Iron cycling during the autocatalytic decomposition of benzoic acid derivatives by Fenton-like and photo-Fenton techniques

Autores
Nichela, Daniela Alejandra; Donadelli, Jorge Andrés; Caram, Bruno Federico; Haddou, Menana; Rodríguez Nieto, Felipe Jorge; Oliveros,Esther; Garcia Einschlag, Fernando Sebastian
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In the context of our work on the oxidative degradation of a series of hydroxyl derivatives of benzoic acid (HBAs) by Fenton-like and photo-Fenton processes, we present a comprehensive study of the factors that affect the reduction of Fe(III) species, the rate limiting step in the Fenton reaction. We have investigated: (i) the formation of Fe(III)-HBA complexes, (ii) the ability of these complexes to participate in reductive pathways, and (iii) the formation of intermediate products capable of reducing ferric species.The results show that salicylate-like HBAs form stable bidentate ferric complexes in aqueous solutions at pH 3.0 and that Fe(III) complexation significantly decreases the overall degradation rates in Fenton systems by slowing down Fe(II) production through both dark and photo-initiated pathways. Interestingly, in contrast to ferric complexes of aliphatic carboxylates that undergo a photo-induced decarboxylation upon excitation in the 300-400. nm wavelength range, ferric-salicylate complexes yield Fe(II) and hydroxyl radicals by oxidation of water molecules in the coordination sphere of the metal center. However, their efficiencies are significantly lower than that of the Fe(III) aqua complex. Moreover, Fe(III)-HBA complexes are inert upon excitation of the LMCT bands involving the organic ligand (i.e., 400-600. nm).As observed for other aromatic compounds, Fe(III)-reducing intermediates formed during the Fenton oxidation of HBAs play a key role in iron cycling. The analysis of the primary oxidation/hydroxylation products as well as Fe(III)-reduction studies showed that, among dihydroxy aromatic derivatives, hydroquinone-like structures were much more efficient than catechol-like structures for reducing Fe(III). Although all trihydroxy derivatives produced Fe(II), ring opening reactions prevailed under the conditions of the Fenton reaction.The results of our investigation on the Fenton oxidation of HBA derivatives show that, in each particular case, the complex interplay of the aforementioned factors should be carefully evaluated for developing optimal applications of Fenton processes at a technological level.
Fil: Nichela, Daniela Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte. Instituto de Investigaciones en Biodiversidad y Medioambiente. Universidad Nacional del Comahue. Centro Regional Universidad Bariloche. Instituto de Investigaciones en Biodiversidad y Medioambiente; Argentina
Fil: Donadelli, Jorge Andrés. 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: Caram, Bruno Federico. 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: Haddou, Menana. Université Toulouse II. Laboratoire des Interactions Moléculaires et Réactivité Chimique et Photochimique; Francia
Fil: Rodríguez Nieto, Felipe Jorge. 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: Oliveros,Esther. Université Toulouse II. Laboratoire des Interactions Moléculaires et Réactivité Chimique et Photochimique; Francia
Fil: Garcia Einschlag, Fernando Sebastian. 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
Autocatalysis
Benzoic Acid Derivatives
Hydroxyl Radicals
Iron(Iii) Complexation
Iron(Iii) Reduction
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/81895
Acceder
id CONICETDig_40ace3d0d4a1f9b69ee38a95865b1f4e
oai_identifier_str oai:ri.conicet.gov.ar:11336/81895
