Distinguishing among All Possible Activation Mechanisms of a Plasmon-Driven Chemical Reaction

Rifat Kamarudheen, Guus J.W. Aalbers, Ruben F. Hamans, Leon P.J. Kamp, Andrea Baldi*

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

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Localized surface plasmon resonances (LSPRs) in metal nanoparticles can drive chemical reactions at their surface, but it is often challenging to disentangle the exact activation mechanism. The decay of LSPRs can lead to photothermal heating, electromagnetic hot spots, and the ejection of nonthermalized charge carriers, but all of these processes typically occur simultaneously and on ultrafast time scales. Here, we develop a plasmon-assisted Au@Ag core@shell nanorod synthesis in which each plasmon-decay mechanism can be independently assessed. Using different illumination wavelengths combined with extinction spectroscopy, transmission electron microscopy, thermal characterization, and finite-difference time-domain simulations, we unequivocally identify the transfer of interband holes to ascorbic acid as the rate-limiting step in the silver shell growth reaction. Our conclusion is corroborated by single-particle studies of gold nanospheres that display isotropic reactivity, consistent with interband hole-driven nanoparticle syntheses. Our strategy for distinguishing among plasmon-activation mechanisms can be extended to a variety of light-driven processes, including photocatalysis, nanoparticle syntheses, and drug delivery.

Original languageEnglish
Pages (from-to)2605-2613
Number of pages9
JournalACS Energy Letters
Issue number8
Early online date9 Jul 2020
Publication statusPublished - 14 Aug 2020


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