Li, JianfengJianfengLiRudnev, AlexanderAlexanderRudnevFu, YongchunYongchunFuBodappa, NatarajuNatarajuBodappaWandlowski, ThomasThomasWandlowski2024-10-142024-10-142013-09-05https://boris-portal.unibe.ch/handle/20.500.12422/112324We have studied Au(55 nm)@SiO2 nanoparticles (NPs) on two low-index phases of gold and platinum single crystal electrodes in ClO4– and SO42– ion-containing electrolytes by both electrochemical methods and in-situ shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS). We showed the blocking of the electrode with surfactants originating from the synthesis of as-prepared SHINERS NPs. We introduce an efficient procedure to overcome this problem, which provides a fundamental platform for the application of SHINERS in surface electrochemistry and beyond. Our method is based on a hydrogen evolution treatment of the SHINERS-NP-modified single-crystal surfaces. The reliability of our preparation strategy is demonstrated in electrochemical SHINERS experiments on the potential-controlled adsorption and phase formation of pyridine on Au(hkl) and Pt(hkl). We obtained high-quality Raman spectra on these well-defined and structurally carefully characterized single-crystal surfaces. The analysis of the characteristic A1 vibrational modes revealed perfect agreement with the interpretation of single-crystal voltammetric and chronoamperometric experiments. Our study demonstrates that the SHINERS protocol developed in this work qualifies this Raman method as a pioneering approach with unique opportunities for in situ structure and reactivity studies at well-defined electrochemical solid/liquid interfaces.ensingle-crystal electrodessurface-enhanced RamanSHINERSAu@SiO2nanoparticlescyclic voltammetrypyridine500 - Science::540 - Chemistryarticle10.7892/boris.3982010.1021/nn403444j