Hot-Carrier Organic Synthesis via the Near-Perfect Absorption of Light

Xiao, Q, Connell, T, Cadusch, J, Roberts, A, Chesman, A and Gomez, D 2018, 'Hot-Carrier Organic Synthesis via the Near-Perfect Absorption of Light', ACS Catalysis, vol. 8, no. 11, pp. 10331-10339.

Document type: Journal Article
Collection: Journal Articles

Title Hot-Carrier Organic Synthesis via the Near-Perfect Absorption of Light
Author(s) Xiao, Q
Connell, T
Cadusch, J
Roberts, A
Chesman, A
Gomez, D
Year 2018
Journal name ACS Catalysis
Volume number 8
Issue number 11
Start page 10331
End page 10339
Total pages 9
Publisher American Chemical Society
Abstract Photocatalysis enables the synthesis of valuable organic compounds by exploiting photons as a chemical reagent. Although light absorption is an intrinsic step, existing approaches rely on poorly absorbing catalysts that require high illumination intensities to afford enhanced efficiencies. Here, we demonstrate that a plasmonic metamaterial capable of near-perfect light absorption (94%) readily catalyzes a model organic reaction with a 29-fold enhancement in conversion relative to controls. The oxidation of benzylamine proceeds via a reactive iminium intermediate with high selectivity at ambient temperature and pressure, using only low-intensity visible irradiation. Control experiments demonstrated that only hot charge carriers produced following photoexcitation facilitate the formation of superoxide radicals, which, in turn, leads to iminium formation. Modeling shows that hot holes with energies that overlap with the highest-occupied molecular orbital (HOMO) of the reactant can participate and initiate the photocatalytic conversion. These results have important implications for hot-carrier photocatalysis and plasmon-hot-carrier extraction.
Subject Physical Chemistry of Materials
Nanofabrication, Growth and Self Assembly
Keyword(s) benzylamine oxidation
charge separation
hot carriers
near-perfect absorber
surface plasmons
DOI - identifier 10.1021/acscatal.8b03486
Copyright notice © 2018 American Chemical Society
ISSN 2155-5435
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