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Thermal effects – an alternative mechanism for plasmon-assisted photocatalysis

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Recent experiments claimed that the catalysis of reaction rates in numerous bond-dissociation reactions occurs via the decrease of activation barriers driven by non-equilibrium (“hot”) electrons in illuminated plasmonic metal nanoparticles.… Click to show full abstract

Recent experiments claimed that the catalysis of reaction rates in numerous bond-dissociation reactions occurs via the 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.

Keywords: effects alternative; assisted photocatalysis; thermal effects; plasmon assisted; photocatalysis

Journal Title: Chemical Science
Year Published: 2020

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