Estudo teórico: da adsorção de etanol em clusters de Cun e Aun (n = 10-20)
Autor(a) principal: | |
---|---|
Data de Publicação: | 2021 |
Tipo de documento: | Dissertação |
Idioma: | por |
Título da fonte: | Repositório Institucional da UFSCAR |
Texto Completo: | https://repositorio.ufscar.br/handle/ufscar/15623 |
Resumo: | In this work, we study aggregates, which we will call clusters of copper and gold with and without the adsorbed ethanol molecule. First, we investigated the most favorable positions for ethanol adsorption to occur in metallic clusters. Then, we used three methods to obtain, a priori, these positions with possession only of the clusters without performing calculations with the adsorbed molecule. These methods are the Fukui indices, the interaction of point charges around the metallic cluster, and a geometric index, which gives how close or far apart the metallic atoms are in the isolated cluster in question. These positions obtained are then confronted with those from a later calculation of the cluster and ethanol set. With this, we established the predictive power of the methods used to obtain the best adsorption positions. Gold and copper nanoclusters have been extensively studied in several theoretical works using density functional theory. The present work used the density functional theory, using the hybrid exchange and correlation functional B3LYP and the base set def-SVP and later def-TZVPP. The objective is to compare energy character between several clusters with sizes of 10 to 20 atoms, obtained from the literature. Our studies do not have the nature of being systematic. Instead, develop and carry out a critical analysis of models that could study the adsorption of molecules in metallic clusters. Several theoretical studies indicate that ethanol preferentially adsorbs on metallic nanoclusters via nucleophilic attack by the oxygen-free electronic pair. This work includes the D3 Grimme scattering approximation to correct for van der Waals (vdW) effects. According to the results obtained, it was observed that there is no clear relationship between the energy analysis of the clusters, such as the binding energy (BE) (or the second energy difference (∆2E)) and the adsorption energy of ethanol (Eads). After adsorption of the ethanol molecule, some gold clusters deform their initial geometry in the region of 12 to 18 atoms. This problem is not frequent in copper clusters. The adsorption energy in copper clusters varies from -0.65 to -1.16 eV and, for gold clusters, the adsorption energy varies from -0.40 to -0.75 eV. Our studies showed that metallic clusters might have different stabilities due to geometric deformation against the adsorption of molecules. The studies carried out here will help the development of ethanol catalysis in metallic clusters. |
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Fuentes Martínez, Manuel RicardoLopez Castillo, Alejandrohttp://lattes.cnpq.br/2599181118729458http://lattes.cnpq.br/33193804347660522022-02-22T10:25:36Z2022-02-22T10:25:36Z2021-08-24FUENTES MARTÍNEZ, Manuel Ricardo. Estudo teórico: da adsorção de etanol em clusters de Cun e Aun (n = 10-20). 2021. Dissertação (Mestrado em Química) – Universidade Federal de São Carlos, São Carlos, 2021. Disponível em: https://repositorio.ufscar.br/handle/ufscar/15623.https://repositorio.ufscar.br/handle/ufscar/15623In this work, we study aggregates, which we will call clusters of copper and gold with and without the adsorbed ethanol molecule. First, we investigated the most favorable positions for ethanol adsorption to occur in metallic clusters. Then, we used three methods to obtain, a priori, these positions with possession only of the clusters without performing calculations with the adsorbed molecule. These methods are the Fukui indices, the interaction of point charges around the metallic cluster, and a geometric index, which gives how close or far apart the metallic atoms are in the isolated cluster in question. These positions obtained are then confronted with those from a later calculation of the cluster and ethanol set. With this, we established the predictive power of the methods used to obtain the best adsorption positions. Gold and copper