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Title: Evidence and implications of direct charge excitation as the dominant mechanism in plasmon-mediated photocatalysis

Abstract

Plasmonic metal nanoparticles enhance chemical reactions on their surface when illuminated with light of particular frequencies. It has been shown that these processes are driven by excitation of localized surface plasmon resonance (LSPR). The interaction of LSPR with adsorbate orbitals can lead to the injection of energized charge carriers into the adsorbate, which can result in chemical transformations. The mechanism of the charge injection process (and role of LSPR) is not well understood. Here we shed light on the specifics of this mechanism by coupling optical characterization methods, mainly wavelength-dependent Stokes and anti-Stokes SERS, with kinetic analysis of photocatalytic reactions in an Ag nanocube–methylene blue plasmonic system. We propose that localized LSPR-induced electric fields result in a direct charge transfer within the molecule–adsorbate system. Lastly, these observations provide a foundation for the development of plasmonic catalysts that can selectively activate targeted chemical bonds, since the mechanism allows for tuning plasmonic nanomaterials in such a way that illumination can selectively enhance desired chemical pathways.

Authors:
 [1];  [1];  [1];  [1]
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  1. Univ. of Michigan, Ann Arbor, MI (United States)
Publication Date:
Research Org.:
Univ. of Michigan, Ann Arbor, MI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1242978
Grant/Contract Number:  
FG02-05ER15686
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 7; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY; chemical sciences; catalysis; physical chemistry

Citation Formats

Boerigter, Calvin, Campana, Robert, Morabito, Matthew, and Linic, Suljo. Evidence and implications of direct charge excitation as the dominant mechanism in plasmon-mediated photocatalysis. United States: N. p., 2016. Web. doi:10.1038/ncomms10545.
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Boerigter, Calvin, Campana, Robert, Morabito, Matthew, & Linic, Suljo. Evidence and implications of direct charge excitation as the dominant mechanism in plasmon-mediated photocatalysis. United States. doi:10.1038/ncomms10545.
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Boerigter, Calvin, Campana, Robert, Morabito, Matthew, and Linic, Suljo. Thu . "Evidence and implications of direct charge excitation as the dominant mechanism in plasmon-mediated photocatalysis". United States. doi:10.1038/ncomms10545. https://www.osti.gov/servlets/purl/1242978.
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@article{osti_1242978,
title = {Evidence and implications of direct charge excitation as the dominant mechanism in plasmon-mediated photocatalysis},
author = {Boerigter, Calvin and Campana, Robert and Morabito, Matthew and Linic, Suljo},
abstractNote = {Plasmonic metal nanoparticles enhance chemical reactions on their surface when illuminated with light of particular frequencies. It has been shown that these processes are driven by excitation of localized surface plasmon resonance (LSPR). The interaction of LSPR with adsorbate orbitals can lead to the injection of energized charge carriers into the adsorbate, which can result in chemical transformations. The mechanism of the charge injection process (and role of LSPR) is not well understood. Here we shed light on the specifics of this mechanism by coupling optical characterization methods, mainly wavelength-dependent Stokes and anti-Stokes SERS, with kinetic analysis of photocatalytic reactions in an Ag nanocube–methylene blue plasmonic system. We propose that localized LSPR-induced electric fields result in a direct charge transfer within the molecule–adsorbate system. Lastly, these observations provide a foundation for the development of plasmonic catalysts that can selectively activate targeted chemical bonds, since the mechanism allows for tuning plasmonic nanomaterials in such a way that illumination can selectively enhance desired chemical pathways.},
doi = {10.1038/ncomms10545},
journal = {Nature Communications},
number = ,
volume = 7,
place = {United States},
year = {2016},
month = {1}
}
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DOI:  10.1038/ncomms10545
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    Works referencing / citing this record:

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