Surface-enhanced Raman scattering (SERS) is a powerful fingerprint vibrational spectroscopy with a single-molecule detection limit, but its applications are generally restricted to 'free-electron-like' metal substrates such as Au, Ag and Cu nanostructures. We have invented a shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) technique, using Au-core silica-shell nanoparticles (Au@SiO(2) NPs), which makes SERS universally applicable to surfaces with any composition and any morphology. This protocol describes how to prepare shell-isolated nanoparticles (SHINs) with different well-controlled core sizes (55 and 120 nm), shapes (nanospheres, nanorods and nanocubes) and shell thicknesses (1-20 nm). It then describes how to apply SHINs to Pt and Au single-crystal surfaces with different facets in an electrochemical environment, on Si wafer surfaces adsorbed with hydrogen, on ZnO nanorods, and on living bacteria and fruit. With this method, SHINs can be prepared for use in ~3 h, and each subsequent procedure for SHINERS measurement requires 1-2 h.
We have developed a combined surface-enhanced Raman spectroscopy (SERS) and break junction method to detect and characterize molecules between two microfabricated electrodes separated with a gap that can be continuously adjusted from a few angstroms to nanometers. It allows us to obtain a vibrational fingerprint of the adjustable molecular junction while performing electron transport measurements on the molecule simultaneously. This new approach will provide not only new insights into electron transport properties of molecule junctions on a chip but also the mechanism of single-molecule-SERS.
Photoinduced interfacial electron transfer (ET) from molecular adsorbates to semiconductor nanoparticles has been a subject of intense recent interest. Unlike intramolecular ET, the existence of a quasicontinuum of electronic states in the solid leads to a dependence of ET rate on the density of accepting states in the semiconductor, which varies with the position of the adsorbate excited-state oxidation potential relative to the conduction band edge. For metal oxide semiconductors, their conduction band edge position varies with the pH of the solution, leading to pH-dependent interfacial ET rates in these materials. In this work we examine this dependence in Re(L P )(CO) 3 Cl (or ReC1P) [L P ) 2,2′-bipyridine-4,4′-bis-CH 2 PO(OH) 2 ] and Re-(L A )(CO) 3 Cl (or ReC1A) [L A ) 2,2′-bipyridine-4,4′-bis-CH 2 COOH] sensitized TiO 2 and ReC1P sensitized SnO 2 nanocrystalline thin films using femtosecond transient IR spectroscopy. ET rates are measured as a function of pH by monitoring the CO stretching modes of the adsorbates and mid-IR absorption of the injected electrons. The injection rate to TiO 2 was found to decrease by 1000-fold from pH 0-9, while it reduced by only a factor of a few to SnO 2 over a similar pH range. Comparison with the theoretical predictions based on Marcus' theory of nonadiabatic interfacial ET suggests that the observed pH-dependent ET rate can be qualitatively accounted for by considering the change of density of electron-accepting states caused by the pH-dependent conduction band edge position.
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