Hot or Not? Reassessing Mechanisms of Photocurrent Generation in Plasmon-Enhanced Electrocatalysis

It is now widely accepted that certain effects arising from localised surface plasmon resonance, such as enhanced electromagnetic fields, hot carriers, and thermal effects, can facilitate electrocatalytic processes. This newly emerging field of research is commonly referred to as plasmon-enhanced electrocatalysis (PEEC) and is attracting increasing interest from the research community, particularly regarding harnessing the high energy of hot carriers. However, this has led to a lack of critical analysis in the literature, where the participation of hot carriers is routinely claimed due to their perceived desirability, while the contribution of other effects is often not sufficiently investigated. As a result, correctly differentiating between the possible mechanisms at play has become a key point of contention. In this review, we specifically focus on the mechanisms behind photocurrents observed in PEEC and critically evaluate the possibility of alternative sources of current enhancement in the reported PEEC systems. Furthermore, we present guidelines for the best experimental practices and methods to distinguish between the various enhancement mechanisms in PEEC.