110C) da γ-alumina |
spellingShingle |
Estudo teórico da interação metal−suporte em aglomerados de paládio depositados sobre as superfícies (110D) e (110C) da γ-alumina Prates, Letícia Maia Metal–support interaction Palladium clusters Paládio Alumina Interação metal-suporte γ-alumina Aglomerados de paládio DFT NBO CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA INORGANICA |
title_short |
Estudo teórico da interação metal−suporte em aglomerados de paládio depositados sobre as superfícies (110D) e (110C) da γ-alumina |
title_full |
Estudo teórico da interação metal−suporte em aglomerados de paládio depositados sobre as superfícies (110D) e (110C) da γ-alumina |
title_fullStr |
Estudo teórico da interação metal−suporte em aglomerados de paládio depositados sobre as superfícies (110D) e (110C) da γ-alumina |
title_full_unstemmed |
Estudo teórico da interação metal−suporte em aglomerados de paládio depositados sobre as superfícies (110D) e (110C) da γ-alumina |
title_sort |
Estudo teórico da interação metal−suporte em aglomerados de paládio depositados sobre as superfícies (110D) e (110C) da γ-alumina |
author |
Prates, Letícia Maia |
author_facet |
Prates, Letícia Maia leticiamaiapr@gmail.com |
author_role |
author |
author2 |
leticiamaiapr@gmail.com |
author2_role |
author |
dc.contributor.advisor1.fl_str_mv |
Cruz, Maurício Tavares de Macedo |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/1753494541981720 |
dc.contributor.advisor-co1.fl_str_mv |
Carneiro, José Walkimar de Mesquita |
dc.contributor.advisor-co1Lattes.fl_str_mv |
http://lattes.cnpq.br/0365017664358426 |
dc.contributor.referee1.fl_str_mv |
Baptista, Leonardo |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/2182432135517042 |
dc.contributor.referee2.fl_str_mv |
Ferreira, Glaucio Braga |
dc.contributor.referee2Lattes.fl_str_mv |
http://lattes.cnpq.br/2670586422627997 |
dc.contributor.referee3.fl_str_mv |
Lage, Mateus Ribeiro |
dc.contributor.referee3Lattes.fl_str_mv |
http://lattes.cnpq.br/7180752938220497 |
dc.contributor.referee4.fl_str_mv |
Delarmelina, Maicon |
dc.contributor.referee4Lattes.fl_str_mv |
http://lattes.cnpq.br/7778812717476251 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/4563992882646426 |
dc.contributor.author.fl_str_mv |
Prates, Letícia Maia leticiamaiapr@gmail.com |
contributor_str_mv |
Cruz, Maurício Tavares de Macedo Carneiro, José Walkimar de Mesquita Baptista, Leonardo Ferreira, Glaucio Braga Lage, Mateus Ribeiro Delarmelina, Maicon |
dc.subject.eng.fl_str_mv |
Metal–support interaction Palladium clusters |
topic |
Metal–support interaction Palladium clusters Paládio Alumina Interação metal-suporte γ-alumina Aglomerados de paládio DFT NBO CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA INORGANICA |
dc.subject.por.fl_str_mv |
Paládio Alumina Interação metal-suporte γ-alumina Aglomerados de paládio DFT NBO |
dc.subject.cnpq.fl_str_mv |
CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA INORGANICA |
description |
The metal−support interaction (MSI) existing in heterogeneous catalysts influences the structure−performance relationship of these materials. Concomitantly with the metal-metal interaction (MMI), the MSI hinders or favors the anchoring of adsorbate species on the catalyst and control the morphology and growth of the metal particle. γ-alumina (γ-Al2O3), an oxide widely used as support, presents a structural arrangement still not well-defined experimentally, being the main discussions regarding the crystal lattice and the distribution of octahedral (Alo) and tetrahedral (Alt) aluminum cations along with the bulk and surface. Quantum-mechanical calculations by Density Functional Theory (DFT) were performed to study the MSI effect in models proposed to represent γ-alumina (spinel-like)-supported palladium catalysts. Two approaches were adopted in this work: I – Analysis of the influence of different surfaces exposed by γ-alumina ((110D) and (110C)) on MSI in Pd4/γ-alumina models, facing the