Mechanisms of Halomethane Adsorption on Functionalized Carbons: How Surface Chemistry Governs Selectivity in Realistic Gas Mixtures

Autores
Farías Hermosilla, María Estefanía; Albesa, Alberto Gustavo
Año de publicación
2026
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Halomethanes (CH3X, where X = F, Cl, Br) are potent atmospheric pollutants, and their removal via adsorption on activated carbons (ACs) is a critical remediation strategy. However, the molecular-level influence of AC surface chemistry on adsorption, especially under realistic environmental conditions, is not fully understood. This work utilizes Grand Canonical Monte Carlo (GCMC) simulations to investigate the adsorption of CH3F, CH3Cl, and CH3Br on realistic carbon models, comparing unfunctionalized graphitic surfaces (AC0) with surfaces functionalized with alcohol (AC1), carbonyl (AC2), and carboxyl (AC3) groups. We analyze the process for both pure components and in realistic mixtures (Quarantine and Pre-Shipment concentrations). Our findings reveal a critical inversion in adsorption preference. For pure components, CH3Br adsorption is highest on the unfunctionalized (AC0) surface, driven by strong adsorbate–adsorbate interactions leading to condensation, characterized by a rising isosteric heat of adsorption (≈35–45 kJ/mol) that matches the enthalpy of sublimation. Conversely, in realistic humid mixtures, the pristine surface suffers a capacity collapse (>90% loss). The functionalized surfaces (especially AC3) demonstrate superior performance, exhibiting a thermodynamic selectivity of 3/>100 (compared to ≈15 for AC0) and retaining approximately 60% of their dry-condition affinity. This study elucidates the distinct roles of surface chemistry and intermolecular forces, providing a molecular basis for designing carbon materials optimized for high selectivity in complex environmental gas streams.
Fil: Farías Hermosilla, María Estefanía. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Albesa, Alberto Gustavo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Materia
Halomethanes
Activated Carbon
Monte Carlo
Pesticides
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/290008
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Mechanisms of Halomethane Adsorption on Functionalized Carbons: How Surface Chemistry Governs Selectivity in Realistic Gas MixturesFarías Hermosilla, María EstefaníaAlbesa, Alberto GustavoHalomethanesActivated CarbonMonte CarloPesticideshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Halomethanes (CH3X, where X = F, Cl, Br) are potent atmospheric pollutants, and their removal via adsorption on activated carbons (ACs) is a critical remediation strategy. However, the molecular-level influence of AC surface chemistry on adsorption, especially under realistic environmental conditions, is not fully understood. This work utilizes Grand Canonical Monte Carlo (GCMC) simulations to investigate the adsorption of CH3F, CH3Cl, and CH3Br on realistic carbon models, comparing unfunctionalized graphitic surfaces (AC0) with surfaces functionalized with alcohol (AC1), carbonyl (AC2), and carboxyl (AC3) groups. We analyze the process for both pure components and in realistic mixtures (Quarantine and Pre-Shipment concentrations). Our findings reveal a critical inversion in adsorption preference. For pure components, CH3Br adsorption is highest on the unfunctionalized (AC0) surface, driven by strong adsorbate–adsorbate interactions leading to condensation, characterized by a rising isosteric heat of adsorption (≈35–45 kJ/mol) that matches the enthalpy of sublimation. Conversely, in realistic humid mixtures, the pristine surface suffers a capacity collapse (>90% loss). The functionalized surfaces (especially AC3) demonstrate superior performance, exhibiting a thermodynamic selectivity of 3/>100 (compared to ≈15 for AC0) and retaining approximately 60% of their dry-condition affinity. This study elucidates the distinct roles of surface chemistry and intermolecular forces, providing a molecular basis for designing carbon materials optimized for high selectivity in complex environmental gas streams.Fil: Farías Hermosilla, María Estefanía. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Albesa, Alberto Gustavo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaMDPI2026-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/290008Farías Hermosilla, María Estefanía; Albesa, Alberto Gustavo; Mechanisms of Halomethane Adsorption on Functionalized Carbons: How Surface Chemistry Governs Selectivity in Realistic Gas Mixtures; MDPI; Journal of Carbon Research; 12; 1; 2-2026; 1-192311-5629CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.mdpi.com/2311-5629/12/1/15info:eu-repo/semantics/altIdentifier/doi/10.3390/c12010015info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2026-08-25T15:01:30Zoai:ri.conicet.gov.ar:11336/290008instacron: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:34982026-08-25 15:01:30.625CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Mechanisms of Halomethane Adsorption on Functionalized Carbons: How Surface Chemistry Governs Selectivity in Realistic Gas Mixtures
title Mechanisms of Halomethane Adsorption on Functionalized Carbons: How Surface Chemistry Governs Selectivity in Realistic Gas Mixtures
spellingShingle Mechanisms of Halomethane Adsorption on Functionalized Carbons: How Surface Chemistry Governs Selectivity in Realistic Gas Mixtures
Farías Hermosilla, María Estefanía
Halomethanes
Activated Carbon
Monte Carlo
Pesticides
