Sol-Gel Synthesis of Ruthenium Oxide Nanowires To Enhance Methanol Oxidation in Supported Platinum Nanoparticle Catalysts.

A template-directed, sol-gel synthesis is utilized to produce crystalline RuO2 nanowires. Crystalline nanowires with a diameter of 128 ± 15 nm were synthesized after treating the nanowires at 600 °C in air. Analysis of these nanowires by X-ray powder diffraction revealed the major crystalline phase to be tetragonal RuO2 with a small quantity of metallic ruthenium present. Further analysis of the nanowire structures by high-resolution transmission electron microscopy reveals that they are polycrystalline and are composed of interconnected, highly crystalline, nanoparticles having an average size of ∼25 nm. Uniform 3 nm Pt nanoparticles were dispersed on the surface of RuO2 nanowires using an ambient, solution-based technique yielding a hybrid catalyst for methanol oxidation. Linear sweep voltammograms (LSVs) and chronoamperometry performed in the presence of methanol in an acidic electrolyte revealed a significant enhancement in the onset potential, mass activity, and long-term stability compared with analogous Pt nanoparticles supported on commercially available Vulcan XC-72R carbon nanoparticles. Formic acid oxidation LSVs and CO stripping voltammetry revealed that the RuO2-supported Pt nanoparticles exhibit significantly higher CO tolerance, which leads to higher catalytic stability over a period of several hours. X-ray photoelectron spectroscopy results suggest that crystalline RuO2 leads to less-significant oxidation of the Pt surface relative to more widely studied hydrous RuO2 supports, thereby increasing catalytic performance.

Ambient surfactantless synthesis, growth mechanism, and size-dependent electrocatalytic behavior of high-quality, single crystalline palladium nanowires.

In this report, we utilize the U-tube double diffusion device as a reliable, environmentally friendly method for the size-controlled synthesis of high-quality, single crystalline Pd nanowires. The nanowires grown in 200 and 15 nm polycarbonate template pores maintain diameters of 270 ± 45 nm and 45 ± 9 nm, respectively, and could be isolated either as individual nanowires or as ordered free-standing arrays. The growth mechanism of these nanowires has been extensively explored, and we have carried out characterization of the isolated nanowires, free-standing nanowire arrays, and cross sections of the filled template in order to determine that a unique two-step growth process predominates within the template pores. Moreover, as-prepared submicrometer and nanosized wires were studied by comparison with ultrathin 2 nm Pd nanowires in order to elucidate the size-dependent trend in oxygen reduction reaction (ORR) electrocatalysis. Subsequently, the desired platinum monolayer overcoating was reliably deposited onto the surface of the Pd nanowires by Cu underpotential deposition (UPD) followed by galvanic displacement of the Cu adatoms. The specific and platinum mass activity of the core-shell catalysts was found to increase from 0.40 mA/cm(2) and 1.01 A/mg to 0.74 mA/cm(2) and 1.74 A/mg as the diameter was decreased from the submicrometer size regime to the ultrathin nanometer range.

Enhanced electrocatalytic performance of processed, ultrathin, supported Pd-Pt core-shell nanowire catalysts for the oxygen reduction reaction.

We report on the synthesis, characterization, and electrochemical performance of novel, ultrathin Pt monolayer shell-Pd nanowire core catalysts. Initially, ultrathin Pd nanowires with diameters of 2.0 ± 0.5 nm were generated, and a method has been developed to achieve highly uniform distributions of these catalysts onto the Vulcan XC-72 carbon support. As-prepared wires are activated by the use of two distinctive treatment protocols followed by selective CO adsorption in order to selectively remove undesirable organic residues. Subsequently, the desired nanowire core-Pt monolayer shell motif was reliably achieved by Cu underpotential deposition followed by galvanic displacement of the Cu adatoms. The surface area and mass activity of the acid and ozone-treated nanowires were assessed, and the ozone-treated nanowires were found to maintain outstanding area and mass specific activities of 0.77 mA/cm(2) and 1.83 A/mg(Pt), respectively, which were significantly enhanced as compared with conventional commercial Pt nanoparticles, core-shell nanoparticles, and acid-treated nanowires. The ozone-treated nanowires also maintained excellent electrochemical durability under accelerated half-cell testing, and it was found that the area-specific activity increased by ~1.5 fold after a simulated catalyst lifetime.

Correlating titania morphology and chemical composition with dye-sensitized solar cell performance.

