Journal
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
Volume 118, Issue 20, Pages -Publisher
NATL ACAD SCIENCES
DOI: 10.1073/pnas.2022109118
Keywords
photocatalysis; plasmon; carrier multiplication; hot electrons; photochemistry
Categories
Funding
- Robert A. Welch Foundation [C-1220, C-1222]
- Air Force Office of Scientific Research (AFOSR) via the Department of Defense Multidisciplinary University Research Initiative under AFOSR Award [FA9550-15-1-0022]
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This study demonstrates that the H2-D2 exchange reaction catalyzed by Cu nanoparticles is primarily driven by thermalized hot carriers, with an intriguing intensity-dependent external quantum yield exceeding 100% at high light intensities. Quantum mechanical research suggests that vibrational excitations of the surface Cu-H bond are the likely activation mechanism, supporting the effectiveness of low-energy thermalized hot carriers in photocatalyzing this reaction.
Light-induced hot carriers derived from the surface plasmons of metal nanostructures have been shown to be highly promising agents for photocatalysis. While both nonthermal and thermalized hot carriers can potentially contribute to this process, their specific role in any given chemical reaction has generally not been identified. Here, we report the observation that the H2-D2 exchange reaction photocatalyzed by Cu nanoparticles is driven primarily by thermalized hot carriers. The external quantum yield shows an intriguing S-shaped intensity dependence and exceeds 100% for high light intensities, suggesting that hot carrier multiplication plays a role. A simplified model for the quantum yield of thermalized hot carriers reproduces the observed kinetic features of the reaction, validating our hypothesis of a thermalized hot carrier mechanism. A quantum mechanical study reveals that vibrational excitations of the surface Cu-H bond is the likely activation mechanism, further supporting the effectiveness of low-energy thermalized hot carriers in photocatalyzing this reaction.
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