nanoclusters have been extensively studied in several theoretical works using density functional theory. The present work used the density functional theory, using the hybrid exchange and correlation functional B3LYP and the base set def-SVP and later def-TZVPP. The objective is to compare energy character between several clusters with sizes of 10 to 20 atoms, obtained from the literature. Our studies do not have the nature of being systematic. Instead, develop and carry out a critical analysis of models that could study the adsorption of molecules in metallic clusters. Several theoretical studies indicate that ethanol preferentially adsorbs on metallic nanoclusters via nucleophilic attack by the oxygen-free electronic pair. This work includes the D3 Grimme scattering approximation to correct for van der Waals (vdW) effects. According to the results obtained, it was observed that there is no clear relationship between the energy analysis of the clusters, such as the binding energy (BE) (or the second energy difference (∆2E)) and the adsorption energy of ethanol (Eads). After adsorption of the ethanol molecule, some gold clusters deform their initial geometry in the region of 12 to 18 atoms. This problem is not frequent in copper clusters. The adsorption energy in copper clusters varies from -0.65 to -1.16 eV and, for gold clusters, the adsorption energy varies from -0.40 to -0.75 eV. Our studies showed that metallic clusters might have different stabilities due to geometric deformation against the adsorption of molecules. The studies carried out here will help the development of ethanol catalysis in metallic clusters.Neste trabalho estudamos agregados, que denominaremos cluster, de cobre e ouro com e sem a molécula de etanol adsorvida. Estudamos as posições mais favoráveis para ocorrer a adsorção do etanol em clusters metálicos. Para obter, a priori, essas posições com posse somente dos clusters, sem realizar cálculos com a molécula adsorvida, utilizamos três elementos. Estes elementos são os índices de Fukui, a interação de cargas pontuais ao redor do cluster metálico e também um índice geométrico, que dá o quão perto ou afastado estão os átomos metálicos um dos outros no cluster isolado em questão. Essas posições obtidas são então confrontadas com aquelas de um cálculo posterior do conjunto cluster e etanol. Com isso, estabelecemos o poder preditivo dos métodos utilizados para obter as melhores posições de adsorção. Os nanoclusters de ouro e cobre têm sido amplamente estudados em diversos trabalhos teóricos fazendo uso da teoria funcional da densidade. No presente trabalho, usou-se a teoria funcional da densidade fazendo uso do funcional híbrido de troca e correlação B3LYP e do conjunto base def-SVP e posteriormente def-TZVPP. O objetivo é fazer uma comparação de caráter energético entre diversos clusters com tamanho de 10 até 20 átomos, os quais foram obtidos através da literatura. Nossos estudos não tem o caráter de serem sistemáticos, mas sim de desenvolver e realizar análise crítica de modelos que poderiam ser utilizados para estudar a adsorção de moléculas em clusters metálicos. Diversos estudos teóricos indicam que o etanol adsorve preferencialmente em nanoclusters metálicos, via ataque nucleofílico pelo par eletrônico livre do oxigênio. Neste trabalho, inclui-se a aproximação de dispersão D3 Grimme para corrigir os efeitos de van der Waals (vdW). De acordo com os resultados obtidos, observou-se que não há uma relação clara entre as análises energéticas dos clusters, como a energia de ligação (BE) (ou a segunda diferença de energia (∆2E)) e a energia de adsorção do etanol (Eads). Depois da adsorção da molécula de etanol, alguns clusters de ouro deformam sua geometria inicial na região de 12 até 18 átomos. Este problema é menos frequente nos clusters de cobre. A energia de adsorção nos clusters de cobre varia desde -0,65 até -1,16 eV e, para os clusters de ouro, a energia de adsorção varia desde -0,40 até -0,75 eV. Nossos estudos permitiram evidenciar que clusters metálicos podem ter estabilidade distintas devido à deformação geométrica frente a adsorção de moléculas. Os estudos aqui realizados permitirão auxiliar o desenvolvimento da catálise do etanol em clusters metálicos.