Teoria do funcional da densidade aplicada ao estudo da interação entre nanogaiolas B12 N12 puras e dopadas com cobre e níquel com os gases tóxicos CO e CNCl
Autor(a) principal: | |
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Data de Publicação: | 2023 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Biblioteca Digital de Teses e Dissertações da UFMA |
Texto Completo: | https://tedebc.ufma.br/jspui/handle/tede/tede/5253 |
Resumo: | This thesis presents a comprehensive study of the adsorption of carbon monoxide (CO) and cyanogen chloride (CNCl) on B12N12 pristine and copper and nickel-doped surfaces using calculations based on density functional theory. Firstly, from our systematic review of the literature, we infer that a pure B12N12 nanocage can selectively detect O3, HNO, NO, CO, CNCl, and CNF gases. In contrast, metal-modified B12N12 nanocage can detect a wider range of gases such as CO, NH3, PH3, AsH3, SO2, O3, COCl2, NCCN, and CNCl. However, few studies have discussed the interference effects due to the presence of other gases in the atmosphere and/or the incorporation of different structural modifications into the nanocage. Secondly, we observed that: i) the increase in the electric field ( ⃗EF⃗⃗⃗⃗ ) in the negative direction favored the adsorption of CO gas, while the increase in ⃗EF⃗⃗⃗⃗ in the positive direction favored the desorption of the CO molecule on the B12N12; ii) increase in the ⃗E⃗⃗⃗F⃗ resulted in an increase in the sensitivity, for the B3LYP and B97D functionals, from –0.514 to +0.514 V/Å; iii) the functional with dispersion correction (B97D) described best system B12N12–CO, as a function of the application of the electric field. Demonstrated the capability of B12N12 as a sensor for potential applications in the detection of CO under an ⃗EF⃗⃗⃗⃗ . Thirdly, it was found that the gas adsorption performance of B12N12 is improved due to the introduction of the Cu atom, but the interaction between CO and B12N11Cu, Cu@B12N12, Cu@b64, and Cu@b66 nanocages is strong, limiting applications for gas detection. Particularly, the CuB11N12 system shows moderate an adsorption energy (Eads = – 0.6 eV) and a high electronic sensitivity (ΔEgap = 81.6%) toward CO gas, compared to other modified systems. Furthermore, it was found that CuB11N12 presented low recovery time (14 ms) and high selectivity for CO detection, setting up as a superior material for applications involving the selective detection of CO gas. Finally, we observed that the CNCl molecule was observed to chemically adsorb on all MB11N12 (M = Fe–Zn) nanocages, but a stronger interaction occurred on the FeB11N12 and CoB11N12 nanocages, a moderate interaction occurred on the B12N12, NiB11N12, CuB11N12, and ZnB11N12 surfaces (σ-donation being more effective than π-back-bonding). However, the NiB11N12 and CuB11N12 nanocages showed the highest ΔEgap values (79.31% and 87.50%, respectively) for the adsorption of CNCl gas. Furthermore, based on performance analysis and comparison with previous results reported in the literature, it was found that NiB11N12 and CuB11N12 nanocages were superior materials for application in the detection of the CNCl toxic gas. |
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VARELA JÚNIOR, Jaldyr de Jesus Gomeshttp://lattes.cnpq.br/5125904184711352VARELA JÚNIOR, Jaldyr de Jesus Gomeshttp://lattes.cnpq.br/5125904184711352BEZERRA, Cícero Wellington Britohttp://lattes.cnpq.br/1474300723265204DAMOS, Flávio Santoshttp://lattes.cnpq.br/0915687070195770MOREIRA, Edvanhttp://lattes.cnpq.br/9406912742121871GONÇALVES JÚNIOR, Paulo Roberto Garcêshttp://lattes.cnpq.br/7405105464035176http://lattes.cnpq.br/4448767122826959SILVA, Adilson Luiś Pereira2024-04-23T15:27:48Z2023-12-20SILVA, Adilson Luiś Pereira. Teoria do funcional da densidade aplicada ao estudo da interação entre nanogaiolas B12 N12 puras e dopadas com cobre e níquel com os gases tóxicos CO e CNCl. 2023. 