Spatial Distributions of Single-Molecule Reactivity in Plasmonic Catalysis

Autores
Ezendam, Simone; Gargiulo, Julian; Sousa Castillo, Ana; Lee, Joong Bum; Nam, Yoon Sung; Maier, Stefan A.; Cortés, Emiliano
Año de publicación
2024
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Plasmonic catalysts have the potential to accelerate and control chemical reactions with light by exploiting localized surface plasmon resonances. However, the mechanisms governing plasmonic catalysis are not simple to decouple. Several plasmon-derived phenomena, such as electromagnetic field enhancements, temperature, or the generation of charge carriers, can affect the reactivity of the system. These effects are convoluted with the inherent (nonplasmonic) catalytic properties of the metal surface. Disentangling these coexisting effects is challenging but is the key to rationally controlling reaction pathways and enhancing reaction rates. This study utilizes super-resolution fluorescence microscopy to examine the mechanisms of plasmonic catalysis at the single-particle level. The reduction reaction of resazurin to resorufin in the presence of Au nanorods coated with a porous silica shell is investigated in situ. This allows the determination of reaction rates with a single-molecule sensitivity and subparticle resolution. By variation of the irradiation wavelength, it is possible to examine two different regimes: photoexcitation of the reactant molecules and photoexcitation of the nanoparticle’s plasmon resonance. In addition, the measured spatial distribution of reactivity allows differentiation between superficial and far-field effects. Our results indicate that the reduction of resazurin can occur through more than one reaction pathway, being most efficient when the reactant is photoexcited and is in contact with the Au surface. In addition, it was found that the spatial distribution of enhancements varies, depending on the underlying mechanism. These findings contribute to the fundamental understanding of plasmonic catalysis and the rational design of future plasmonic nanocatalysts.
Fil: Ezendam, Simone. Ludwig Maximilians Universitat; Alemania
Fil: Gargiulo, Julian. Ludwig Maximilians Universitat; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Sousa Castillo, Ana. Ludwig Maximilians Universitat; Alemania
Fil: Lee, Joong Bum. Korea Advanced Institute Of Science And Technology; República Checa
Fil: Nam, Yoon Sung. Korea Advanced Institute Of Science And Technology; República Checa
Fil: Maier, Stefan A.. Ludwig Maximilians Universitat; Alemania. Imperial College London; Reino Unido. Monash University; Australia
Fil: Cortés, Emiliano. Ludwig Maximilians Universitat; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Materia
HOT CARRIERS
PLASMONIC CATALYSIS
SINGLE-MOLECULE CATALYSIS
SINGLE-PARTICLE CATALYSIS
SUPER-RESOLUTION MICROSCOPY
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:11336/230653
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/230653
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Spatial Distributions of Single-Molecule Reactivity in Plasmonic CatalysisEzendam, SimoneGargiulo, JulianSousa Castillo, AnaLee, Joong BumNam, Yoon SungMaier, Stefan A.Cortés, EmilianoHOT CARRIERSPLASMONIC CATALYSISSINGLE-MOLECULE CATALYSISSINGLE-PARTICLE CATALYSISSUPER-RESOLUTION MICROSCOPYhttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1https://purl.org/becyt/ford/2.10https://purl.org/becyt/ford/2https://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Plasmonic catalysts have the potential to accelerate and control chemical reactions with light by exploiting localized surface plasmon resonances. However, the mechanisms governing plasmonic catalysis are not simple to decouple. Several plasmon-derived phenomena, such as electromagnetic field enhancements, temperature, or the generation of charge carriers, can affect the reactivity of the system. These