Direct SERS tracking of a chemical reaction at a single 13 nm gold nanoparticle.

Metal nanoparticles (NPs) with decreased sizes are promising catalysts in energy and medicine. Measuring the local reactions and simultaneously acquiring molecular insights at single small NPs, however, remain an experimental challenge. Here we report on surface-enhanced Raman spectroscopic (SERS) tracking of catalytic reactions of single 13 nm gold NPs (GNPs) in situ. We designed spatially isolated (>1.5 μm of inter-dimer space) GNP dimers, each of which consisted of two GNPs with sizes of ∼200 and ∼13 nm, respectively. This design integrates the SERS and catalytic activities into a single entity, while eliminating the crosstalk between adjacent particles, which allows us to trace the redox-derived spectral evolution at single 13 nm GNPs for the first time. We also quantified the reaction kinetics of each individual GNP and analyzed the average behavior of multiple GNPs. There is a large variability among different particles, which underscores the significance of single particle analysis.