We have investigated the use of various morphologies, including nanoparticles, nanowires, and sea-urchins of TiO(2) as the semiconducting material used as components of dye-sensitized solar cells (DSSCs). Analysis of the solar cells under AM 1.5 solar irradiation reveals the superior performance of hydrothermally derived nanoparticles, by comparison with two readily available commercial nanoparticle materials, within the DSSC architecture. The sub-structural morphology of films of these nanostructured materials has been directly characterized using SEM and indirectly probed using dye desorption. Furthermore, the surfaces of these nanomaterials were studied using TEM in order to visualize their structure, prior to their application within DSSCs. Surface areas of the materials have been quantitatively analyzed by collecting BET adsorption and dye desorption data. Additional investigation using open circuit voltage decay measurements reveals the efficiency of electron conduction through each TiO(2) material. Moreover, the utilization of various chemically distinctive titanate materials within the DSSCs has also been investigated, demonstrating the deficiencies of using these particular chemical compositions within traditional DSSCs.

Size-dependent infrared phonon modes and ferroelectric phase transition in BiFeO3 nanoparticles.

One emergent property of ferroelectric nanoparticles is the sized-induced structural distortion to a high-symmetry paraelectric phase at small particle sizes. Finite length scale effects can thus be advantageously employed to elucidate ferroelectric transition mechanisms. In this work, we combine infrared spectroscopy with group theory and lattice dynamics calculations to reveal the displacive nature of the ferroelectric transition in BiFeO3, a room temperature multiferroic. Systematic intensity and frequency trends in selected vibrational modes show that the paraelectric phase is Pm3m and the lowest frequency A1 feature is the soft mode that drives the first order transition. Finite length scale effects are also evident in the electronic structure with a red-shifted band gap in nanoscale BiFeO3 compared with that of the rhombohedral film, a result that can impact the development of ferroelectric photovoltaics and oxide-based electronics. Taken together, these findings demonstrate the foundational importance of size effects for enhancing the rich functionality and broad utility of transition metal oxides.

Solution-based synthetic strategies for one-dimensional metal-containing nanostructures.

One-dimensional (1D) nanostructures, such as nanowires, nanotubes, nanorods, and nanoribbons, have attracted significant attention stemming from the plethora of interesting size-dependent and, more importantly, structure-related properties resulting from confinement effects. In particular, the novel properties of 1D nanostructures of metals and metal oxides (binary and ternary) render them as prime candidates for a wide range of applications including the fabrication of nanoscale devices associated with solar cells, energy storage, fuel cells, molecular computing and information storage, medical imaging, diagnosis and detection, drug delivery, sensors and catalysis. Thus, it has been simultaneously necessary and critical to create synthetic protocols for the production of these materials which not only are reliable and reproducible, but also can generate compositionally pure, monodisperse, highly crystalline products of a desired 1D morphology. Solution-based methodologies have demonstrated significant advantages over other approaches, as they are facile, simple, flexible, 'green' by nature, and can be applied to a wide range of nanomaterials with diverse chemical compositions. Moreover, these methods can often be scaled so as to produce large quantities of products which are advantageous from an applications' standpoint. Herein, we present synthetic advances associated with solution-based approaches. Specifically solvothermal/hydrothermal, molten salt, electrospinning, template-directed, solution/one-pot, and sol-gel methodologies are discussed with the primary goal of achieving the reproducible synthesis of 1D motifs of metals, binary metal oxides, and ternary metal oxide systems.

Evaluating cytotoxicity and cellular uptake from the presence of variously processed TiO2 nanostructured morphologies.

We evaluated the cytotoxicity of various morphological classes of TiO(2) nanostructures (including 0-D nanoparticles, 1-D nanorods, and 3-D assemblies) toward living cells. These TiO(2) nanostructures were modified with fluorescent dye molecules, mediated via a dopamine linkage, in order to facilitate a confocal study of their internalization. Specifically, we noted that both TiO(2) 1-D nanorods and 0-D nanoparticles could internalize into cells after 24 h of incubation time. However, only incubation with TiO(2) 1-D nanorods and 3-D micrometer-scale sea urchin-like assemblies at concentrations of up to 125 microg/mL yielded data suggestive of cell viabilities of close to 100%. Moreover, upon irradiation with UV light for periods of a few minutes at energy densities of up to 1 J/cm(2), we observed up to 60% mortality rates, indicative of the cytotoxic potential of photoirradiated TiO(2) nanostructures due to the generation of reactive oxygen species.

Synthesis and characterization of V2O3 nanorods.

In this work, VO2 nanorods have been initially generated as reactive nanoscale precursors to their subsequent conversion to large quantities of highly crystalline V2O3 with no detectable impurities. Structural changes in VO2, associated with the metallic-to-insulating transition from the monoclinic form to the rutile form, have been investigated and confirmed using X-ray diffraction and synchrotron data, showing that the structural transition is reversible and occurs at around 63 degrees C. When this VO2 one-dimensional sample was subsequently heated to 800 degrees C in a reducing atmosphere, it was successfully transformed into V2O3 with effective retention of its nanorod morphology. We have also collected magnetic and transport data on these systems that are comparable to bulk behavior and consistent with trends observed in previous experiments.