Dark-field scattering spectroelectrochemistry is used to analyze the electrochemical formation of individual Ag nanoparticles (NPs) at the surface of an indium tin oxide electrode. Heterogeneities in redox potentials among NPs not visible in bulk electrochemical measurements are presented for the first time. Through correlated electron microscopy, single NP light scattering intensity is related to particle size according to Mie theory, enabling rapid particle size determination and the construction of voltammetric curves for individual NPs.

Here, a new methodology is proposed for treating electrochemical current densities in metal-insulator-metal nanoparticle (M-I-MNP) systems. The described model provides broad, practical insights about MNP-mediated electron transfer to redox species in solution, where electron transfer from the underlying electrode to a MNP via tunneling and heterogeneous electron transfer from the MNP to redox species in solution are treated as sequential steps. Tunneling is treated through an adaptation of the Simmons model of tunneling in metal-insulator-metal structures, and explicit equations are provided for tunneling currents, which demonstrate the effect of various experimental parameters, such as insulator thickness and MNP size. Overall, a general approach is demonstrated for determining experimental conditions where tunneling will have a measurable impact on the electrochemistry of M-I-MNP systems.

A novel analytical methodology based on correlated optical and electroanalytical measurements was developed to probe electrocatalytic reactions at individual nanoparticles (NPs) with well-defined geometries. The developed methodology, Optically Targeted ElectroChemical Cell Microscopy (OTECCM), relies on a combination of optical hyperspectral imaging, to locate individual NPs and provide structural information, and Scanning ElectroChemical Cell Microscopy (SECCM), to provide direct information on the electrochemical behavior of the same NPs. This complementary strategy allows for SECCM measurements to be carried out in a "targeted" fashion, offering significant throughput advantages over conventional, scanning-based approaches. The developed methodology was applied to study the electrocatalytic oxidation of hydrazine at individual Au nanorods (NRs). Correlated electron microscopy investigations were carried out to conclusively demonstrate the ability of the proposed methodology to probe electrochemical reactions at individual NRs. A wide variety in behavior of the individual NRs was observed, with surface reactions at Au playing a prominent role in the observed response. In situ spectroscopic investigations at individual NRs suggest surface restructuring and/or residual ligand desorption leads to significant changes in catalytic activity over time. Results from the correlated electron microscopy investigations as well as the statistical analyses of data obtained for hundreds of individual nanostructures suggest that the gross geometry of a NR is a poor predictor of its electrocatalytic performance.

The spectroelectrochemical properties of individual luminescent, plasmonic silver nanoparticles (Ag NPs) are investigated using the combined methods of dark-field scattering (DFS) and photoluminescence (PL) spectroelectrochemistry. Individual NP light scattering and PL intensities are measured while the substrate’s electrochemical potential is controlled to produce and oxidize the NPs. The spectroelectrochemical responses of individual NPs are used to study heterogeneities in their redox properties not visible in bulk voltammetric measurements. Our studies show that the Ag NPs exhibit a range of redox potentials, and their statistical distribution is dependent on the electrolyte system used. No variations in the spectral profile of bulk NP samples are observed, implying no correlation between the redox potentials of individual NPs and the energy of emitted photons from fluorescent sites on Ag NPs. This is due to a negligible difference in the redox potentials for individual emissive sites on a given Ag NP and/or the shrinking of the polarizable bulk of the Ag NP.

Spatial variations in photoelectrochemical reaction rates within individual p-type WSe2 nanosheets were mapped through the application of scanning electrochemical cell microscopy (SECCM). The simultaneous topographical and electrochemical information provided via SECCM directly revealed how both sheet thickness and the presence of defect structures affect the local rate of photoelectrochemical reactions for both outer sphere and inner sphere redox couples. Sheet thickness was found to play a dramatic role in reaction rates, with onset potentials shifting by as much as 0.5 V over thicknesses of 20–120 nm, attributable to the inability of thin sheets to support independent space charge layers. Step/edge features were found to play a detrimental role for the outer sphere redox couple investigated (Ru­(NH3)6 3+ reduction), with taller steps having larger effects on performance. Shorter step features were found to be beneficial for hydrogen evolution, showing a controlled density of defect features is desirable for inner sphere processes. The studies presented here not only provide valuable, quantitative insights into the behavior of transitional metal dichalcogenide materials but also demonstrate the power of applying SECCM to the study of photoelectrochemical systems, particularly those involving two-dimensional (2D) materials.