title_short Mechanisms of Halomethane Adsorption on Functionalized Carbons: How Surface Chemistry Governs Selectivity in Realistic Gas Mixtures
title_full Mechanisms of Halomethane Adsorption on Functionalized Carbons: How Surface Chemistry Governs Selectivity in Realistic Gas Mixtures
title_fullStr Mechanisms of Halomethane Adsorption on Functionalized Carbons: How Surface Chemistry Governs Selectivity in Realistic Gas Mixtures
title_full_unstemmed Mechanisms of Halomethane Adsorption on Functionalized Carbons: How Surface Chemistry Governs Selectivity in Realistic Gas Mixtures
title_sort Mechanisms of Halomethane Adsorption on Functionalized Carbons: How Surface Chemistry Governs Selectivity in Realistic Gas Mixtures
dc.creator.none.fl_str_mv Farías Hermosilla, María Estefanía
Albesa, Alberto Gustavo
author Farías Hermosilla, María Estefanía
author_facet Farías Hermosilla, María Estefanía
Albesa, Alberto Gustavo
author_role author
author2 Albesa, Alberto Gustavo
author2_role author
dc.subject.none.fl_str_mv Halomethanes
Activated Carbon
Monte Carlo
Pesticides
topic Halomethanes
Activated Carbon
Monte Carlo
Pesticides
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Halomethanes (CH3X, where X = F, Cl, Br) are potent atmospheric pollutants, and their removal via adsorption on activated carbons (ACs) is a critical remediation strategy. However, the molecular-level influence of AC surface chemistry on adsorption, especially under realistic environmental conditions, is not fully understood. This work utilizes Grand Canonical Monte Carlo (GCMC) simulations to investigate the adsorption of CH3F, CH3Cl, and CH3Br on realistic carbon models, comparing unfunctionalized graphitic surfaces (AC0) with surfaces functionalized with alcohol (AC1), carbonyl (AC2), and carboxyl (AC3) groups. We analyze the process for both pure components and in realistic mixtures (Quarantine and Pre-Shipment concentrations). Our findings reveal a critical inversion in adsorption preference. For pure components, CH3Br adsorption is highest on the unfunctionalized (AC0) surface, driven by strong adsorbate–adsorbate interactions leading to condensation, characterized by a rising isosteric heat of adsorption (≈35–45 kJ/mol) that matches the enthalpy of sublimation. Conversely, in realistic humid mixtures, the pristine surface suffers a capacity collapse (>90% loss). The functionalized surfaces (especially AC3) demonstrate superior performance, exhibiting a thermodynamic selectivity of 3/>100 (compared to ≈15 for AC0) and retaining approximately 60% of their dry-condition affinity. This study elucidates the distinct roles of surface chemistry and intermolecular forces, providing a molecular basis for designing carbon materials optimized for high selectivity in complex environmental gas streams.
Fil: Farías Hermosilla, María Estefanía. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Albesa, Alberto Gustavo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
description Halomethanes (CH3X, where X = F, Cl, Br) are potent atmospheric pollutants, and their removal via adsorption on activated carbons (ACs) is a critical remediation strategy. However, the molecular-level influence of AC surface chemistry on adsorption, especially under realistic environmental conditions, is not fully understood. This work utilizes Grand Canonical Monte Carlo (GCMC) simulations to investigate the adsorption of CH3F, CH3Cl, and CH3Br on realistic carbon models, comparing unfunctionalized graphitic surfaces (AC0) with surfaces functionalized with alcohol (AC1), carbonyl (AC2), and carboxyl (AC3) groups. We analyze the process for both pure components and in realistic mixtures (Quarantine and Pre-Shipment concentrations). Our findings reveal a critical inversion in adsorption preference. For pure components, CH3Br adsorption is highest on the unfunctionalized (AC0) surface, driven by strong adsorbate–adsorbate interactions leading to condensation, characterized by a rising isosteric heat of adsorption (≈35–45 kJ/mol) that matches the enthalpy of sublimation. Conversely, in realistic humid mixtures, the pristine surface suffers a capacity collapse (>90% loss). The functionalized surfaces (especially AC3) demonstrate superior performance, exhibiting a thermodynamic selectivity of 3/>100 (compared to ≈15 for AC0) and retaining approximately 60% of their dry-condition affinity. This study elucidates the distinct roles of surface chemistry and intermolecular forces, providing a molecular basis for designing carbon materials optimized for high selectivity in complex environmental gas streams.
publishDate 2026
dc.date.none.fl_str_mv 2026-02
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/11336/290008
Farías Hermosilla, María Estefanía; Albesa, Alberto Gustavo; Mechanisms of Halomethane Adsorption on Functionalized Carbons: How Surface Chemistry Governs Selectivity in Realistic Gas Mixtures; MDPI; Journal of Carbon Research; 12; 1; 2-2026; 1-19
2311-5629
CONICET Digital
CONICET
url http://hdl.handle.net/11336/290008
identifier_str_mv Farías Hermosilla, María Estefanía; Albesa, Alberto Gustavo; Mechanisms of Halomethane Adsorption on Functionalized Carbons: How Surface Chemistry Governs Selectivity in Realistic Gas Mixtures; MDPI; Journal of Carbon Research; 12; 1; 2-2026; 1-19
2311-5629
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.mdpi.com/2311-5629/12/1/15
info:eu-repo/semantics/altIdentifier/doi/10.3390/c12010015
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv MDPI
publisher.none.fl_str_mv MDPI
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
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