Surface-enhanced Raman spectroscopic detection of molecular chemo- and plasmo-catalysis on noble metal nanoparticles.

The in situ detection of reactions catalyzed by metal NPs is challenging because the underlying chemical transformations occur at interfaces. Surface-enhanced Raman scattering (SERS), a surface-selective, sensitive and label-free vibrational spectroscopic technique, is ideally suited for monitoring of heterogeneous catalysis with high chemical specificity. A major limitation in the past, however, was that small, catalytically active metal NPs do not exhibit the high plasmonic activity required for SERS. This feature article focuses on the design, synthesis and use of bifunctional NPs with both catalytic and plasmonic activity for in situ SERS detection of reactions catalyzed by metal NPs. We focus on model reactions induced by chemical reducing agents such as hydride or molecular hydrogen as well as on plasmon-induced photo-catalysis including both photo-oxidation and photo-reduction. Finally, we highlight the concept of photo-recycling on halide-containing silver surfaces for unprecedented multi-electron reduction chemistry.