Abstract
Abstract Illumination of noble metal nanostructures by electromagnetic radiation induces coherent oscillations of conductive electrons on their surfaces. These coherent oscillations of electrons, also known as localized surface plasmon resonances (LSPR), are the underlying physical cause of the electromagnetic enhancement of Raman scattering from analytes located in a close proximity to the metal surface. This physical phenomenon is broadly known as surface-enhanced Raman scattering (SERS). LSPR can decay via direct interband, phonon-assisted intraband, and geometry-assisted transitions forming hot carriers, highly energetic species that are responsible for a large variety of chemical transformations. This review critically discusses the most recent progress in mechanistic elucidation of hot carrier-driven chemistry and catalytic processes at the nanoscale. The review provides a brief description of tip-enhanced Raman spectroscopy (TERS), modern analytical technique that possesses single-molecule sensitivity and angstrom spatial resolution, showing the advantage of this technique for spatiotemporal characterization of plasmon-driven reactions. The review also discusses experimental and theoretical findings that reported novel plasmon-driven reactivity which can be used to catalyze redox, coupling, elimination and scissoring reactions. Lastly, the review discusses the impact of the most recently reported findings on both plasmonic catalysis and TERS imaging.
Highlights
Noble metal nanostructures absorb light in the visible and infrared (IR) parts of electromagnetic spectrum
localized surface plasmon resonances (LSPR) can decay via direct interband, phonon-assisted intraband, and geometry-assisted transitions forming hot carriers, highly energetic species that are responsible for a large variety of chemical transformations
Our group discovered that the edges of Au nanoplates (AuNPs) exhibited much higher plasmon-driven oxidation activity comparing to the center of these nanoplates (Figure 9) [89]
Summary
Noble metal nanostructures absorb light in the visible and infrared (IR) parts of electromagnetic spectrum. Hot carriers are highly energetic species that persist for a few tens of femtoseconds to picoseconds [22, 23] They can further decay via electron–electron or electron–phonon scattering, or they can populate unoccupied orbitals in molecules located near metal surfaces [24, 25]. Measuring Stokes and anti-Stokes vibrations of 16-mercaptohexadodecanoic acid adsorbed to the metal surface, Richard-Lacroix and Deckert found that an average temperature at the tip-sample junction was about 80 °C when 100 μW of 532 nm laser light was used [27] These theoretical and experimental findings show that observed by TERS plasmon-driven chemistry is attributed to hot carriers rather than an increase in temperature
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Free) 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call