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)2019-00/88887.342230porUniversidade Federal de São CarlosCâmpus São CarlosPrograma de Pós-Graduação em Química - PPGQUFSCarAttribution-NonCommercial-NoDerivs 3.0 Brazilhttp://creativecommons.org/licenses/by-nc-nd/3.0/br/info:eu-repo/semantics/openAccessAdsorção molecularDFTClusterCIENCIAS EXATAS E DA TERRA::QUIMICAEstudo teórico: da adsorção de etanol em clusters de Cun e Aun (n = 10-20)Estudio teórico: de la adsorción de etanol en clusters de Cun y Aun (n= 10-20)info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARCC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8811https://repositorio.ufscar.br/bitstream/ufscar/15623/9/license_rdfe39d27027a6cc9cb039ad269a5db8e34MD59ORIGINALDissertação_ManuelFuentesMartinez.pdfDissertação_ManuelFuentesMartinez.pdfDissertação_ManuelFuentesMartinezapplication/pdf2940352https://repositorio.ufscar.br/bitstream/ufscar/15623/7/Disserta%c3%a7%c3%a3o_ManuelFuentesMartinez.pdf44898bab462021b62b3dcfc30fa535c6MD57modelo-carta-comprovante_homologacao_Manuel_assinado.pdfmodelo-carta-comprovante_homologacao_Manuel_assinado.pdfCarta_Comprovanteapplication/pdf345967https://repositorio.ufscar.br/bitstream/ufscar/15623/8/modelo-carta-comprovante_homologacao_Manuel_assinado.pdfa2a879db3c29485ff400e4ecb88806beMD58TEXTDissertação_ManuelFuentesMartinez.pdf.txtDissertação_ManuelFuentesMartinez.pdf.txtExtracted texttext/plain173107https://repositorio.ufscar.br/bitstream/ufscar/15623/10/Disserta%c3%a7%c3%a3o_ManuelFuentesMartinez.pdf.txt777f1c07840117bbf21a71c2ebb5f474MD510modelo-carta-comprovante_homologacao_Manuel_assinado.pdf.txtmodelo-carta-comprovante_homologacao_Manuel_assinado.pdf.txtExtracted texttext/plain1435https://repositorio.ufscar.br/bitstream/ufscar/15623/12/modelo-carta-comprovante_homologacao_Manuel_assinado.pdf.txt72fc3dfc16ee395176d14fb20b476313MD512THUMBNAILDissertação_ManuelFuentesMartinez.pdf.jpgDissertação_ManuelFuentesMartinez.pdf.jpgIM Thumbnailimage/jpeg7503https://repositorio.ufscar.br/bitstream/ufscar/15623/11/Disserta%c3%a7%c3%a3o_ManuelFuentesMartinez.pdf.jpg9c55b81fb6154b5e90022b56286c2019MD511modelo-carta-comprovante_homologacao_Manuel_assinado.pdf.jpgmodelo-carta-comprovante_homologacao_Manuel_assinado.pdf.jpgIM Thumbnailimage/jpeg11917https://repositorio.ufscar.br/bitstream/ufscar/15623/13/modelo-carta-comprovante_homologacao_Manuel_assinado.pdf.jpgd8943287942bd1ed9b9d08d9c3c0fc4dMD513ufscar/156232022-02-23 03:34:17.537oai:repositorio.ufscar.br:ufscar/15623Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222022-02-23T03:34:17Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.por.fl_str_mv |
Estudo teórico: da adsorção de etanol em clusters de Cun e Aun (n = 10-20) |
dc.title.alternative.spa.fl_str_mv |
Estudio teórico: de la adsorción de etanol en clusters de Cun y Aun (n= 10-20) |
title |
Estudo teórico: da adsorção de etanol em clusters de Cun e Aun (n = 10-20) |
spellingShingle |
Estudo teórico: da adsorção de etanol em clusters de Cun e Aun (n = 10-20) Fuentes Martínez, Manuel Ricardo Adsorção molecular DFT Cluster CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Estudo teórico: da adsorção de etanol em clusters de Cun e Aun (n = 10-20) |
title_full |
Estudo teórico: da adsorção de etanol em clusters de Cun e Aun (n = 10-20) |
title_fullStr |
Estudo teórico: da adsorção de etanol em clusters de Cun e Aun (n = 10-20) |
title_full_unstemmed |
Estudo teórico: da adsorção de etanol em clusters de Cun e Aun (n = 10-20) |
title_sort |
Estudo teórico: da adsorção de etanol em clusters de Cun e Aun (n = 10-20) |
author |
Fuentes Martínez, Manuel Ricardo |
author_facet |
Fuentes Martínez, Manuel Ricardo |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/3319380434766052 |
dc.contributor.author.fl_str_mv |
Fuentes Martínez, Manuel Ricardo |
dc.contributor.advisor1.fl_str_mv |
Lopez Castillo, Alejandro |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/2599181118729458 |
contributor_str_mv |
Lopez Castillo, Alejandro |
dc.subject.por.fl_str_mv |
Adsorção molecular DFT |
topic |
Adsorção molecular DFT Cluster CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Cluster |
dc.subject.cnpq.fl_str_mv |
CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
In this work, we study aggregates, which we will call clusters of copper and gold with and without the adsorbed ethanol molecule. First, we investigated the most favorable positions for ethanol adsorption to occur in metallic clusters. Then, we used three methods to obtain, a priori, these positions with possession only of the clusters without performing calculations with the adsorbed molecule. These methods are the Fukui indices, the interaction of point charges around the metallic cluster, and a geometric index, which gives how close or far apart the metallic atoms are in the isolated cluster in question. These positions obtained are then confronted with those from a later calculation of the cluster and ethanol set. With this, we established the predictive power of the methods used to obtain the best adsorption positions. Gold and copper nanoclusters have been extensively studied in several theoretical works using density functional theory. The present work used the density functional theory, using the hybrid exchange and correlation functional B3LYP and the base set def-SVP and later def-TZVPP. The objective is to compare energy character between several clusters with sizes of 10 to 20 atoms, obtained from the literature. Our studies do not have the nature of being systematic. Instead, develop and carry out a critical analysis of models that could study the adsorption of molecules in metallic clusters. Several theoretical studies indicate that ethanol preferentially adsorbs on metallic nanoclusters via nucleophilic attack by the oxygen-free electronic pair. This work includes the D3 Grimme scattering approximation to correct for van der Waals (vdW) effects. According to the results obtained, it was observed that there is no clear relationship between the energy analysis of the clusters, such as the binding energy (BE) (or the second energy difference (∆2E)) and the adsorption energy of ethanol (Eads). After adsorption of the ethanol molecule, some gold clusters deform their initial geometry in the region of 12 to 18 atoms. This problem is not frequent in copper clusters. The adsorption energy in copper clusters varies from -0.65 to -1.16 eV and, for gold clusters, the adsorption energy varies from -0.40 to -0.75 eV. Our studies showed that metallic clusters might have different stabilities due to geometric deformation against the adsorption of molecules. The studies carried out here will help the development of ethanol catalysis in metallic clusters. |
publishDate |
2021 |
dc.date.issued.fl_str_mv |
2021-08-24 |
dc.date.accessioned.fl_str_mv |
2022-02-22T10:25:36Z |
dc.date.available.fl_str_mv |
2022-02-22T10:25:36Z |
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info:eu-repo/semantics/publishedVersion |
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info:eu-repo/semantics/masterThesis |
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masterThesis |
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publishedVersion |
dc.identifier.citation.fl_str_mv |
FUENTES MARTÍNEZ, Manuel Ricardo. Estudo teórico: da adsorção de etanol em clusters de Cun e Aun (n = 10-20). 2021. Dissertação (Mestrado em Química) – Universidade Federal de São Carlos, São Carlos, 2021. Disponível em: https://repositorio.ufscar.br/handle/ufscar/15623. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/15623 |
identifier_str_mv |
FUENTES MARTÍNEZ, Manuel Ricardo. Estudo teórico: da adsorção de etanol em clusters de Cun e Aun (n = 10-20). 2021. Dissertação (Mestrado em Química) – Universidade Federal de São Carlos, São Carlos, 2021. Disponível em: https://repositorio.ufscar.br/handle/ufscar/15623. |
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https://repositorio.ufscar.br/handle/ufscar/15623 |
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Universidade Federal de São Carlos Câmpus São Carlos |
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Programa de Pós-Graduação em Química - PPGQ |
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UFSCar |
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Universidade Federal de São Carlos Câmpus São Carlos |
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