Thermal effects - an alternative mechanism for plasmonic-assisted photo-catalysis

Abstract

Recent experiments claimed that the enhancement of catalytic reaction rates occurs via the reduction of activation barriers driven by non-equilibrium (``hot'') electrons in plasmonic metal nanoparticles. These experiments place plasmonic photo-catalysis as a promising path for enhancing the efficiency of various chemical reactions. Here, we argue that what appears to be photo-catalysis is in fact 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 uniform external heating is effectively amplified by the exponential sensitivity of the reaction, and very likely to be interpreted incorrectly as ``hot'' electron effects.