In this study, we showed that nanocrystals of the degenerately doped plasmonic semiconductor Cu 2−x Se show enhancement factors comparable to those of noble metals and can drive the dimerization of 4-NBT to give DMAB with similar ef f iciencies.

Plasmonic materials are a promising category of photocatalysts for solar energy harvesting and conversion. However, there are some significant obstacles that need to be overcome to make plasmonic catalysts commercially available. One major challenge is to obtain a systematic understanding of how to design and optimize plasmonic systems from the perspective of both plasmonic materials and reagent molecules to achieve highly efficient and selective catalysis. It is wellknown that the contributions of plasmon−molecule interactions such as plasmon-induced resonant energy transfer and charge transfer to the catalytic mechanism are rather complicated and possibly multifold. Observation of these phenomena is challenging due to the highly heterogeneous nature of plasmonic substrates as well as the large difference in sizes and optical cross sections between plasmonic materials and molecules. In this work, we use a molecular perspective to examine the crucial process of energy transfer between plasmons and molecules, with the goal of determining which experimental parameters can be used to control this energy flow. We employ ultrafast surface-enhanced anti-Stokes and Stokes Raman spectroscopy to investigate vibrational energy transfer in plasmonic−molecule systems. By comparing the energy transfer kinetics of five different aromatic thiols on the picosecond time scale, we find that intermolecular forces play an important role in energy distribution in molecules adsorbed to plasmonic materials, which changes the amount of energy deposited onto the molecule and the lifetime of the energy deposited. Our work implies that careful consideration of catalyst loading and molecule adsorption geometry is crucial for enhancing or suppressing the rate and efficiency of plasmon-driven energy transfer.

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The optical excitation of surface plasmons leads to the generation of highly enhanced nanoscale local fields and an abundance of harvestable hot carriers. When certain analytes are positioned within these unique environments, surface plasmons may be able to induce chemical reactions that are energetically unfavorable under standard conditions. Sometimes, the plasmonic environments can initiate entirely new reaction pathways for the chemical adsorbates. Here, we investigate the nature of plasmon-driven reactions on three viologen derivatives: methyl viologen, ethyl viologen, and benzyl viologen. Viologens have traditionally been employed as excellent redox agents due to their ability to reversibly stabilize additional electrons in their molecular structures. However, by using surface-enhanced Raman spectroscopy, we were able to directly observe a C–N bond cleavage on benzyl and ethyl viologen to form 4,4′-bipyridine on the surface of gold film-over-nanosphere substrates. Surprisingly, methyl viologen does not undergo a similar process. We posit that this differing reactivity may be due to changes in adsorption geometry or in reduction potential. Using both spectroscopic and theoretical methods, we were able to confirm 4,4′-bipyridine as the plasmon-mediated photoproduct. This work highlights the novelty of using plasmonic environments to access new chemical reactions and adds to the expanding library of plasmon-mediated chemical reactions.

The optical and chemical properties of plasmonic materials have sparked extensive research in exploring their applications in various areas such as photocatalysts, chemical sensors, and photonic devices. However, complicated plasmonmolecule interactions have posed substantial obstacles for the development of plasmonic material-based technologies. Quantifying plasmon-molecule energy transfer processes is a crucial step to understand the complex interplay between plasmonic materials and molecules. Here we report an anomalous steadystate reduction in the anti-Stokes to Stokes surface-enhanced Raman spectroscopy (SERS) scattering intensity ratio of aromatic thiols adsorbed on plasmonic gold nanoparticles under continuous-wave laser irradiation. The observed reduction of the scattering intensity ratio is closely related to the excitation wavelength, the surrounding media, and component of the plasmonic substrates used. Moreover, we observed a similar extent of scattering intensity ratio reduction with a range of aromatic thiols and under different external temperatures. Our discovery implies that there are either unexplained wavelengthdependent SERS outcoupling effects, or some unrecognized plasmon-molecule interactions which lead to a nanoscale plasmon refrigerator for molecules. This effect should be taken into consideration for the design of plasmonic catalysts and plasmonic photonic devices. Moreover, it could be useful for cooling large molecules under ambient conditions.