effects are convoluted with the inherent (nonplasmonic) catalytic properties of the metal surface. Disentangling these coexisting effects is challenging but is the key to rationally controlling reaction pathways and enhancing reaction rates. This study utilizes super-resolution fluorescence microscopy to examine the mechanisms of plasmonic catalysis at the single-particle level. The reduction reaction of resazurin to resorufin in the presence of Au nanorods coated with a porous silica shell is investigated in situ. This allows the determination of reaction rates with a single-molecule sensitivity and subparticle resolution. By variation of the irradiation wavelength, it is possible to examine two different regimes: photoexcitation of the reactant molecules and photoexcitation of the nanoparticle’s plasmon resonance. In addition, the measured spatial distribution of reactivity allows differentiation between superficial and far-field effects. Our results indicate that the reduction of resazurin can occur through more than one reaction pathway, being most efficient when the reactant is photoexcited and is in contact with the Au surface. In addition, it was found that the spatial distribution of enhancements varies, depending on the underlying mechanism. These findings contribute to the fundamental understanding of plasmonic catalysis and the rational design of future plasmonic nanocatalysts.Fil: Ezendam, Simone. Ludwig Maximilians Universitat; AlemaniaFil: Gargiulo, Julian. Ludwig Maximilians Universitat; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Sousa Castillo, Ana. Ludwig Maximilians Universitat; AlemaniaFil: Lee, Joong Bum. Korea Advanced Institute Of Science And Technology; República ChecaFil: Nam, Yoon Sung. Korea Advanced Institute Of Science And Technology; República ChecaFil: Maier, Stefan A.. Ludwig Maximilians Universitat; Alemania. Imperial College London; Reino Unido. Monash University; AustraliaFil: Cortés, Emiliano. Ludwig Maximilians Universitat; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaAmerican Chemical Society2024-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/230653Ezendam, Simone; Gargiulo, Julian; Sousa Castillo, Ana; Lee, Joong Bum; Nam, Yoon Sung; et al.; Spatial Distributions of Single-Molecule Reactivity in Plasmonic Catalysis; American Chemical Society; ACS Nano; 18; 1; 1-2024; 451-4601936-08511936-086XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/acsnano.3c07833info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:01:43Zoai:ri.conicet.gov.ar:11336/230653instacron: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:34982025-09-10 13:01:44.004CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Spatial Distributions of Single-Molecule Reactivity in Plasmonic Catalysis
title Spatial Distributions of Single-Molecule Reactivity in Plasmonic Catalysis
spellingShingle Spatial Distributions of Single-Molecule Reactivity in Plasmonic Catalysis
Ezendam, Simone
HOT CARRIERS
PLASMONIC CATALYSIS
SINGLE-MOLECULE CATALYSIS
SINGLE-PARTICLE CATALYSIS
SUPER-RESOLUTION MICROSCOPY
title_short Spatial Distributions of Single-Molecule Reactivity in Plasmonic Catalysis
title_full Spatial Distributions of Single-Molecule Reactivity in Plasmonic Catalysis
title_fullStr Spatial Distributions of Single-Molecule Reactivity in Plasmonic Catalysis
title_full_unstemmed Spatial Distributions of Single-Molecule Reactivity in Plasmonic Catalysis
title_sort Spatial Distributions of Single-Molecule Reactivity in Plasmonic Catalysis
dc.creator.none.fl_str_mv Ezendam, Simone
Gargiulo, Julian
Sousa Castillo, Ana
Lee, Joong Bum
Nam, Yoon Sung
Maier, Stefan A.
Cortés, Emiliano
author Ezendam, Simone
author_facet Ezendam, Simone
Gargiulo, Julian
Sousa Castillo, Ana
Lee, Joong Bum
Nam, Yoon Sung
Maier, Stefan A.
Cortés, Emiliano
author_role author
author2 Gargiulo, Julian
Sousa Castillo, Ana
Lee, Joong Bum
Nam, Yoon Sung
Maier, Stefan A.
