Hot carrier multiplication in plasmonic photocatalysis

Linan Zhou, Minhan Lou, Junwei Lucas Bao, Chao Zhang, Jun G. Liu, John Mark P. Martirez, Shu Tian, Lin Yuan, Dayne F. Swearer, Hossein Robatjazi, Emily A. Carter, Peter Nordlander, Naomi J. Halas

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

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.

Original languageEnglish (US)
Article numbere2022109118
JournalProceedings of the National Academy of Sciences of the United States of America
Volume118
Issue number20
DOIs
StatePublished - May 18 2021

All Science Journal Classification (ASJC) codes

  • General

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