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Iron cycling during the autocatalytic decomposition of benzoic acid derivatives by Fenton-like and photo-Fenton techniquesNichela, Daniela AlejandraDonadelli, Jorge AndrésCaram, Bruno FedericoHaddou, MenanaRodríguez Nieto, Felipe JorgeOliveros,EstherGarcia Einschlag, Fernando SebastianAutocatalysisBenzoic Acid DerivativesHydroxyl RadicalsIron(Iii) ComplexationIron(Iii) Reductionhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1In the context of our work on the oxidative degradation of a series of hydroxyl derivatives of benzoic acid (HBAs) by Fenton-like and photo-Fenton processes, we present a comprehensive study of the factors that affect the reduction of Fe(III) species, the rate limiting step in the Fenton reaction. We have investigated: (i) the formation of Fe(III)-HBA complexes, (ii) the ability of these complexes to participate in reductive pathways, and (iii) the formation of intermediate products capable of reducing ferric species.The results show that salicylate-like HBAs form stable bidentate ferric complexes in aqueous solutions at pH 3.0 and that Fe(III) complexation significantly decreases the overall degradation rates in Fenton systems by slowing down Fe(II) production through both dark and photo-initiated pathways. Interestingly, in contrast to ferric complexes of aliphatic carboxylates that undergo a photo-induced decarboxylation upon excitation in the 300-400. nm wavelength range, ferric-salicylate complexes yield Fe(II) and hydroxyl radicals by oxidation of water molecules in the coordination sphere of the metal center. However, their efficiencies are significantly lower than that of the Fe(III) aqua complex. Moreover, Fe(III)-HBA complexes are inert upon excitation of the LMCT bands involving the organic ligand (i.e., 400-600. nm).As observed for other aromatic compounds, Fe(III)-reducing intermediates formed during the Fenton oxidation of HBAs play a key role in iron cycling. The analysis of the primary oxidation/hydroxylation products as well as Fe(III)-reduction studies showed that, among dihydroxy aromatic derivatives, hydroquinone-like structures were much more efficient than catechol-like structures for reducing Fe(III). Although all trihydroxy derivatives produced Fe(II), ring opening reactions prevailed under the conditions of the Fenton reaction.The results of our investigation on the Fenton oxidation of HBA derivatives show that, in each particular case, the complex interplay of the aforementioned factors should be carefully evaluated for developing optimal applications of Fenton processes at a technological level.Fil: Nichela, Daniela Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte. Instituto de Investigaciones en Biodiversidad y Medioambiente. Universidad Nacional del Comahue. Centro Regional Universidad Bariloche. Instituto de Investigaciones en Biodiversidad y Medioambiente; ArgentinaFil: Donadelli, Jorge Andrés. 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: Caram, Bruno Federico. 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: Haddou, Menana. Université Toulouse II. Laboratoire des Interactions Moléculaires et Réactivité Chimique et Photochimique; FranciaFil: Rodríguez Nieto, Felipe Jorge. 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: Oliveros,Esther. Université Toulouse II. Laboratoire des Interactions Moléculaires et Réactivité Chimique et Photochimique; FranciaFil: Garcia Einschlag, Fernando Sebastian. 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; ArgentinaElsevier Science2015-07-21info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/81895Nichela, Daniela Alejandra; Donadelli, Jorge Andrés; Caram, Bruno Federico; Haddou, Menana; Rodríguez Nieto, Felipe Jorge; et al.; Iron cycling during the autocatalytic decomposition of benzoic acid derivatives by Fenton-like and photo-Fenton techniques; Elsevier Science; Applied Catalysis B: Environmental; 170-171; 21-7-2015; 312-3210926-3373CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0926337315000338info:eu-repo/semantics/altIdentifier/doi/10.1016/j.apcatb.2015.01.028info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:59:58Zoai:ri.conicet.gov.ar:11336/81895instacron: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:34982025-09-03 09:59:59.121CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Iron cycling during the autocatalytic decomposition of benzoic acid derivatives by Fenton-like and photo-Fenton techniques
