The paradox of thermal vs. non-thermal effects in plasmonic photocatalysis.

The debate surrounding the roles of thermal and non-thermal pathways in plasmonic catalysis has captured the attention of researchers and sparked vibrant discussions within the scientific community. In this review, we embark on a thorough exploration of this intriguing discourse, starting from fundamental principles and culminating in a detailed understanding of the divergent viewpoints. We probe into the core of the debate by elucidating the behavior of excited charge carriers in illuminated plasmonic nanostructures, which serves as the foundation for the two opposing schools of thought. We present the key arguments and evidence put forth by proponents of both the non-thermal and thermal pathways, providing a perspective on their respective positions. Beyond the theoretical divide, we discussed the evolving methodologies used to unravel these mechanisms. We discuss the use of Arrhenius equations and their variations, shedding light on the ensuing debates about their applicability. Our review emphasizes the significance of localized surface plasmon resonance (LSPR), investigating its role in collective charge oscillations and the decay dynamics that influence catalytic processes. We also talked about the nuances of activation energy, exploring its relationship with the nonlinearity of temperature and light intensity dependence on reaction rates. Additionally, we address the intricacies of catalyst surface temperature measurements and their implications in understanding light-triggered reaction dynamics. The review further discusses wavelength-dependent reaction rates, kinetic isotope effects, and competitive electron transfer reactions, offering an all-inclusive view of the field. This review not only maps the current landscape of plasmonic photocatalysis but also facilitates future explorations and innovations to unlock the full potential of plasmon-mediated catalysis, where synergistic approaches could lead to different vistas in chemical transformations.