RESUMEN
Single entity electrochemical measurements enable insight into the electrocatalytic activity of individual particles based on composition, shape, and crystallographic orientation. In addition to structural effects, particle size can further influence electrocatalytic activity and reaction mechanisms through mass transport effects. In this work, electrodeposition was used to grow well-separated silver particles of varying sizes from 100 to 500 nm in radius. Using a multimicroscopy approach of scanning electrochemical cell microscopy combined with scanning electron microscopy, the electrocatalytic current of individual silver particles toward the oxygen reduction reaction was evaluated as a function of their size. It was found that the current density increased with decreasing particle radius, which was correlated to the mass transport of oxygen to the silver particle, demonstrating the importance of size dependent mass transport effects that can occur at the single particle level using scanning electrochemical cell microscopy and opening new opportunities for quantitative electrocatalysis measurements.
RESUMEN
N-Heterocyclic carbene (NHC)-stabilized metal nanoparticles (NPs) have recently attracted considerable attention. While most efforts in the field have been devoted to the development of NHC-tethered monometallic NPs and enhancing their stabilities under various conditions, their bimetallic counterparts are rare in the literature. Herein, we demonstrate that the covalent immobilization of Au and Ag atoms on polymerized NHCs is a powerful method to access bimetallic AuAg NPs. In addition, we show that while AuAg alloy NPs are often obtained via this method, the use of bimetallic polymeric substrates with lower Ag content, relative to Au, results in the formation of core-shell NPs with Au core and Ag shell. Application of these nanomaterials for oxygen reduction reaction is demonstrated with all materials exhibiting electrocatalytic activity. This work demonstrates for the first time that while bimetallic poly(NHC-metal)s are viable substrates to access NHC-stabilized bimetallic NPs, careful adjustment of metal content in the polymeric substrates can finetune the microstructure of the resulting NPs, i.e. alloy vs. core-shell.