Small Gold Nanoparticles Interfaced to Electrodes through Molecular Linkers: A Platform to Enhance Electron Transfer and Increase Electrochemically Active Surface Area.

For the smallest nanostructures (<5 nm), small changes in structure can lead to significant changes in properties and reactivity. In the case of nanoparticle (NP)-functionalized electrodes, NP structure and composition, and the nature of the NP-electrode interface have a strong influence upon electrochemical properties that are critical in applications such as amperometric sensing, photocatalysis and electrocatalysis. Existing methods to fabricate NP-functionalized electrodes do not allow for precise control over all these variables, especially the NP-electrode interface, making it difficult to understand and predict how structural changes influence NP activity. We investigated the electrochemical properties of small (dcore < 2.5 nm) gold nanoparticles (AuNPs) on boron doped diamond electrodes using three different electrode fabrication techniques with varying degrees of nanoparticle-electrode interface definition. Two methods to attach AuNPs to the electrode through a covalently bound molecular linker were developed and compared to NP-functionalized electrodes fabricated using solution deposition methods (drop-casting and physiadsorption of a monolayer). In each case, a ferrocene redox probe was tethered to the AuNP surface to evaluate electron transfer through the AuNPs. The AuNPs that were molecularly interfaced with the electrode exhibited nearly ideal, reproducible electrochemical behavior with narrow redox peaks and small peak separations, whereas the solution deposited NPs had broader redox peaks with large peak separations. These data suggest that the molecular tether facilitates AuNP-mediated electron transfer. Interestingly, the molecularly tethered NPs also had significantly more electrochemically active surface area than the solution deposited NPs. The enhanced electrochemical behavior of the molecularly interfaced NPs demonstrates the significant influence of the interface on NP-mediated electron transfer and suggests that similar modified electrodes can serve as versatile platforms for studies and applications of nanoparticles.

Revised Oxygen Evolution Reaction Activity Trends for First-Row Transition-Metal (Oxy)hydroxides in Alkaline Media.

First-row transition-metal oxides and (oxy)hydroxides catalyze the oxygen evolution reaction (OER) in alkaline media. Understanding the intrinsic catalytic activity provides insight into improved catalyst design. Experimental and computationally predicted activity trends, however, have varied substantially. Here we describe a new OER activity trend for nominally oxyhydroxide thin films of Ni(Fe)O(x)H(y) > Co(Fe)O(x)H(y) > FeO(x)H(y)-AuO(x) > FeO(x)H(y) > CoO(x)H(y) > NiO(x)H(y) > MnO(x)H(y). This intrinsic trend has been previously obscured by electrolyte impurities, potential-dependent electrical conductivity, and difficulty in correcting for surface-area or mass-loading differences. A quartz-crystal microbalance was used to monitor mass in situ and X-ray photoelectron spectroscopy to measure composition and impurity levels. These new results provide a basis for comparison to theory and help guide the design of improved catalyst systems.