150 f. Tese (Programa de Pós-Graduação Doutorado em Química) - Universidade Federal do Maranhão, São Luís, 2023.https://tedebc.ufma.br/jspui/handle/tede/tede/5253This thesis presents a comprehensive study of the adsorption of carbon monoxide (CO) and cyanogen chloride (CNCl) on B12N12 pristine and copper and nickel-doped surfaces using calculations based on density functional theory. Firstly, from our systematic review of the literature, we infer that a pure B12N12 nanocage can selectively detect O3, HNO, NO, CO, CNCl, and CNF gases. In contrast, metal-modified B12N12 nanocage can detect a wider range of gases such as CO, NH3, PH3, AsH3, SO2, O3, COCl2, NCCN, and CNCl. However, few studies have discussed the interference effects due to the presence of other gases in the atmosphere and/or the incorporation of different structural modifications into the nanocage. Secondly, we observed that: i) the increase in the electric field ( ⃗EF⃗⃗⃗⃗ ) in the negative direction favored the adsorption of CO gas, while the increase in ⃗EF⃗⃗⃗⃗ in the positive direction favored the desorption of the CO molecule on the B12N12; ii) increase in the ⃗E⃗⃗⃗F⃗ resulted in an increase in the sensitivity, for the B3LYP and B97D functionals, from –0.514 to +0.514 V/Å; iii) the functional with dispersion correction (B97D) described best system B12N12–CO, as a function of the application of the electric field. Demonstrated the capability of B12N12 as a sensor for potential applications in the detection of CO under an ⃗EF⃗⃗⃗⃗ . Thirdly, it was found that the gas adsorption performance of B12N12 is improved due to the introduction of the Cu atom, but the interaction between CO and B12N11Cu, Cu@B12N12, Cu@b64, and Cu@b66 nanocages is strong, limiting applications for gas detection. Particularly, the CuB11N12 system shows moderate an adsorption energy (Eads = – 0.6 eV) and a high electronic sensitivity (ΔEgap = 81.6%) toward CO gas, compared to other modified systems. Furthermore, it was found that CuB11N12 presented low recovery time (14 ms) and high selectivity for CO detection, setting up as a superior material for applications involving the selective detection of CO gas. Finally, we observed that the CNCl molecule was observed to chemically adsorb on all MB11N12 (M = Fe–Zn) nanocages, but a stronger interaction occurred on the FeB11N12 and CoB11N12 nanocages, a moderate interaction occurred on the B12N12, NiB11N12, CuB11N12, and ZnB11N12 surfaces (σ-donation being more effective than π-back-bonding). However, the NiB11N12 and CuB11N12 nanocages showed the highest ΔEgap values (79.31% and 87.50%, respectively) for the adsorption of CNCl gas. Furthermore, based on performance analysis and comparison with previous results reported in the literature, it was found that NiB11N12 and CuB11N12 nanocages were superior materials for application in the detection of the CNCl toxic gas.Esta tese apresenta um estudo da adsorção de CO e CNCl em superfícies de B12N12 puras e dopadas com cobre e níquel usando cálculos baseados na teoria do funcional da densidade. Primeiramente, a partir da revisão sistemática da literatura, inferiu-se que uma nanogaiola B12N12 pode interagir seletivamente os gases O3, HNO, NO, CO, CNCl e CNF. Já a nanogaiola B12N12 modificada com metal pode interagir com uma gama mais ampla de gases, como CO, NH3, PH3, AsH3, SO2, O3, COCl2, NCCN e CNCl. No entanto, poucos estudos têm discutido os efeitos de gases interferentes presentes na atmosfera e/ou incorporação de diferentes modificações estruturais na nanogaiola. Em segundo lugar, observou-se que: i) o aumento do campo elétrico (⃗EF⃗⃗⃗⃗ ) no sentido negativo favoreceu a adsorção do gás CO, enquanto o aumento do ⃗EF⃗⃗⃗⃗ no sentido positivo favoreceu a dessorção da molécula de CO no B12N12; ii) o aumento no ⃗EF⃗⃗⃗⃗ de -0,514 para +0,514 V/Å, resultou em aumento da sensibilidade, para os funcionais B3LYP e B97D; iii) o funcional com correção de dispersão (B97D) descreveu melhor o sistema B12N12–CO, em função da aplicação do campo elétrico. Assim, demonstrou-se a capacidade de B12N12 como um sensor para