Decoding Chemical and Physical Processes Driving Plasmonic Photocatalysis Using Surface-Enhanced Raman Spectroscopies.

In order to mitigate the advancing effects of environmental pollution and climate change, immediate action is needed on social, political, and industrial fronts. One segment of industry that contributes significantly to this current crisis is bulk chemical production, where fossil fuels are primarily used to drive reactions at high temperatures and pressures. Toward mitigating the environmental impact of these processes, solar energy has shown promise as a clean and renewable alternative for the photocatalytic synthesis of chemicals. In recent decades, plasmonic materials have emerged as candidates for making this a reality. Because of their unique and tunable interactions with light, plasmonic materials can be used to create energy-rich nanoscale environments. In fact, there is a growing library of chemical reactions that can utilize this plasmonic energy to drive industrially relevant chemistries under standard ambient conditions. However, the efficiency of these reactions is typically low, and a lack of mechanistic understanding of how energy is transferred from plasmons to molecules hinders reaction optimization for use on large scales.To decode the complex chemical and physical processes involved in plasmon-driven photocatalytic reactions, we use surface-enhanced Raman spectroscopy (SERS). In this Account, we detail SERS techniques that we have used and are developing to study molecular transformations, charge transfer, and plasmonic heating in dynamic plasmon-molecule systems on time scales ranging from seconds to femtoseconds. SERS is an ideal analytical tool for understanding plasmon-molecule interactions, as it gives highly specific information about molecular vibrations with high sensitivity, down to the single-molecule level. Importantly, SERS allows for simultaneous pumping of a plasmonic resonance and probing of the enhanced Raman signal from nearby molecules. We have already used these techniques to study a plasmon-driven methyl migration with nanoscale spatial specificity and to understand the charge transfer mechanism and role of heating in the plasmon-mediated dimerization of 4-nitrobenzenethiol. Importantly, from this work we conclude that direct charge transfer, not heating, may play a significant role in driving many plasmon-driven reactions. Despite these recent insights, more work is needed in order to obtain a comprehensive understanding of the broad range of chemistries accessible in plasmon-molecule systems. In the future, our continued development of these SERS-based techniques shows promise in answering questions regarding direct charge transfer, resonance energy transfer, and excitation conditions in plasmon-mediated chemistries.