Thermal effects - an alternative mechanism for plasmon-assisted photocatalysis

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128 Scopus citations

Abstract

Recent experiments claimed that the catalysis of reaction rates in numerous bond-dissociation reactions occursviathe decrease of activation barriers driven by non-equilibrium (“hot”) electrons in illuminated plasmonic metal nanoparticles. Thus, these experiments identify plasmon-assisted photocatalysis as a promising path for enhancing the efficiency of various chemical reactions. Here, we argue that what appears to be photocatalysis is much more likely thermo-catalysis, driven by the well-known plasmon-enhanced ability of illuminated metallic nanoparticles to serve as heat sources. Specifically, we point to some of the most important papers in the field, and show that a simple theory of illumination-induced heating can explain the extracted experimental data to remarkable agreement, with minimal to no fit parameters. We further show that any small temperature difference between the photocatalysis experiment and a control experiment performed under external heating is effectively amplified by the exponential sensitivity of the reaction, and is very likely to be interpreted incorrectly as “hot” electron effects.

Original languageEnglish
Pages (from-to)5017-5027
Number of pages11
JournalChemical Science
Volume11
Issue number19
DOIs
StatePublished - 21 May 2020

ASJC Scopus subject areas

  • General Chemistry

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