title Iron cycling during the autocatalytic decomposition of benzoic acid derivatives by Fenton-like and photo-Fenton techniques
spellingShingle Iron cycling during the autocatalytic decomposition of benzoic acid derivatives by Fenton-like and photo-Fenton techniques
Nichela, Daniela Alejandra
Autocatalysis
Benzoic Acid Derivatives
Hydroxyl Radicals
Iron(Iii) Complexation
Iron(Iii) Reduction
title_short Iron cycling during the autocatalytic decomposition of benzoic acid derivatives by Fenton-like and photo-Fenton techniques
title_full Iron cycling during the autocatalytic decomposition of benzoic acid derivatives by Fenton-like and photo-Fenton techniques
title_fullStr Iron cycling during the autocatalytic decomposition of benzoic acid derivatives by Fenton-like and photo-Fenton techniques
title_full_unstemmed Iron cycling during the autocatalytic decomposition of benzoic acid derivatives by Fenton-like and photo-Fenton techniques
title_sort Iron cycling during the autocatalytic decomposition of benzoic acid derivatives by Fenton-like and photo-Fenton techniques
dc.creator.none.fl_str_mv Nichela, Daniela Alejandra
Donadelli, Jorge Andrés
Caram, Bruno Federico
Haddou, Menana
Rodríguez Nieto, Felipe Jorge
Oliveros,Esther
Garcia Einschlag, Fernando Sebastian
author Nichela, Daniela Alejandra
author_facet Nichela, Daniela Alejandra
Donadelli, Jorge Andrés
Caram, Bruno Federico
Haddou, Menana
Rodríguez Nieto, Felipe Jorge
Oliveros,Esther
Garcia Einschlag, Fernando Sebastian
author_role author
author2 Donadelli, Jorge Andrés
Caram, Bruno Federico
Haddou, Menana
Rodríguez Nieto, Felipe Jorge
Oliveros,Esther
Garcia Einschlag, Fernando Sebastian
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Autocatalysis
Benzoic Acid Derivatives
Hydroxyl Radicals
Iron(Iii) Complexation
Iron(Iii) Reduction
topic Autocatalysis
Benzoic Acid Derivatives
Hydroxyl Radicals
Iron(Iii) Complexation
Iron(Iii) Reduction
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv In the context of our work on the oxidative degradation of a series of hydroxyl derivatives of benzoic acid (HBAs) by Fenton-like and photo-Fenton processes, we present a comprehensive study of the factors that affect the reduction of Fe(III) species, the rate limiting step in the Fenton reaction. We have investigated: (i) the formation of Fe(III)-HBA complexes, (ii) the ability of these complexes to participate in reductive pathways, and (iii) the formation of intermediate products capable of reducing ferric species.The results show that salicylate-like HBAs form stable bidentate ferric complexes in aqueous solutions at pH 3.0 and that Fe(III) complexation significantly decreases the overall degradation rates in Fenton systems by slowing down Fe(II) production through both dark and photo-initiated pathways. Interestingly, in contrast to ferric complexes of aliphatic carboxylates that undergo a photo-induced decarboxylation upon excitation in the 300-400. nm wavelength range, ferric-salicylate complexes yield Fe(II) and hydroxyl radicals by oxidation of water molecules in the coordination sphere of the metal center. However, their efficiencies are significantly lower than that of the Fe(III) aqua complex. Moreover, Fe(III)-HBA complexes are inert upon excitation of the LMCT bands involving the organic ligand (i.e., 400-600. nm).As observed for other aromatic compounds, Fe(III)-reducing intermediates formed during the Fenton oxidation of HBAs play a key role in iron cycling. The analysis of the primary oxidation/hydroxylation products as well as Fe(III)-reduction studies showed that, among dihydroxy aromatic derivatives, hydroquinone-like structures were much more efficient than catechol-like structures for reducing Fe(III). Although all trihydroxy derivatives produced Fe(II), ring opening reactions prevailed under the conditions of the Fenton reaction.The results of our investigation on the Fenton oxidation of HBA derivatives show that, in each particular case, the complex interplay of the aforementioned factors should be carefully evaluated for developing optimal applications of Fenton processes at a technological level.
