The Role of Heat Generation and Fluid Flow in Plasmon-Enhanced Reduction-Oxidation Reactions

Recently, we have shown that thermal effects play a crucial role in speeding up the rate of bond-dissociation reactions. This was done by applying a simple temperature-shifted Arrhenius law to the experimental data, corroborated with a detailed account of the heat diffusion occurring within the relevant samples and identification of errors in the temperature measurements. Here, we provide three important extensions of our previous studies. First, we analyze thermal effects in reduction-oxidation (redox) reactions, where charge transfer is an integral part of the reaction. Second, we analyze not only the spatial distribution of the temperature but also its temporal dynamics. Third, we also model the fluid convection and stirring. An analysis of two exemplary experimental studies allows us to show that thermal effects can explain the experimental data in one of the experiments (Baumberg and co-workers) but not in the other (Jain and co-workers), showing that redox reactions are not necessarily driven by nonthermal charge carriers.