Deciphering plasmonic photocatalysis using plasmon-enhanced Raman spectroscopy

Plasmonic photocatalysis, which represents a paradigm-shifting approach to solar-to-chemical energy conversion, has become a rapidly evolving research field full of opportunities, challenges, and open questions. Plasmon-driven photocatalytic reactions are mechanistically complex, dictated not only by multiple interplaying photophysical effects but also by local chemical environments at the catalyst-adsorbate interfaces. This review article highlights the unique value of plasmon-enhanced Raman spectroscopy in mechanistic studies of plasmonic photocatalysis. Using plasmon-driven reductive coupling of nitroarene derivative adsorbates as a model reaction system, this article elaborates on how the rich information extracted from deliberately designed plasmon-enhanced Raman spectroscopic measurements can be carefully analyzed and further rationalized to generate critical insights into the exact roles of hot carriers, photothermal transduction, and catalyst-adsorbate interactions in plasmonic photocatalysis.