potenciais aplicações na detecção de CO sob um ⃗EF⃗⃗⃗⃗ . Em terceiro lugar, verificou-se que o desempenho da adsorção do gás é melhorado devido à introdução do átomo de Cu no B12N12, mas a interação entre CO e nanogaiolas de B12N11Cu, Cu@B12N12, Cu@b64 e Cu@b66 é forte, limitando as aplicações para a detecção de gases. Particularmente, o sistema CuB11N12 apresenta uma energia de adsorção moderada (Eads = -0,6 eV) e alta sensibilidade eletrônica (ΔEgap = 81,6%) em relação ao gás CO, em comparação com outros sistemas modificados. Constatou-se, ainda, que o CuB11N12 apresentou baixo tempo de recuperação (14 ms) e alta seletividade para detecção de CO, configurando-se como um material superior para aplicações envolvendo a detecção seletiva de gás CO. Por fim, observou- se que a molécula de CNCl adsorve quimicamente em todas as nanogaiolas MB11N12 (M = Fe– Zn), porém uma interação mais forte ocorreu nas nanogaiolas FeB11N12 e CoB11N12, uma interação moderada ocorreu nas superfícies B12N12, NiB11N12, CuB11N12 e ZnB11N12 (doação σ sendo mais eficaz do que retrodoação π). No entanto, as nanogaiolas NiB11N12 e CuB11N12 apresentaram os maiores valores de ΔEgap (79,31% e 87,50%, respectivamente) para a adsorção do gás CNCl. Ademais, com base na análise de desempenho e na comparação com resultados anteriores relatados na literatura, demonstrou-se que as nanogaiolas de NiB11N12 e CuB11N12 constituem-se como materiais superiores para aplicação na detecção do gás tóxico CNCl.Submitted by Jonathan Sousa de Almeida (jonathan.sousa@ufma.br) on 2024-04-23T15:27:48Z No. of bitstreams: 1 ADILSONLUÍSPEREIRASILVA.pdf: 4637974 bytes, checksum: 27ed083db7b4f337b5f157a6ae3c389c (MD5)Made available in DSpace on 2024-04-23T15:27:48Z (GMT). No. of bitstreams: 1 ADILSONLUÍSPEREIRASILVA.pdf: 4637974 bytes, checksum: 27ed083db7b4f337b5f157a6ae3c389c (MD5) Previous issue date: 2023-12-20application/pdfporUniversidade Federal do MaranhãoPROGRAMA DE PÓS-GRADUAÇÃO DOUTORADO EM QUÍMICAUFMABrasilDEPARTAMENTO DE QUÍMICA/CCETNanogaiola B12N12;B12N12 dopada com cobre e níquel;CO.;CNCl.;B12N12 nanocage.Cu- and Ni-doped B12N12;CO;CNCl;QuímicaCiências Exatas e da TerraTeoria do funcional da densidade aplicada ao estudo da interação entre nanogaiolas B12 N12 puras e dopadas com cobre e níquel com os gases tóxicos CO e CNClDensity functional theory applied to the study of the interaction between pure and copper- and nickel-doped B12 N12 nanocages with the toxic gases CO and CNClinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisinfo:eu-repo/semantics/openAccessreponame:Biblioteca Digital de Teses e Dissertações da UFMAinstname:Universidade Federal do Maranhão (UFMA)instacron:UFMAORIGINALADILSONLUÍSPEREIRASILVA.pdfADILSONLUÍSPEREIRASILVA.pdfapplication/pdf4637974http://tedebc.ufma.br:8080/bitstream/tede/5253/2/ADILSONLU%C3%8DSPEREIRASILVA.pdf27ed083db7b4f337b5f157a6ae3c389cMD52LICENSElicense.txtlicense.txttext/plain; charset=utf-82255http://tedebc.ufma.br:8080/bitstream/tede/5253/1/license.txt97eeade1fce43278e63fe063657f8083MD51tede/52532024-04-23 12:27:48.838oai:tede2: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Biblioteca Digital de Teses e Dissertaçõeshttps://tedebc.ufma.br/jspui/PUBhttp://tedebc.ufma.br:8080/oai/requestrepositorio@ufma.br||repositorio@ufma.bropendoar:21312024-04-23T15:27:48Biblioteca Digital de Teses e Dissertações da UFMA - Universidade Federal do Maranhão (UFMA)false |
dc.title.por.fl_str_mv |
Teoria do funcional da densidade aplicada ao estudo da interação entre nanogaiolas B12 N12 puras e dopadas com cobre e níquel com os gases tóxicos CO e CNCl |
dc.title.alternative.eng.fl_str_mv |
Density functional theory applied to the study of the interaction between pure and copper- and nickel-doped B12 N12 nanocages with the toxic gases CO and CNCl |
title |
Teoria do funcional da densidade aplicada ao estudo da interação entre nanogaiolas B12 N12 puras e dopadas com cobre e níquel com os gases tóxicos CO e CNCl |
spellingShingle |
