Visible‐Light‐Driven CO 2 Photoreduction Assisted by Reduced Methyl Viologen Using MIL‐125‐NH 2 as a Light Harvester and Scaffold for FDH Immobilization

Autores
Aguirre, Matías Ezequiel; Slaboch, María Victoria; González, Pablo Javier; Ramirez, Cristina Lujan; Di Iorio, Yesica Dolores
Año de publicación
2025
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Metal-organic frameworks (MOFs)-enzyme composites are promising catalysts for energy production and climate change mitigation through CO2 reduction. However, many biocatalysts are limited by their dependence on reduced nicotinamide adenine dinucleotide (NADH) as a cofactor. Here, we report a simple system using formate dehydrogenase (FDH) adsorbed onto MIL-125-NH2, enabling visible-light-driven formic acid (HCOOH) production without NADH. The MOF serves as both support and photoactive material, achieving a maximum enzyme loading of 3.84% (w/w) at neutral pH. Upon excitation at 470 nm and using triethanolamine (TEOA) as electron donor, the system produced 134.9 μmol HCOOH gFDH−1 h−1 . This increased to 655 μmol HCOOH gFDH−1 h−1 using photoreduced methyl viologen (MV+●), which transfers electrons 10.8 times more efficiently than NADH. pH significantly influences enzyme loading and activity; while lower pH enhances loading, it causes irreversible deactivation. Optimal results were achieved by immobilizing FDH at pH 7.0 and performing the reaction at pH 8.0, yielding 2005 μmol HCOOH gFDH−1 in 4 h. Reduced activity in acidic media was attributed to protonation of TEOA and MV+●, rather than enzyme denaturation, suggesting a protective effect from the MOF scaffold. These results highlight pH tuning as a key factor for optimizing catalytic efficiency in MOF-enzyme systems.
Fil: Aguirre, Matías Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Físicas de Mar del Plata. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Físicas de Mar del Plata; Argentina
Fil: Slaboch, María Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Físicas de Mar del Plata. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Físicas de Mar del Plata; Argentina
Fil: González, Pablo Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Físicas de Mar del Plata. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Físicas de Mar del Plata; Argentina
Fil: Ramirez, Cristina Lujan. Universidad Nacional de Mar del Plata; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; Argentina
Fil: Di Iorio, Yesica Dolores. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Físicas de Mar del Plata. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Físicas de Mar del Plata; Argentina
Materia
(MOFs)-enzyme composites
Visible-Light-DrivenCO2Photoreduction
FDHImmobilization
MIL-125-NH2
(MOFs)-enzyme composites
MIL-125-NH2
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/283119
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/283119
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Visible‐Light‐Driven CO 2 Photoreduction Assisted by Reduced Methyl Viologen Using MIL‐125‐NH 2 as a Light Harvester and Scaffold for FDH ImmobilizationAguirre, Matías EzequielSlaboch, María VictoriaGonzález, Pablo JavierRamirez, Cristina LujanDi Iorio, Yesica Dolores(MOFs)-enzyme compositesVisible-Light-DrivenCO2PhotoreductionFDHImmobilizationMIL-125-NH2(MOFs)-enzyme compositesMIL-125-NH2https://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Metal-organic frameworks (MOFs)-enzyme composites are promising catalysts for energy production and climate change mitigation through CO2 reduction. However, many biocatalysts are limited by their dependence on reduced nicotinamide adenine dinucleotide (NADH) as a cofactor. Here, we report a simple system using formate dehydrogenase (FDH) adsorbed onto MIL-125-NH2, enabling visible-light-driven formic acid (HCOOH) production without NADH. The MOF serves as both support and photoactive material, achieving a maximum enzyme loading of 3.84% (w/w) at neutral pH. Upon excitation at 470 nm and using triethanolamine (TEOA) as electron donor, the system produced 134.9 μmol HCOOH gFDH−1 h−1 . This increased to 655 μmol HCOOH gFDH−1 h−1 using photoreduced methyl viologen (MV+●), which transfers electrons 10.8 times more efficiently than NADH. pH significantly influences enzyme loading and activity; while lower pH enhances loading, it causes irreversible deactivation. Optimal results were achieved by immobilizing FDH at pH 7.0 and performing the reaction at pH 8.0, yielding 2005 μmol HCOOH gFDH−1 in 4 h. Reduced activity in acidic media was attributed to protonation of TEOA and MV+●, rather than enzyme denaturation, suggesting a protective effect from the MOF scaffold. These results highlight pH tuning as a key factor for optimizing catalytic efficiency in MOF-enzyme systems.Fil: Aguirre, Matías Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Físicas de Mar del Plata. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Físicas de Mar del Plata; ArgentinaFil: Slaboch, María Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Físicas de Mar del Plata. