Semi-automated computational investigation of the oxidative degradation mechanisms of bisphenol A in Fenton-type processes

Bisphenol A (BPA) is a widespread industrial contaminant and endocrine disruptor whose efficient removal remains challenging because multiple, competing radical channels operate under Fenton-type advanced oxidation conditions. Here, we present a semi-automated first-principles approach to elucidate...

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Detalhes bibliográficos
Autores: Chacón Morales, Pablo A., Fernández Ramos, Antonio, González-Rodríguez, Jorge, Moreira Vilar, María Teresa, Martínez Núñez, Emilio, Ferro Costas, David
Formato: artículo
Fecha de publicación:2025
País:España
Recursos:Universidad de Santiago de Compostela (USC)
Repositorio:Minerva. Repositorio Institucional de la Universidad de Santiago de Compostela
Idioma:inglés
OAI Identifier:oai:minerva.usc.gal:10347/43289
Acesso em linha:https://hdl.handle.net/10347/43289
Access Level:acceso abierto
Palavra-chave:BPA oxidative degradation
Autonomous reaction mechanism discovery
Kinetic modeling
AutoMeKin
Pilgrim
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dc.title.none.fl_str_mv Semi-automated computational investigation of the oxidative degradation mechanisms of bisphenol A in Fenton-type processes
title Semi-automated computational investigation of the oxidative degradation mechanisms of bisphenol A in Fenton-type processes
spellingShingle Semi-automated computational investigation of the oxidative degradation mechanisms of bisphenol A in Fenton-type processes
Chacón Morales, Pablo A.
BPA oxidative degradation
Autonomous reaction mechanism discovery
Kinetic modeling
AutoMeKin
Pilgrim
title_short Semi-automated computational investigation of the oxidative degradation mechanisms of bisphenol A in Fenton-type processes
title_full Semi-automated computational investigation of the oxidative degradation mechanisms of bisphenol A in Fenton-type processes
title_fullStr Semi-automated computational investigation of the oxidative degradation mechanisms of bisphenol A in Fenton-type processes
title_full_unstemmed Semi-automated computational investigation of the oxidative degradation mechanisms of bisphenol A in Fenton-type processes
title_sort Semi-automated computational investigation of the oxidative degradation mechanisms of bisphenol A in Fenton-type processes
dc.creator.none.fl_str_mv Chacón Morales, Pablo A.
Fernández Ramos, Antonio
González-Rodríguez, Jorge
Moreira Vilar, María Teresa
Martínez Núñez, Emilio
Ferro Costas, David
author Chacón Morales, Pablo A.
author_facet Chacón Morales, Pablo A.
Fernández Ramos, Antonio
González-Rodríguez, Jorge
Moreira Vilar, María Teresa
Martínez Núñez, Emilio
Ferro Costas, David
author_role author
author2 Fernández Ramos, Antonio
González-Rodríguez, Jorge
Moreira Vilar, María Teresa
Martínez Núñez, Emilio
Ferro Costas, David
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Universidade de Santiago de Compostela. Departamento de Química Física
Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS)
Universidade de Santiago de Compostela. Centro Interdisciplinar de Investigación en Tecnoloxías Ambientais (CRETUS)
Universidade de Santiago de Compostela. Departamento de Enxeñaría Química
dc.subject.none.fl_str_mv BPA oxidative degradation
Autonomous reaction mechanism discovery
Kinetic modeling
AutoMeKin
Pilgrim
topic BPA oxidative degradation
Autonomous reaction mechanism discovery
Kinetic modeling
AutoMeKin
Pilgrim
description Bisphenol A (BPA) is a widespread industrial contaminant and endocrine disruptor whose efficient removal remains challenging because multiple, competing radical channels operate under Fenton-type advanced oxidation conditions. Here, we present a semi-automated first-principles approach to elucidate this process, comprising: (i) exhaustive discovery of unimolecular radical transformations with AutoMeKin; (ii) targeted manual construction of initial •OH addition and hydrogen-abstraction transition states; (iii) DFT refinement at ωB97XD/def2-TZVPP with SMD solvation model; (iv) selective microsolvation (up to two water molecules) for high potential energy barriers; (v) transition state theory rate constants evaluation for all elementary steps, and unified statistical treatment of dual bottlenecks for bimolecular •OH reactions; and (vi) Kinetic Monte Carlo (KMC) simulations with Pilgrim to obtain product distributions. The reaction network maps all feasible early •OH additions (ipso/ortho/meta/para), phenolic O–H abstraction, multistep hydroxylations, attempted dehydration steps, epoxidation, ring opening, and C–C scission leading to hydroxylated, quinonoid, lactone, and cleavage products. Selective microsolvation lowers critical rearrangement barriers, converting otherwise rate-determining steps into kinetically viable channels. KMC analysis identifies a characteristic ≈2:1 [•OH]:[BPA] threshold. Below it, early hydroxylated and ketone intermediates persist (e.g., catecholic and cyclohexadienone forms), whereas above it they are rapidly converted into trihydroxylated derivatives, ring-cleavage fragments, and quinone products. A reduced mechanism derived from sensitivity analysis reproduces the kinetics of the full network while retaining only essential OH-addition and phenolic H-abstraction steps. This integrated workflow thus provides mechanistic insight and a predictive, computationally efficient kinetic model readily transferable to other organic contaminants in advanced oxidation processes.