Teoria do funcional da densidade aplicada ao estudo da interação entre nanogaiolas B12 N12 puras e dopadas com cobre e níquel com os gases tóxicos CO e CNCl SILVA, Adilson Luiś Pereira Nanogaiola B12N12; B12N12 dopada com cobre e níquel; CO.; CNCl.; B12N12 nanocage. Cu- and Ni-doped B12N12; CO; CNCl; Química Ciências Exatas e da Terra |
title_short |
Teoria do funcional da densidade aplicada ao estudo da interação entre nanogaiolas B12 N12 puras e dopadas com cobre e níquel com os gases tóxicos CO e CNCl |
title_full |
Teoria do funcional da densidade aplicada ao estudo da interação entre nanogaiolas B12 N12 puras e dopadas com cobre e níquel com os gases tóxicos CO e CNCl |
title_fullStr |
Teoria do funcional da densidade aplicada ao estudo da interação entre nanogaiolas B12 N12 puras e dopadas com cobre e níquel com os gases tóxicos CO e CNCl |
title_full_unstemmed |
Teoria do funcional da densidade aplicada ao estudo da interação entre nanogaiolas B12 N12 puras e dopadas com cobre e níquel com os gases tóxicos CO e CNCl |
title_sort |
Teoria do funcional da densidade aplicada ao estudo da interação entre nanogaiolas B12 N12 puras e dopadas com cobre e níquel com os gases tóxicos CO e CNCl |
author |
SILVA, Adilson Luiś Pereira |
author_facet |
SILVA, Adilson Luiś Pereira |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
VARELA JÚNIOR, Jaldyr de Jesus Gomes |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/5125904184711352 |
dc.contributor.referee1.fl_str_mv |
VARELA JÚNIOR, Jaldyr de Jesus Gomes |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/5125904184711352 |
dc.contributor.referee2.fl_str_mv |
BEZERRA, Cícero Wellington Brito |
dc.contributor.referee2Lattes.fl_str_mv |
http://lattes.cnpq.br/1474300723265204 |
dc.contributor.referee3.fl_str_mv |
DAMOS, Flávio Santos |
dc.contributor.referee3Lattes.fl_str_mv |
http://lattes.cnpq.br/0915687070195770 |
dc.contributor.referee4.fl_str_mv |
MOREIRA, Edvan |
dc.contributor.referee4Lattes.fl_str_mv |
http://lattes.cnpq.br/9406912742121871 |
dc.contributor.referee5.fl_str_mv |
GONÇALVES JÚNIOR, Paulo Roberto Garcês |
dc.contributor.referee5Lattes.fl_str_mv |
http://lattes.cnpq.br/7405105464035176 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/4448767122826959 |
dc.contributor.author.fl_str_mv |
SILVA, Adilson Luiś Pereira |
contributor_str_mv |
VARELA JÚNIOR, Jaldyr de Jesus Gomes VARELA JÚNIOR, Jaldyr de Jesus Gomes BEZERRA, Cícero Wellington Brito DAMOS, Flávio Santos MOREIRA, Edvan GONÇALVES JÚNIOR, Paulo Roberto Garcês |
dc.subject.por.fl_str_mv |
Nanogaiola B12N12; B12N12 dopada com cobre e níquel; CO.; CNCl.; |
topic |
Nanogaiola B12N12; B12N12 dopada com cobre e níquel; CO.; CNCl.; B12N12 nanocage. Cu- and Ni-doped B12N12; CO; CNCl; Química Ciências Exatas e da Terra |
dc.subject.eng.fl_str_mv |
B12N12 nanocage. Cu- and Ni-doped B12N12; CO; CNCl; |
dc.subject.cnpq.fl_str_mv |
Química Ciências Exatas e da Terra |
description |
This thesis presents a comprehensive study of the adsorption of carbon monoxide (CO) and cyanogen chloride (CNCl) on B12N12 pristine and copper and nickel-doped surfaces using calculations based on density functional theory. Firstly, from our systematic review of the literature, we infer that a pure B12N12 nanocage can selectively detect O3, HNO, NO, CO, CNCl, and CNF gases. In contrast, metal-modified B12N12 nanocage can detect a wider range of gases such as CO, NH3, PH3, AsH3, SO2, O3, COCl2, NCCN, and CNCl. However, few studies have discussed the interference effects due to the presence of other gases in the atmosphere and/or the incorporation of different structural modifications into the nanocage. Secondly, we observed that: i) the increase in the electric field ( ⃗EF⃗⃗⃗⃗ ) in the negative direction favored the adsorption of CO gas, while the increase in ⃗EF⃗⃗⃗⃗ in the positive direction favored the desorption of the CO molecule on the B12N12; ii) increase in the ⃗E⃗⃗⃗F⃗ resulted in an increase in the sensitivity, for the B3LYP and B97D functionals, from –0.514 