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Físicas de Mar del Plata; ArgentinaFil: González, Pablo Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Físicas de Mar del Plata. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Físicas de Mar del Plata; ArgentinaFil: Ramirez, Cristina Lujan. Universidad Nacional de Mar del Plata; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; ArgentinaFil: Di Iorio, Yesica Dolores. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Físicas de Mar del Plata. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Físicas de Mar del Plata; ArgentinaWiley VCH Verlag2025-10info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/283119Aguirre, Matías Ezequiel; Slaboch, María Victoria; González, Pablo Javier; Ramirez, Cristina Lujan; Di Iorio, Yesica Dolores; Visible‐Light‐Driven CO 2 Photoreduction Assisted by Reduced Methyl Viologen Using MIL‐125‐NH 2 as a Light Harvester and Scaffold for FDH Immobilization; Wiley VCH Verlag; Chemcatchem; 17; 23; 10-2025; 1-131867-3880CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cctc.202501120info:eu-repo/semantics/altIdentifier/doi/10.1002/cctc.202501120info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2026-08-25T14:34:41Zoai:ri.conicet.gov.ar:11336/283119instacron: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 14:34:42.009CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Visible‐Light‐Driven CO 2 Photoreduction Assisted by Reduced Methyl Viologen Using MIL‐125‐NH 2 as a Light Harvester and Scaffold for FDH Immobilization
title Visible‐Light‐Driven CO 2 Photoreduction Assisted by Reduced Methyl Viologen Using MIL‐125‐NH 2 as a Light Harvester and Scaffold for FDH Immobilization
spellingShingle Visible‐Light‐Driven CO 2 Photoreduction Assisted by Reduced Methyl Viologen Using MIL‐125‐NH 2 as a Light Harvester and Scaffold for FDH Immobilization
Aguirre, Matías Ezequiel
(MOFs)-enzyme composites
Visible-Light-DrivenCO2Photoreduction
FDHImmobilization
MIL-125-NH2
(MOFs)-enzyme composites
MIL-125-NH2
title_short Visible‐Light‐Driven CO 2 Photoreduction Assisted by Reduced Methyl Viologen Using MIL‐125‐NH 2 as a Light Harvester and Scaffold for FDH Immobilization
title_full Visible‐Light‐Driven CO 2 Photoreduction Assisted by Reduced Methyl Viologen Using MIL‐125‐NH 2 as a Light Harvester and Scaffold for FDH Immobilization
title_fullStr Visible‐Light‐Driven CO 2 Photoreduction Assisted by Reduced Methyl Viologen Using MIL‐125‐NH 2 as a Light Harvester and Scaffold for FDH Immobilization
title_full_unstemmed Visible‐Light‐Driven CO 2 Photoreduction Assisted by Reduced Methyl Viologen Using MIL‐125‐NH 2 as a Light Harvester and Scaffold for FDH Immobilization
title_sort Visible‐Light‐Driven CO 2 Photoreduction Assisted by Reduced Methyl Viologen Using MIL‐125‐NH 2 as a Light Harvester and Scaffold for FDH Immobilization
dc.creator.none.fl_str_mv Aguirre, Matías Ezequiel
Slaboch, María Victoria
González, Pablo Javier
Ramirez, Cristina Lujan
Di Iorio, Yesica Dolores
author Aguirre, Matías Ezequiel
author_facet Aguirre, Matías Ezequiel
Slaboch, María Victoria
González, Pablo Javier
Ramirez, Cristina Lujan
Di Iorio, Yesica Dolores
author_role author
author2 Slaboch, María Victoria
González, Pablo Javier
Ramirez, Cristina Lujan
Di Iorio, Yesica Dolores
author2_role author
author
author
author
dc.subject.none.fl_str_mv (MOFs)-enzyme composites
Visible-Light-DrivenCO2Photoreduction
FDHImmobilization
MIL-125-NH2
(MOFs)-enzyme composites
MIL-125-NH2
topic (MOFs)-enzyme composites
Visible-Light-DrivenCO2Photoreduction
FDHImmobilization
MIL-125-NH2
(MOFs)-enzyme composites
MIL-125-NH2
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Metal-organic frameworks (MOFs)-enzyme composites are promising catalysts for energy production and climate change mitigation through CO2 reduction. However, many biocatalysts are limited by their dependence on reduced nicotinamide adenine dinucleotide (NADH) as a cofactor. Here, we report a simple system using formate dehydrogenase (FDH) adsorbed onto MIL-125-NH2, enabling visible-light-driven formic acid (HCOOH) production without NADH. The MOF serves as both support and photoactive material, achieving a maximum enzyme loading of 3.84% (w/w) at neutral pH. Upon excitation at 470 nm and using triethanolamine (TEOA) as electron donor, the system produced 134.9 μmol HCOOH gFDH−1 h−1 . This increased to 655 μmol HCOOH gFDH−1 h−1 using photoreduced methyl viologen (MV+●), which transfers electrons 10.8 times more efficiently than NADH. pH significantly influences enzyme loading and activity; while lower pH enhances loading, it causes irreversible deactivation. Optimal results were achieved by immobilizing FDH at pH 7.0 and performing the reaction at pH 8.0, yielding 2005 μmol HCOOH gFDH−1 in 4 h. Reduced activity in acidic media was attributed to protonation of TEOA and MV+●, rather than enzyme denaturation, suggesting a protective effect from the MOF scaffold. These results highlight pH tuning as a key factor for optimizing catalytic efficiency in MOF-enzyme systems.
