Optical Metasurfaces for Energy Conversion.

Nanostructured surfaces with designed optical functionalities, such as metasurfaces, allow efficient harvesting of light at the nanoscale, enhancing light-matter interactions for a wide variety of material combinations. Exploiting light-driven matter excitations in these artificial materials opens up a new dimension in the conversion and management of energy at the nanoscale. In this review, we outline the impact, opportunities, applications, and challenges of optical metasurfaces in converting the energy of incoming photons into frequency-shifted photons, phonons, and energetic charge carriers. A myriad of opportunities await for the utilization of the converted energy. Here we cover the most pertinent aspects from a fundamental nanoscopic viewpoint all the way to applications.

Spatial Distributions of Single-Molecule Reactivity in Plasmonic Catalysis.

Plasmonic catalysts have the potential to accelerate and control chemical reactions with light by exploiting localized surface plasmon resonances. However, the mechanisms governing plasmonic catalysis are not simple to decouple. Several plasmon-derived phenomena, such as electromagnetic field enhancements, temperature, or the generation of charge carriers, can affect the reactivity of the system. These effects are convoluted with the inherent (nonplasmonic) catalytic properties of the metal surface. Disentangling these coexisting effects is challenging but is the key to rationally controlling reaction pathways and enhancing reaction rates. This study utilizes super-resolution fluorescence microscopy to examine the mechanisms of plasmonic catalysis at the single-particle level. The reduction reaction of resazurin to resorufin in the presence of Au nanorods coated with a porous silica shell is investigated in situ. This allows the determination of reaction rates with a single-molecule sensitivity and subparticle resolution. By variation of the irradiation wavelength, it is possible to examine two different regimes: photoexcitation of the reactant molecules and photoexcitation of the nanoparticle's plasmon resonance. In addition, the measured spatial distribution of reactivity allows differentiation between superficial and far-field effects. Our results indicate that the reduction of resazurin can occur through more than one reaction pathway, being most efficient when the reactant is photoexcited and is in contact with the Au surface. In addition, it was found that the spatial distribution of enhancements varies, depending on the underlying mechanism. These findings contribute to the fundamental understanding of plasmonic catalysis and the rational design of future plasmonic nanocatalysts.

Impact of bimetallic interface design on heat generation in plasmonic Au/Pd nanostructures studied by single-particle thermometry.

Localized surface plasmons are lossy and generate heat. However, accurate measurement of the temperature of metallic nanoparticles under illumination remains an open challenge, creating difficulties in the interpretation of results across plasmonic applications. Particularly, there is a quest for understanding the role of temperature in plasmon-assisted catalysis. Bimetallic nanoparticles combining plasmonic with catalytic metals are raising increasing interest in artificial photosynthesis and the production of solar fuels. Here, we perform single-particle thermometry measurements to investigate the link between morphology and light-to-heat conversion of colloidal Au/Pd nanoparticles with two different configurations: core-shell and core-satellite. It is observed that the inclusion of Pd as a shell strongly reduces the photothermal response in comparison to the bare cores, while the inclusion of Pd as satellites keeps photothermal properties almost unaffected. These results contribute to a better understanding of energy conversion processes in plasmon-assisted catalysis.

Hybrid Plasmonic Nanomaterials for Hydrogen Generation and Carbon Dioxide Reduction.

The successful development of artificial photosynthesis requires finding new materials able to efficiently harvest sunlight and catalyze hydrogen generation and carbon dioxide reduction reactions. Plasmonic nanoparticles are promising candidates for these tasks, due to their ability to confine solar energy into molecular regions. Here, we review recent developments in hybrid plasmonic photocatalysis, including the combination of plasmonic nanomaterials with catalytic metals, semiconductors, perovskites, 2D materials, metal-organic frameworks, and electrochemical cells. We perform a quantitative comparison of the demonstrated activity and selectivity of these materials for solar fuel generation in the liquid phase. In this way, we critically assess the state-of-the-art of hybrid plasmonic photocatalysts for solar fuel production, allowing its benchmarking against other existing heterogeneous catalysts. Our analysis allows the identification of the best performing plasmonic systems, useful to design a new generation of plasmonic catalysts.