Mechanistic Studies of Plasmon Chemistry on Metal Catalysts

Abstract

Chemical reactions induced by the localized surface plasmon (LSP) of metal nanostructures could be important for a sustainable society to achieve highly efficient conversion from solar energy to chemical energy. However, the reaction mechanism of plasmon chemistry in metal catalysis is still controversial. Mechanistic studies of plasmon chemistry involving direct interactions between the LSP and molecules are reviewed and discussed in terms of the excitation mechanisms of the molecules. We focus on the studies performed using plasmonic metal nanoparticles and highlight the recent progress in plasmon chemistry investigated using scanning probe microscopy with high spatial resolution to obtain mechanistic insights that cannot be obtained by macroscopic analytical methods. This Minireview delivers an overview of the mechanistic understanding of plasmon chemistry in metal catalysis at the current stage, and provides guidance for future studies with respect to clarifying reaction mechanisms.

Collective photothermal effect of Al2O3‐supported spheroidal plasmonic Ru nanoparticle catalysts in the sunlight‐powered Sabatier reaction

“…Plasmon catalysis makes use of the localized surface plasmon resonance (LSPR) of metal nanocatalysts for light harvesting. Upon illumination of a plasmonic nanocatalyst a coherent electron oscillation occurs in these particles, which dephases and generates hot electrons [5] . These can then either transfer into an electron accepting orbital of a nearby adsorbate, or thermalize resulting in an increased temperature of the catalyst.…”

“…Upon illumination of a plasmonic nanocatalyst a coherent electron oscillation occurs in these particles, which dephases and generates hot electrons. [5] These can then either transfer into an electron accepting orbital of a nearby adsorbate, or thermalize resulting in an increased temperature of the catalyst. Because of the electronic oscillation, the plasmonic catalyst may also behave as an electromagnetic dipole and emit light coherently at the same frequency.…”

Nanoscale Chemical Reaction Imaging at the Solid–Liquid Interface via TERS

“…[18][19][20][21]24,26 Several mechanistic investigations have subsequently been performed, with an emerging consensus that hot-electrons drive azo bond formation to yield DMAB. 21,[27][28][29][30] Note that all of the aforementioned works investigated DMAB formation through (nominally diffraction-limited) surface-enhanced Raman scattering measurements that nonetheless track plasmon-induced chemical transformations with high sensitivity and chemical selectivity.…”

Roles of silver nanoclusters in surface-enhanced Raman spectroscopy

“…6 The surface plasmon effect has been investigated combining with scanning tunneling microscopic techniques to potentiate its spectroscopic measurement in the size-regime down to singlemolecule scale. [7][8][9] Many theoretical studies have so far been performed to make clear the roles of the surface plasmon in these applications. 10,11 In the field of chemistry, the surface plasmon resonance has also been intensively studied due to the anticipated significant role in the remarkable enhancement of resonance Raman scattering cross sections, which pave the way for single-molecule-scale spectroscopies and microscopies.…”