Quantifying the ultrafast and steady-state molecular reduction potential of a plasmonic photocatalyst.

Plasmonic materials are promising photocatalysts as they are well suited to convert light into hot carriers and heat. Hot electron transfer is suggested as the driving force in many plasmon-driven reactions. However, to date, there are no direct molecular measures of the rate and yield of plasmon-to-molecule electron transfer or energy of these electrons on the timescale of plasmon decay. Here, we use ultrafast and spectroelectrochemical surface-enhanced Raman spectroscopy to quantify electron transfer from a plasmonic substrate to adsorbed methyl viologen molecules. We observe a reduction yield of 2.4 to 3.5% on the picosecond timescale, with plasmon-induced potentials ranging from [Formula: see text]3.1 to [Formula: see text]4.5 mV. Excitingly, some of these reduced species are stabilized and persist for tens of minutes. This work provides concrete metrics toward optimizing material-molecule interactions for efficient plasmon-driven photocatalysis.

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.

Plasmon-Mediated Intramolecular Methyl Migration with Nanoscale Spatial Control.

Plasmonic materials interact strongly with light to focus and enhance electromagnetic radiation down to nanoscale volumes. Due to this localized confinement, materials that support localized surface plasmon resonances are capable of driving energetically unfavorable chemical reactions. In certain cases, the plasmonic nanostructures are able to preferentially catalyze the formation of specific photoproducts, which offers an opportunity for the development of solar-driven chemical synthesis. Here, using plasmonic environments, we report inducing an intramolecular methyl migration reaction, forming 4-methylpyridine from N-methylpyridinium. Using both experimental and computational methods, we were able to confirm the identity of the N-methylpyridinium by making spectral comparisons against possible photoproducts. This reaction involves breaking a C-N bond and forming a new C-C bond, highlighting the ability of plasmonic materials to drive complex and selective reactions. Additionally, we observe that the product yield depends strongly on optical illumination conditions. This is likely due to steric hindrance in specific regions on the nanostructured plasmonic substrate, providing an optical handle for driving plasmonic catalysis with spatial specificity. This work adds yet another class of reactions accessible by surface plasmon excitation to the ever-growing library of plasmon-mediated chemical reactions.

Plasmon-Enhanced Chemical Conversion Using Copper Selenide Nanoparticles.

The syntheses, properties, and broad utility of noble metal plasmonic nanomaterials are now well-established. To capitalize on this exceptional utility, mitigate its cost, and potentially expand it, non-noble metal plasmonic materials have become a topic of widespread interest. As new plasmonic materials come online, it is important to understand and assess their ability to generate comparable or complementary plasmonic properties to their noble metal counterparts, including as both sensing and photoredox materials. Here, we study plasmon-driven chemistry on degenerately doped copper selenide (Cu2- xSe) nanoparticles. In particular, we observe plasmon-driven dimerization of 4-nitrobenzenethiol to 4,4'-dimercaptoazobenzene on Cu2- xSe surfaces with yields comparable to those observed from noble metal nanoparticles. Overall, our results indicate that doped semiconductor nanoparticles are promising for light-driven chemistry technologies.