Thermal effects - an alternative mechanism for plasmon-assisted photocatalysis.

Chemical Science
Yonatan DubiYonatan Sivan

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.

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Citations

Jun 23, 2021·ACS Nano·Christopher TiburskiChristoph Langhammer
Aug 19, 2020·Nature Materials·Guillaume BaffouRomain Quidant
Feb 9, 2021·Journal of the American Society for Mass Spectrometry·Kwan-Ming NgJun Yang
Jun 29, 2021·Light, Science & Applications·Guillaume BaffouRomain Quidant
Apr 7, 2021·ACS Nano·Guillaume Baffou
Apr 28, 2021·ACS Nano·Yonatan Sivan, Yonatan Dubi
Apr 29, 2021·Accounts of Chemical Research·Zhandong Li, Dmitry Kurouski
May 13, 2021·Advanced Materials·Yuchao ZhangWei David Wei
Aug 14, 2020·The Journal of Physical Chemistry. a·Thomas JollansMichel Orrit
Dec 15, 2020·ACS Nano·Emiliano CortésPrineha Narang
Oct 6, 2021·Nature Nanotechnology·Eitan OksenbergErik C Garnett

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