Uncovering the complex mechanisms behind nanomaterials-based plasmon-driven photocatalysis through the utilization of Surface-Enhanced Raman Spectroscopies

TL;DR

This paper uses ultrafast Surface-Enhanced Raman Spectroscopy to elucidate the mechanisms of plasmon-driven photocatalysis, revealing charge transfer processes and the potential of non-noble metal nanoparticles for sustainable chemical reactions.

Contribution

It demonstrates the application of ultrafast SERS to uncover charge transfer mechanisms and explores alternative plasmonic materials beyond noble metals in photocatalysis.

Findings

Charge transfer is the primary mechanism in the photocatalytic reaction.

Nanoparticles other than noble metals can effectively drive dimerization reactions.

Plasmonic heating alone is insufficient for photocatalytic conversions.

Abstract

Plasmonic materials have got wide attention as a potential candidate for light driven catalysis of chemical conversions by harnessing solar energy to reduce the environmental issues generated by fossil fuels-based bulk chemical industries. Toward diluting this crisis, many reported the utilization of plasmonic nanostructured materials in driving industrially important reactions at normal temperature and pressure. However, these chemical conversions often suffer from low yield difficulties, and poor efficiency problems. Also, the mechanism of energy transfer from plasmon to desired molecules is still not properly understood which retards the efforts of scaling them up. Recent endeavors of using SERS to explore the complex mechanisms associated with plasmonic photocatalysis have shown great promises because of the higher sensitivity of the technique. In this article, our aim is to analyze the role of ultrafast SERS in revealing charge transfer as the primary mechanism of photocatalytic reaction of 4-nitrothiophenol to azobenzene-4,4-dithiol and how nanoparticles other than noble metals can also drive this dimerization reaction with similar potential of noble metals. We also intend to investigate why plasmonic heating occurring at metal surface is inadequate to run photocatalytic conversions. A series of analysis has been done in these works using SERS to gather data and understand the mechanisms involved in the processes by pumping plasmonic resonance simultaneously and investigating signals from molecules at various time delays. These results open the door for researchers to consider SERS as a promising technique to uncover the physical and chemical processes involved in plasmon-driven photocatalysis and to advance toward environment friendly and cost-efficient photochemical conversions in future.