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Role of Valence Band States and Plasmonic Enhancement in Electron-Transfer-Induced Transformation of Nitrothiophenol

[Image: see text] Hot-electron-induced reactions are more and more recognized as a critical and ubiquitous reaction in heterogeneous catalysis. However, the kinetics of these reactions is still poorly understood, which is also due to the complexity of plasmonic nanostructures. We determined the reac...

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Autores principales: Schürmann, Robin, Ebel, Kenny, Nicolas, Christophe, Milosavljević, Aleksandar R., Bald, Ilko
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2019
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6569622/
https://www.ncbi.nlm.nih.gov/pubmed/31117676
http://dx.doi.org/10.1021/acs.jpclett.9b00848
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author Schürmann, Robin
Ebel, Kenny
Nicolas, Christophe
Milosavljević, Aleksandar R.
Bald, Ilko
author_facet Schürmann, Robin
Ebel, Kenny
Nicolas, Christophe
Milosavljević, Aleksandar R.
Bald, Ilko
author_sort Schürmann, Robin
collection PubMed
description [Image: see text] Hot-electron-induced reactions are more and more recognized as a critical and ubiquitous reaction in heterogeneous catalysis. However, the kinetics of these reactions is still poorly understood, which is also due to the complexity of plasmonic nanostructures. We determined the reaction rates of the hot-electron-mediated reaction of 4-nitrothiophenol (NTP) on gold nanoparticles (AuNPs) using fractal kinetics as a function of the laser wavelength and compared them with the plasmonic enhancement of the system. The reaction rates can be only partially explained by the plasmonic response of the NPs. Hence, synchrotron X-ray photoelectron spectroscopy (XPS) measurements of isolated NTP-capped AuNP clusters have been performed for the first time. In this way, it was possible to determine the work function and the accessible valence band states of the NP systems. The results show that besides the plasmonic enhancement, the reaction rates are strongly influenced by the local density of the available electronic states of the system.
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spelling pubmed-65696222019-06-20 Role of Valence Band States and Plasmonic Enhancement in Electron-Transfer-Induced Transformation of Nitrothiophenol Schürmann, Robin Ebel, Kenny Nicolas, Christophe Milosavljević, Aleksandar R. Bald, Ilko J Phys Chem Lett [Image: see text] Hot-electron-induced reactions are more and more recognized as a critical and ubiquitous reaction in heterogeneous catalysis. However, the kinetics of these reactions is still poorly understood, which is also due to the complexity of plasmonic nanostructures. We determined the reaction rates of the hot-electron-mediated reaction of 4-nitrothiophenol (NTP) on gold nanoparticles (AuNPs) using fractal kinetics as a function of the laser wavelength and compared them with the plasmonic enhancement of the system. The reaction rates can be only partially explained by the plasmonic response of the NPs. Hence, synchrotron X-ray photoelectron spectroscopy (XPS) measurements of isolated NTP-capped AuNP clusters have been performed for the first time. In this way, it was possible to determine the work function and the accessible valence band states of the NP systems. The results show that besides the plasmonic enhancement, the reaction rates are strongly influenced by the local density of the available electronic states of the system. American Chemical Society 2019-05-22 2019-06-06 /pmc/articles/PMC6569622/ /pubmed/31117676 http://dx.doi.org/10.1021/acs.jpclett.9b00848 Text en Copyright © 2019 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle Schürmann, Robin
Ebel, Kenny
Nicolas, Christophe
Milosavljević, Aleksandar R.
Bald, Ilko
Role of Valence Band States and Plasmonic Enhancement in Electron-Transfer-Induced Transformation of Nitrothiophenol
title Role of Valence Band States and Plasmonic Enhancement in Electron-Transfer-Induced Transformation of Nitrothiophenol
title_full Role of Valence Band States and Plasmonic Enhancement in Electron-Transfer-Induced Transformation of Nitrothiophenol
title_fullStr Role of Valence Band States and Plasmonic Enhancement in Electron-Transfer-Induced Transformation of Nitrothiophenol
title_full_unstemmed Role of Valence Band States and Plasmonic Enhancement in Electron-Transfer-Induced Transformation of Nitrothiophenol
title_short Role of Valence Band States and Plasmonic Enhancement in Electron-Transfer-Induced Transformation of Nitrothiophenol
title_sort role of valence band states and plasmonic enhancement in electron-transfer-induced transformation of nitrothiophenol
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6569622/
https://www.ncbi.nlm.nih.gov/pubmed/31117676
http://dx.doi.org/10.1021/acs.jpclett.9b00848
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