Toward a mechanistic understanding of plasmon-mediated photocatalysis

One of the most exciting new developments in the plasmonic nanomaterials field is the discovery of their ability to mediate a number of photocatalytic reactions. Since the initial prediction of driving chemical reactions with plasmons in the 1980s, the field has rapidly expanded in recent years, demonstrating the ability of plasmons to drive chemical reactions, such as water splitting, ammonia generation, and CO₂ reduction, among many other examples. Unfortunately, the efficiencies of these processes are currently suboptimal for practical widespread applications. The limitations in recorded outputs can be linked to the current lack of a knowledge pertaining to mechanisms of the partitioning of plasmonic energy after photoexcitation. Providing a descriptive and quantitative mechanism of the processes involved in driving plasmon-induced photochemical reactions, starting at the initial plasmon excitation, followed by hot carrier generation, energy transfer, and thermal effects, is critical for the advancement of the field as a whole. Here, we provide a mechanistic perspective on plasmonic photocatalysis by reviewing select experimental approaches. We focus on spectroscopic and electrochemical techniques that provide molecular-scale information on the processes that occur in the coupled molecular-plasmonic system after photoexcitation. To conclude, we evaluate several promising techniques for future applications in elucidating the mechanism of plasmon-mediated photocatalysis.