Fil: Nichela, Daniela Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte. Instituto de Investigaciones en Biodiversidad y Medioambiente. Universidad Nacional del Comahue. Centro Regional Universidad Bariloche. Instituto de Investigaciones en Biodiversidad y Medioambiente; Argentina
Fil: Donadelli, Jorge Andrés. 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: Caram, Bruno Federico. 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: Haddou, Menana. Université Toulouse II. Laboratoire des Interactions Moléculaires et Réactivité Chimique et Photochimique; Francia
Fil: Rodríguez Nieto, Felipe Jorge. 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: Oliveros,Esther. Université Toulouse II. Laboratoire des Interactions Moléculaires et Réactivité Chimique et Photochimique; Francia
Fil: Garcia Einschlag, Fernando Sebastian. 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 In the context of our work on the oxidative degradation of a series of hydroxyl derivatives of benzoic acid (HBAs) by Fenton-like and photo-Fenton processes, we present a comprehensive study of the factors that affect the reduction of Fe(III) species, the rate limiting step in the Fenton reaction. We have investigated: (i) the formation of Fe(III)-HBA complexes, (ii) the ability of these complexes to participate in reductive pathways, and (iii) the formation of intermediate products capable of reducing ferric species.The results show that salicylate-like HBAs form stable bidentate ferric complexes in aqueous solutions at pH 3.0 and that Fe(III) complexation significantly decreases the overall degradation rates in Fenton systems by slowing down Fe(II) production through both dark and photo-initiated pathways. Interestingly, in contrast to ferric complexes of aliphatic carboxylates that undergo a photo-induced decarboxylation upon excitation in the 300-400. nm wavelength range, ferric-salicylate complexes yield Fe(II) and hydroxyl radicals by oxidation of water molecules in the coordination sphere of the metal center. However, their efficiencies are significantly lower than that of the Fe(III) aqua complex. Moreover, Fe(III)-HBA complexes are inert upon excitation of the LMCT bands involving the organic ligand (i.e., 400-600. nm).As observed for other aromatic compounds, Fe(III)-reducing intermediates formed during the Fenton oxidation of HBAs play a key role in iron cycling. The analysis of the primary oxidation/hydroxylation products as well as Fe(III)-reduction studies showed that, among dihydroxy aromatic derivatives, hydroquinone-like structures were much more efficient than catechol-like structures for reducing Fe(III). Although all trihydroxy derivatives produced Fe(II), ring opening reactions prevailed under the conditions of the Fenton reaction.The results of our investigation on the Fenton oxidation of HBA derivatives show that, in each particular case, the complex interplay of the aforementioned factors should be carefully evaluated for developing optimal applications of Fenton processes at a technological level.
publishDate 2015
dc.date.none.fl_str_mv 2015-07-21
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/11336/81895
Nichela, Daniela Alejandra; Donadelli, Jorge Andrés; Caram, Bruno Federico; Haddou, Menana; Rodríguez Nieto, Felipe Jorge; et al.; Iron cycling during the autocatalytic decomposition of benzoic acid derivatives by Fenton-like and photo-Fenton techniques; Elsevier Science; Applied Catalysis B: Environmental; 170-171; 21-7-2015; 312-321
0926-3373
CONICET Digital
CONICET
url http://hdl.handle.net/11336/81895
identifier_str_mv Nichela, Daniela Alejandra; Donadelli, Jorge Andrés; Caram, Bruno Federico; Haddou, Menana; Rodríguez Nieto, Felipe Jorge; et al.; Iron cycling during the autocatalytic decomposition of benzoic acid derivatives by Fenton-like and photo-Fenton techniques; Elsevier Science; Applied Catalysis B: Environmental; 170-171; 21-7-2015; 312-321
0926-3373
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0926337315000338
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.apcatb.2015.01.028
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier Science
publisher.none.fl_str_mv Elsevier Science
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
_version_ 1842269612838748160
score 12.885934

Publicaciones similares