publishDate 2025
dc.date.none.fl_str_mv 2025
2025-10-06
2025
2025-10-06
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/10347/43289
url https://hdl.handle.net/10347/43289
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023 PID2022-142334OB-I00 TRANSICION DEL TRATAMIENTO DE AGUAS RESIDUALES HACIA LA ECONOMIA CIRCULAR Y LA SOSTENIBILIDAD MEDIANTE LA RECUPERACION DE RECURSOS Y AGUA DE CORRIENTES LIQUIDAS Y GASEOSAS
Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020 PDC2021-121540-I00 LA FOTOCATALISIS BASADA EN NANOPARTICULAS EN EL PUNTO DE MIRA DE LOS PROCESOS DE OXIDACION AVANZADA EN EL TRATAMIENTO DESCENTRALIZADAO DE AGUAS RESIDUALES
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
http://creativecommons.org/licenses/by/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv reponame:Minerva. Repositorio Institucional de la Universidad de Santiago de Compostela
instname:Universidad de Santiago de Compostela (USC)
instname_str Universidad de Santiago de Compostela (USC)
reponame_str Minerva. Repositorio Institucional de la Universidad de Santiago de Compostela
collection Minerva. Repositorio Institucional de la Universidad de Santiago de Compostela
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spelling Semi-automated computational investigation of the oxidative degradation mechanisms of bisphenol A in Fenton-type processesChacón Morales, Pablo A.Fernández Ramos, AntonioGonzález-Rodríguez, JorgeMoreira Vilar, María TeresaMartínez Núñez, EmilioFerro Costas, DavidBPA oxidative degradationAutonomous reaction mechanism discoveryKinetic modelingAutoMeKinPilgrimBisphenol A (BPA) is a widespread industrial contaminant and endocrine disruptor whose efficient removal remains challenging because multiple, competing radical channels operate under Fenton-type advanced oxidation conditions. Here, we present a semi-automated first-principles approach to elucidate this process, comprising: (i) exhaustive discovery of unimolecular radical transformations with AutoMeKin; (ii) targeted manual construction of initial •OH addition and hydrogen-abstraction transition states; (iii) DFT refinement at ωB97XD/def2-TZVPP with SMD solvation model; (iv) selective microsolvation (up to two water molecules) for high potential energy barriers; (v) transition state theory rate constants evaluation for all elementary steps, and unified statistical treatment of dual bottlenecks for bimolecular •OH reactions; and (vi) Kinetic Monte Carlo (KMC) simulations with Pilgrim to obtain product distributions. The reaction network maps all feasible early •OH additions (ipso/ortho/meta/para), phenolic O–H abstraction, multistep hydroxylations, attempted dehydration steps, epoxidation, ring opening, and C–C scission leading to hydroxylated, quinonoid, lactone, and cleavage products. Selective microsolvation lowers critical rearrangement barriers, converting otherwise rate-determining steps into kinetically viable channels. KMC analysis identifies a characteristic ≈2:1 [•OH]:[BPA] threshold. Below it, early hydroxylated and ketone intermediates persist (e.g., catecholic and cyclohexadienone forms), whereas above it they are rapidly converted into trihydroxylated derivatives, ring-cleavage fragments, and quinone products. A reduced mechanism derived from sensitivity analysis reproduces the kinetics of the full network while retaining only essential OH-addition and phenolic H-abstraction steps. This integrated workflow thus provides mechanistic insight and a predictive, computationally efficient kinetic model readily transferable to other organic contaminants in advanced oxidation processes.ElsevierUniversidade de Santiago de Compostela. Departamento de Química FísicaUniversidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS)Universidade de Santiago de Compostela. Centro Interdisciplinar de Investigación en Tecnoloxías Ambientais (CRETUS)Universidade de Santiago de Compostela. Departamento de Enxeñaría Química20252025-10-0620252025-10-06journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/10347/43289reponame:Minerva. Repositorio Institucional de la Universidad de Santiago de Compostelainstname:Universidad de Santiago de Compostela (USC)InglésengAgencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023 PID2022-142334OB-I00 TRANSICION DEL TRATAMIENTO DE AGUAS RESIDUALES HACIA LA ECONOMIA CIRCULAR Y LA SOSTENIBILIDAD MEDIANTE LA RECUPERACION DE RECURSOS Y AGUA DE CORRIENTES LIQUIDAS Y GASEOSASAgencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020 PDC2021-121540-I00 LA FOTOCATALISIS BASADA EN NANOPARTICULAS EN EL PUNTO DE MIRA DE LOS PROCESOS DE OXIDACION AVANZADA EN EL TRATAMIENTO DESCENTRALIZADAO DE AGUAS RESIDUALESopen accesshttp://purl.org/coar/access_right/c_abf2© 2025 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license. Attribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:minerva.usc.gal:10347/432892026-06-15T12:47:27Z
score 15.812429

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