Fil: Aguirre, Matías Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Físicas de Mar del Plata. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Físicas de Mar del Plata; Argentina
Fil: Slaboch, María Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Físicas de Mar del Plata. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Físicas de Mar del Plata; Argentina
Fil: González, Pablo Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Físicas de Mar del Plata. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Físicas de Mar del Plata; Argentina
Fil: Ramirez, Cristina Lujan. Universidad Nacional de Mar del Plata; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; Argentina
Fil: Di Iorio, Yesica Dolores. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Físicas de Mar del Plata. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Físicas de Mar del Plata; Argentina
description Metal-organic frameworks (MOFs)-enzyme composites are promising catalysts for energy production and climate change mitigation through CO2 reduction. However, many biocatalysts are limited by their dependence on reduced nicotinamide adenine dinucleotide (NADH) as a cofactor. Here, we report a simple system using formate dehydrogenase (FDH) adsorbed onto MIL-125-NH2, enabling visible-light-driven formic acid (HCOOH) production without NADH. The MOF serves as both support and photoactive material, achieving a maximum enzyme loading of 3.84% (w/w) at neutral pH. Upon excitation at 470 nm and using triethanolamine (TEOA) as electron donor, the system produced 134.9 μmol HCOOH gFDH−1 h−1 . This increased to 655 μmol HCOOH gFDH−1 h−1 using photoreduced methyl viologen (MV+●), which transfers electrons 10.8 times more efficiently than NADH. pH significantly influences enzyme loading and activity; while lower pH enhances loading, it causes irreversible deactivation. Optimal results were achieved by immobilizing FDH at pH 7.0 and performing the reaction at pH 8.0, yielding 2005 μmol HCOOH gFDH−1 in 4 h. Reduced activity in acidic media was attributed to protonation of TEOA and MV+●, rather than enzyme denaturation, suggesting a protective effect from the MOF scaffold. These results highlight pH tuning as a key factor for optimizing catalytic efficiency in MOF-enzyme systems.
publishDate 2025
dc.date.none.fl_str_mv 2025-10
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/11336/283119
Aguirre, Matías Ezequiel; Slaboch, María Victoria; González, Pablo Javier; Ramirez, Cristina Lujan; Di Iorio, Yesica Dolores; Visible‐Light‐Driven CO 2 Photoreduction Assisted by Reduced Methyl Viologen Using MIL‐125‐NH 2 as a Light Harvester and Scaffold for FDH Immobilization; Wiley VCH Verlag; Chemcatchem; 17; 23; 10-2025; 1-13
1867-3880
CONICET Digital
CONICET
url http://hdl.handle.net/11336/283119
identifier_str_mv Aguirre, Matías Ezequiel; Slaboch, María Victoria; González, Pablo Javier; Ramirez, Cristina Lujan; Di Iorio, Yesica Dolores; Visible‐Light‐Driven CO 2 Photoreduction Assisted by Reduced Methyl Viologen Using MIL‐125‐NH 2 as a Light Harvester and Scaffold for FDH Immobilization; Wiley VCH Verlag; Chemcatchem; 17; 23; 10-2025; 1-13
1867-3880
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://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cctc.202501120
info:eu-repo/semantics/altIdentifier/doi/10.1002/cctc.202501120
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Wiley VCH Verlag
publisher.none.fl_str_mv Wiley VCH Verlag
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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