Optical probes of heterogeneous catalytic reactions are of great importance for in situ determination of the catalytic activity and monitoring of the reaction process. Surface-enhanced Raman scattering (SERS) spectroscopy could be used as a sensitive optical probe for this purpose provided that plasmonic metal nanoparticles for Raman enhancement are properly integrated with catalytic metals to form a single entity. Herein we present a facile approach for synthesizing Au@Pt core-shell nanostructures with a controllable surface density of sub-5 nm Pt nanoparticles on the surface of Au nanorods. Systematic investigations on both SERS and catalytic activities of the hybrid nanostructures reveal an optimized surface coverage of Pt. More importantly, we demonstrate that, due to their dual functionalities, the hybrid nanostructures are able to track the Pt-catalysed reaction in real time by measuring the SERS signals of the reactant, intermediate and final products. This SERS-based synergy technique provides a novel approach for quantitatively studying catalytic chemical reaction processes and is suitable for many applications such as reduction and oxidation reactions in fuel cells and catalytic water splitting.

The last decade has witnessed the remarkable research progress of lanthanide‐doped upconversion nanocrystals (UCNCs) at the forefront of promising applications. However, the future development and application of UCNCs are constrained greatly by their underlying shortcomings such as significant nonradiative processes, low quantum efficiency, and single emission colors. Here a hybrid plasmonic upconversion nanostructure consisting of a GNR@SiO2 coupled with NaGdF4:Yb3+,Nd3+@NaGdF4:Yb3+,Er3+@NaGdF4 core–shell–shell UCNCs is rationally designed and fabricated, which exhibits strongly enhanced UC fluorescence (up to 20 folds) and flexibly tunable UC colors. The experimental findings show that controlling the SiO2 spacer thickness enables readily manipulating the intensity ratio of the Er3+ red, green, and blue emissions, thereby allowing us to achieve the emission color tuning from pale yellow to green upon excitation at 808 nm. Electrodynamic simulations reveal that the tunable UC colors are due to the interplay of plasmon‐mediated simultaneous excitation and emission enhancements in the Er3+ green emission yet only excitation enhancement in the blue and red emissions. The results not only provide an upfront experimental design for constructing hybrid plasmonic UC nanostructures with high efficiency and color tunability, but also deepen the understanding of the interaction mechanism between the Er3+ emissions and plasmon resonances in such complex hybrid nanostructure.

No abstract

The interplay between local field enhancement and backaction determines plasmonic chiral responses and leads to widely tunable geometry-dependent optical activities.