Cortés, Emiliano
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv HOT CARRIERS
PLASMONIC CATALYSIS
SINGLE-MOLECULE CATALYSIS
SINGLE-PARTICLE CATALYSIS
SUPER-RESOLUTION MICROSCOPY
topic HOT CARRIERS
PLASMONIC CATALYSIS
SINGLE-MOLECULE CATALYSIS
SINGLE-PARTICLE CATALYSIS
SUPER-RESOLUTION MICROSCOPY
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
https://purl.org/becyt/ford/2.10
https://purl.org/becyt/ford/2
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Plasmonic catalysts have the potential to accelerate and control chemical reactions with light by exploiting localized surface plasmon resonances. However, the mechanisms governing plasmonic catalysis are not simple to decouple. Several plasmon-derived phenomena, such as electromagnetic field enhancements, temperature, or the generation of charge carriers, can affect the reactivity of the system. These effects are convoluted with the inherent (nonplasmonic) catalytic properties of the metal surface. Disentangling these coexisting effects is challenging but is the key to rationally controlling reaction pathways and enhancing reaction rates. This study utilizes super-resolution fluorescence microscopy to examine the mechanisms of plasmonic catalysis at the single-particle level. The reduction reaction of resazurin to resorufin in the presence of Au nanorods coated with a porous silica shell is investigated in situ. This allows the determination of reaction rates with a single-molecule sensitivity and subparticle resolution. By variation of the irradiation wavelength, it is possible to examine two different regimes: photoexcitation of the reactant molecules and photoexcitation of the nanoparticle’s plasmon resonance. In addition, the measured spatial distribution of reactivity allows differentiation between superficial and far-field effects. Our results indicate that the reduction of resazurin can occur through more than one reaction pathway, being most efficient when the reactant is photoexcited and is in contact with the Au surface. In addition, it was found that the spatial distribution of enhancements varies, depending on the underlying mechanism. These findings contribute to the fundamental understanding of plasmonic catalysis and the rational design of future plasmonic nanocatalysts.
Fil: Ezendam, Simone. Ludwig Maximilians Universitat; Alemania
Fil: Gargiulo, Julian. Ludwig Maximilians Universitat; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Sousa Castillo, Ana. Ludwig Maximilians Universitat; Alemania
Fil: Lee, Joong Bum. Korea Advanced Institute Of Science And Technology; República Checa
Fil: Nam, Yoon Sung. Korea Advanced Institute Of Science And Technology; República Checa
Fil: Maier, Stefan A.. Ludwig Maximilians Universitat; Alemania. Imperial College London; Reino Unido. Monash University; Australia
Fil: Cortés, Emiliano. Ludwig Maximilians Universitat; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
description Plasmonic catalysts have the potential to accelerate and control chemical reactions with light by exploiting localized surface plasmon resonances. However, the mechanisms governing plasmonic catalysis are not simple to decouple. Several plasmon-derived phenomena, such as electromagnetic field enhancements, temperature, or the generation of charge carriers, can affect the reactivity of the system. These effects are convoluted with the inherent (nonplasmonic) catalytic properties of the metal surface. Disentangling these coexisting effects is challenging but is the key to rationally controlling reaction pathways and enhancing reaction rates. This study utilizes super-resolution fluorescence microscopy to examine the mechanisms of plasmonic catalysis at the single-particle level. The reduction reaction of resazurin to resorufin in the presence of Au nanorods coated with a porous silica shell is investigated in situ. This allows the determination of reaction rates with a single-molecule sensitivity and subparticle resolution. By variation of the irradiation wavelength, it is possible to examine two different regimes: photoexcitation of the reactant molecules and photoexcitation of the nanoparticle’s plasmon resonance. In addition, the measured spatial distribution of reactivity allows differentiation between superficial and far-field effects. Our results indicate that the reduction of resazurin can occur through more than one reaction pathway, being most efficient when the reactant is photoexcited and is in contact with the Au surface. In addition, it was found that the spatial distribution of enhancements varies, depending on the underlying mechanism. These findings contribute to the fundamental understanding of plasmonic catalysis and the rational design of future plasmonic nanocatalysts.
publishDate 2024
dc.date.none.fl_str_mv 2024-01
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/11336/230653
Ezendam, Simone; Gargiulo, Julian; Sousa Castillo, Ana; Lee, Joong Bum; Nam, Yoon Sung; et al.; Spatial Distributions of Single-Molecule Reactivity in Plasmonic Catalysis; American Chemical Society; ACS Nano; 18; 1; 1-2024; 451-460
1936-0851
1936-086X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/230653
identifier_str_mv Ezendam, Simone; Gargiulo, Julian; Sousa Castillo, Ana; Lee, Joong Bum; Nam, Yoon Sung; et al.; Spatial Distributions of Single-Molecule Reactivity in Plasmonic Catalysis; American Chemical Society; ACS Nano; 18; 1; 1-2024; 451-460
1936-0851
1936-086X
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/acsnano.3c07833
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
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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_ 1842979968418578432
score 12.993085

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