Surface- and Tip-Enhanced Raman Spectroscopy as Operando Probes for Monitoring and Understanding Heterogeneous Catalysis

Abstract

Surface-enhanced Raman spectroscopy (SERS) and tip-enhanced Raman spectroscopy (TERS) were until recently limited in their applicability to the majority of heterogeneous catalytic reactions. Recent developments begin to resolve the conflicting experimental requirements for SERS and TERS on the one hand, and heterogeneous catalysis on the other hand. This article discusses the development and use of SERS and TERS to study heterogeneous catalytic reactions, and the exciting possibilities that may now be within reach thanks to the latest technical developments. This will be illustrated with showcase examples from photo- and electrocatalysis. Graphical Abstract

Thermally Stable TiO2‐ and SiO2‐Shell‐Isolated Au Nanoparticles for In Situ Plasmon‐Enhanced Raman Spectroscopy of Hydrogenation Catalysts

“…The first step is to find an optimal core size for enhancing Raman scattering under 785 nm wavelength laser illumination. A 785 nm laser as excitation source in combination with Au nanoparticles (NPs) are used to limit potential plasmonic side reactions . Au NPs of various sizes were prepared between approximately 40 and 100 nm by using a seed‐mediated growth to realize satisfying control over the Au particle size .…”

“…A7 85 nm laser as excitation source in combination with Au nanoparticles (NPs) are used to limit potential plasmonic side reactions. [29][30][31] Au NPs of various sizes were prepared between approximately 40 and 100 nm by using as eed-mediated growth to realize satisfying control over the Au particle size. [32][33][34] The Au cores were then coated with ultrathinT iO 2 in ac ontrolled manner by modifying two existing methods (Figure 2, more TEM and SEM images are found in the Supporting Information;F iguresS1-S6).…”

Advances in surface-enhanced vibrational spectroscopy at electrochemical interfaces

“…A significant issue that has precluded widespread uptake of TERS relates to the reliable fabrication and availability of suitable probes [118,121], although recent advances have improved the measurement and understanding of enhancement factors [122,123] as well as probe degradation mechanisms [124]. Despite these challenges, the potential of TERS for studying surface reactions in situ is well-recognised and advances have been demonstrated in a number of cases [125][126][127][128][129].…”

Raman Under Water – Nonlinear and Nearfield Approaches for Electrochemical Surface Science

“…One way to generate a substrate‐independent ‘hot spot’ close to a sample interface is by means of tip‐enhanced Raman spectroscopy (TERS; Figure d), where a coinage‐metal scanning‐probe tip is brought in close vicinity to the surface and acts as a nano‐antenna to provide high field‐enhancement at the location of interest. With TERS, similar Raman signal enhancement as with SERS can be achieved to probe, for example, molecular catalytic properties and interactions of a few scatterers underneath the tip at a chemical spatial resolution in the order of around 5 nm …”