RESUMEN
Metallic nanostructures exhibit superior catalytic performance for diverse chemical reactions and the in-depth understanding of reaction mechanisms requires versatile characterization methods. Plasmon-enhanced Raman spectroscopy (PERS), including surface-enhanced Raman spectroscopy (SERS), shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS), and tip-enhanced Raman spectroscopy (TERS), appears as a powerful technique to characterize the Raman fingerprint information of surface species with high chemical sensitivity and spatial resolution. To expand the range of catalytic reactions studied by PERS, catalytically active metals are integrated with plasmonic metals to produce bifunctional metallic nanostructures. In this minireview, we discuss the recent advances in PERS techniques to probe the chemical reactions catalysed by bifunctional metallic nanostructures. First, we introduce different architectures of these dual-functionality nanostructures. We then highlight the recent works using PERS to investigate important catalytic reactions as well as the electronic and catalytic properties of these nanostructures. Finally, we provide some perspectives for future PERS studies in this field.
RESUMEN
Active oxygen species (AOS) play key roles in many important catalytic reactions relevant to clean energy and environment. However, it remains challenging to characterize the active sites for producing AOS and to image the surface properties of AOS, especially on multicomponent metallic catalyst surfaces. Herein, we utilize tip-enhanced Raman spectroscopy (TERS) to probe the local generation and diffusion of OH radicals on a Pd/Au(111) bimetallic catalyst surface. The reactive OH radicals can be catalytically generated from hydrogen peroxide (H2O2) at the metal surface, which then oxidizes the surface adsorbed thiolate, a reactant that is used as the TERS probe. By TERS imaging of the spatial distribution of unreacted thiolate molecules, we demonstrate that the Pd surface is active for generation of OH radicals and the Pd step edge shows much higher activity than the Pd terrace, whereas the Au surface is inactive. Furthermore, we find that the locally generated OH radicals at the Pd step edge could diffuse to both the Au and the Pd surface sites to induce oxidative reactions, with a diffusion length estimated to be about 5.4 nm. Our TERS imaging with few-nanometer spatial resolution not only unravels the active sites but also characterizes in real space the diffusion behavior of OH radicals. The results are highly valuable to understand AOS-triggered catalytic reactions. The strategy of using reactants with large Raman cross sections as TERS probes may broaden the application of TERS for studying catalysis with reactive small molecules.