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Nanorod arrays of chromium (Cr) were grown on glassy carbon (GC) electrodes by a dc magnetron sputtering glancing angle deposition (GLAD) technique. The Cr nanorods were used as low-cost, high surface area, metallic supports for a conformal layer of Pt thin film catalyst, as a potential low-loading electrocatalyst for the oxygen reduction reaction (ORR) in polymer electrolyte membrane (PEM) fuel cells. A dc magnetron sputtering small angle deposition (SAD) technique was utilized for a conformal coating of Pt on Cr nanorods. The ORR activity of SAD-Pt/GLAD-Cr electrodes was investigated using cyclic voltammetry (CV) and rotating-disk electrode (RDE) techniques in a 0.1 M HClO4 solution at room temperature. A reference sample consisting of GLAD Cr nanorods coated with a Pt thin film deposited at normal incidence (θ = 0o) was prepared and compared with the SAD-Pt/GLAD-Cr nanorods. Compared to GLAD Cr nanorods coated with Pt thin film at θ = 0o, the SAD-Pt/GLAD-Cr nanorod electrode exhibited higher ECSA and area-specific and mass-specific ORR activity. These results indicate that the growth of catalyst layer on the base-metal nanorods by the SAD technique provides a more conformal and possibly a nanostructured coating, significantly enhancing the catalyst utilization.
In this work, we investigated the electrocatalytic oxygen reduction reaction (ORR) activity of vertically aligned, single-layer, carbon-free, and single crystal Pt nanorod arrays utilizing cyclic voltammetry (CV) and rotating-disk electrode (RDE) techniques. A glancing angle deposition (GLAD) technique was used to fabricate 200 nm long Pt nanorods, which corresponds to Pt loading of 0.16 mg/cm2, on glassy carbon (GC) electrode at a glancing angle of 85° as measured from the substrate normal. An electrode comprised of conventional carbon-supported Pt nanoparticles (Pt/C) was also prepared for comparison with the electrocatalytic ORR activity and stability of Pt nanorods. CV results showed that the Pt nanorod electrocatalyst exhibits a more positive oxide reduction peak potential compared to Pt/C, indicating that GLAD Pt nanorods are less oxophilic. In addition, a series of CV cycles in acidic electrolyte revealed that Pt nanorods are significantly more stable against electrochemically-active surface area loss than Pt/C. Moreover, room temperature RDE results demonstrated that GLAD Pt nanorods exhibit higher area-specific ORR activity than Pt/C. The enhanced electrocatalytic ORR activity of Pt nanorods is attributed to their larger crystallite size, single-crystal property, and the dominance of (110) crystal planes on the large surface area nanorods sidewalls, which has been found to be the most active plane for ORR. However, the Pt nanorods showed lower mass specific activity than the Pt/C electrocatalyst due to the large diameter of the Pt nanorods.
Nanostructured thin films were assembled on interdigited microelectrode (IME) arrays as sensitive interfacial materials of an electrochemical detector, which can be integrated into microfluidic sensor devices. The goal is to produce sensor devices at extremes of miniaturization. The IME were created on glass wafers using conventional lithographic techniques. Open channels were etched on quartz or glass, and covered by PDMS materials, which were created using soft-lithography. The capability of chemical recognition was provided by the ligand framework structures of the nanostructured thin films on the electrode surface. A model system for such nanostructures involved the use of monolayer-capped gold nanoparticles of ∼2 nm core sizes which were assembled by carboxylic acid functionalized alkyl thiol linkers. The detection of dopamine was studied as a redox probe to test the feasibility of the microfluidic device. Results of cyclic voltammetric and chronoamperometric experiments are presented. Implications of the findings to the development of sensitive, selective, rapid and portable microanalytical devices for chemical/biological sensing are also discussed.
This paper describes the results of an investigation of the structure and composition of core-shell gold and alloy nanoparticles as catalytically active nanomaterials for potential fuel cell catalysis. Centered on the electrocatalytic methanol oxidation, we show three sets of results based on electrochemical, surface, and composition characterizations. First, electrochemical studies have revealed that the nanostructured catalysts are active towards the electrooxidation of methanol and carbon monoxide. Second, X-ray photoelectron spectroscopy (XPS) data have shown that the organic encapsulating shells can be effectively removed electrochemically or thermally, which involves the formation of oxides on the nanocrystals. Thirdly, direct current plasma - atomic emission spectrometry (DCP-AES) has revealed insights for the correlation of the composition of alloy nanoparticles with the catalytic activities. Implications of these results to the design of nanostructured catalysts will also be discussed.
Thin films derived from nanocrystal cores and functionalized linkers provide large surface-to-volume ratio and three-dimensional ligand framework. This paper describes the results of an investigation of the interfacial ion fluxes associated with redox reactivity and structural properties of such films using cyclic voltammetry, electrochemical quartz-crystal nanobalance, surface infrared reflection spectroscopy, and X-ray photoelectron spectroscopy. Films from gold nanocrystals of 2 nm core sizes and 11-mercaptoundecanoic acid were studied as a model system. First, the film coated on electrode surface displays redox-like voltammetric waves characteristic of the deprotonation-reprotonation of the carboxylic acid groups in the nanostructured network. This process is accompanied by mass changes. Secondly, the film exhibits capability for the complexation of copper ions via the nanostructured carboxylate framework. This process is also accompanied by interfacial fluxes of electrolyte cations across the electrode | film | electrolyte interface which compensate electrostatically the fixed negative charges in the reduction process.
Nanostructured thin films were assembled as metal-responsive electrode materials from monolayer-capped gold nanoparticles (2 nm) and carboxylic acid functionalized alkyl thiol linkers via an exchange-crosslinking-precipitation reaction pathway. The network assemblies have open frameworks in which void space forms channels or chambers with the nanometer sized cores defining its size and the shell structures defining its chemical specificity. Such nanostructures were investigated as responsive materials for the detection of metal ion fluxes. Cyclic voltammetry, in-situ electrochemical quartz-crystal nanobalance, and surface infrared reflection spectroscopy techniques were used to characterize the interfacial redox reactivity and mass fluxes at the nanostructured electrode materials. The system showed remarkable reversible mass loading arising from incorporation of ionic species into the film. The diagnostic stretching bands of the carboxylic and carboxylate groups at the shell allowed the identification and assessment of the interfacial carboxylate-metal ion reactivity.
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