to +0.514 V/Å; iii) the functional with dispersion correction (B97D) described best system B12N12–CO, as a function of the application of the electric field. Demonstrated the capability of B12N12 as a sensor for potential applications in the detection of CO under an ⃗EF⃗⃗⃗⃗ . Thirdly, it was found that the gas adsorption performance of B12N12 is improved due to the introduction of the Cu atom, but the interaction between CO and B12N11Cu, Cu@B12N12, Cu@b64, and Cu@b66 nanocages is strong, limiting applications for gas detection. Particularly, the CuB11N12 system shows moderate an adsorption energy (Eads = – 0.6 eV) and a high electronic sensitivity (ΔEgap = 81.6%) toward CO gas, compared to other modified systems. Furthermore, it was found that CuB11N12 presented low recovery time (14 ms) and high selectivity for CO detection, setting up as a superior material for applications involving the selective detection of CO gas. Finally, we observed that the CNCl molecule was observed to chemically adsorb on all MB11N12 (M = Fe–Zn) nanocages, but a stronger interaction occurred on the FeB11N12 and CoB11N12 nanocages, a moderate interaction occurred on the B12N12, NiB11N12, CuB11N12, and ZnB11N12 surfaces (σ-donation being more effective than π-back-bonding). However, the NiB11N12 and CuB11N12 nanocages showed the highest ΔEgap values (79.31% and 87.50%, respectively) for the adsorption of CNCl gas. Furthermore, based on performance analysis and comparison with previous results reported in the literature, it was found that NiB11N12 and CuB11N12 nanocages were superior materials for application in the detection of the CNCl toxic gas. |
publishDate |
2023 |
dc.date.issued.fl_str_mv |
2023-12-20 |
dc.date.accessioned.fl_str_mv |
2024-04-23T15:27:48Z |
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 |
SILVA, Adilson Luiś Pereira. Teoria do funcional da densidade aplicada ao estudo da interação entre nanogaiolas B12 N12 puras e dopadas com cobre e níquel com os gases tóxicos CO e CNCl. 2023. 150 f. Tese (Programa de Pós-Graduação Doutorado em Química) - Universidade Federal do Maranhão, São Luís, 2023. |
dc.identifier.uri.fl_str_mv |
https://tedebc.ufma.br/jspui/handle/tede/tede/5253 |
identifier_str_mv |
SILVA, Adilson Luiś Pereira. Teoria do funcional da densidade aplicada ao estudo da interação entre nanogaiolas B12 N12 puras e dopadas com cobre e níquel com os gases tóxicos CO e CNCl. 2023. 150 f. Tese (Programa de Pós-Graduação Doutorado em Química) - Universidade Federal do Maranhão, São Luís, 2023. |
url |
https://tedebc.ufma.br/jspui/handle/tede/tede/5253 |
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 Federal do Maranhão |
dc.publisher.program.fl_str_mv |
PROGRAMA DE PÓS-GRADUAÇÃO DOUTORADO EM QUÍMICA |
dc.publisher.initials.fl_str_mv |
UFMA |
dc.publisher.country.fl_str_mv |
Brasil |
dc.publisher.department.fl_str_mv |
DEPARTAMENTO DE QUÍMICA/CCET |
publisher.none.fl_str_mv |
Universidade Federal do Maranhão |
dc.source.none.fl_str_mv |
reponame:Biblioteca Digital de Teses e Dissertações da UFMA instname:Universidade Federal do Maranhão (UFMA) instacron:UFMA |
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Universidade Federal do Maranhão (UFMA) |
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UFMA |
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UFMA |
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Biblioteca Digital de Teses e Dissertações da UFMA |
collection |
Biblioteca Digital de Teses e Dissertações da UFMA |
bitstream.url.fl_str_mv |
http://tedebc.ufma.br:8080/bitstream/tede/5253/2/ADILSONLU%C3%8DSPEREIRASILVA.pdf http://tedebc.ufma.br:8080/bitstream/tede/5253/1/license.txt |
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MD5 MD5 |
repository.name.fl_str_mv |
Biblioteca Digital de Teses e Dissertações da UFMA - Universidade Federal do Maranhão (UFMA) |
repository.mail.fl_str_mv |
repositorio@ufma.br||repositorio@ufma.br |
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1809926218562142208 |