The role of heat generation and fluid flow in plasmon-enhanced reduction-oxidation reactions

TL;DR

This paper investigates how heat generation and fluid flow influence plasmon-enhanced redox reactions, extending previous thermal effect studies to include charge transfer, temporal temperature dynamics, and fluid convection, with mixed results on experimental data explanation.

Contribution

It introduces a comprehensive analysis of thermal effects in redox reactions, including spatial and temporal temperature dynamics and fluid flow modeling, advancing understanding of plasmon-enhanced processes.

Findings

Thermal effects can explain some experimental data on redox reactions.

Charge transfer in redox reactions is not always thermally driven.

Fluid convection impacts temperature distribution and reaction rates.

Abstract

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 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 experiments (Baumberg and coworkers), but not in the other (Jain and coworkers), showing that redox reactions are not necessarily driven by non-thermal charge carriers.