interaction with a fifth palladium atom and with one NO molecule and II – Study of the sequential growth (atom to atom) of a Pdn cluster (n = 1−7) on the (110D) surface of γ-alumina. The main results show that the magnitude of the MSI is twice as high when the (110C) surface is exposed. Distinct arrangements for Pd4 are produced on (110) terminations: boat (110D) and butterfly (110C). Natural Bond Orbital (NBO) calculations show that an electronic MSI (EMSI) is promoted at Pd/(110) interfaces, with Pd4→γ-alumina backdonation being the preferential direction. The EMSI effect modifies the intensity of the MMI, making the butterfly arrangement more cohesive than the boat. The MSI and the MMI act synergistically, decreasing the bonding energy of individual palladium atoms at most sites, mainly on the (110D) surface. Energy Decomposition Analysis (EDA) shows that the nature of the Pd−Al interaction depends on the coordination environment of the cation and the exposed surface of the γ-alumina, while Pd−O is mostly electrostatic. The most acidic sites on surfaces are Alo at (110D) and Alt at (110C). Palladium atoms bonded to oxygen anions also behave as acid centers, attracting adsorbates preferentially. The MSI/MMI effects make the nucleation of a fifth palladium atom more favored on Pd4/(110D), indicating lesser stability of this system face to Pd4/(110C). On the other hand, NO anchors preferentially in bridge − mode that most favors N−O bond break − on (110D) termination only. MSI and MMI effects are competitive along with the growth of Pdn on γ-alumina. From n=6, the MMI starts to command the process, suggesting an energetic favoring of sintering from this point on. |
publishDate |
2021 |
dc.date.issued.fl_str_mv |
2021-12-14 |
dc.date.accessioned.fl_str_mv |
2023-01-27T12:56:35Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
format |
doctoralThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
PRATES, Letícia Maia. Estudo teórico da interação metal−suporte em aglomerados de paládio depositados sobre as superfícies (110D) e (110C) da γ-alumina. 2021. 264 f. Tese (Doutorado em Química) - Instituto de Química, Universidade do Estado do Rio de Janeiro, Rio de Janeiro, 2021. |
dc.identifier.uri.fl_str_mv |
http://www.bdtd.uerj.br/handle/1/18973 |
identifier_str_mv |
PRATES, Letícia Maia. Estudo teórico da interação metal−suporte em aglomerados de paládio depositados sobre as superfícies (110D) e (110C) da γ-alumina. 2021. 264 f. Tese (Doutorado em Química) - Instituto de Química, Universidade do Estado do Rio de Janeiro, Rio de Janeiro, 2021. |
url |
http://www.bdtd.uerj.br/handle/1/18973 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
Universidade do Estado do Rio de Janeiro |
dc.publisher.program.fl_str_mv |
Programa de Pós-Graduação em Química |
dc.publisher.initials.fl_str_mv |
UERJ |
dc.publisher.country.fl_str_mv |
Brasil |
dc.publisher.department.fl_str_mv |
Centro de Tecnologia e Ciências::Instituto de Química |
publisher.none.fl_str_mv |
Universidade do Estado do Rio de Janeiro |
dc.source.none.fl_str_mv |
reponame:Biblioteca Digital de Teses e Dissertações da UERJ instname:Universidade do Estado do Rio de Janeiro (UERJ) instacron:UERJ |
instname_str |
Universidade do Estado do Rio de Janeiro (UERJ) |
instacron_str |
UERJ |
institution |
UERJ |
reponame_str |
Biblioteca Digital de Teses e Dissertações da UERJ |
collection |
Biblioteca Digital de Teses e Dissertações da UERJ |
bitstream.url.fl_str_mv |
http://www.bdtd.uerj.br/bitstream/1/18973/2/Tese+-+Let%C3%ADcia+Maia+Prates+-+2021+-+Completa.pdf http://www.bdtd.uerj.br/bitstream/1/18973/1/license.txt |
bitstream.checksum.fl_str_mv |
8d5469c16ff7c18b5b006871aac0d3b3 e5502652da718045d7fcd832b79fca29 |
bitstream.checksumAlgorithm.fl_str_mv |
MD5 MD5 |
repository.name.fl_str_mv |
Biblioteca Digital de Teses e Dissertações da UERJ - Universidade do Estado do Rio de Janeiro (UERJ) |
repository.mail.fl_str_mv |
bdtd.suporte@uerj.br |
_version_ |
1792352372494696448 |