Enhanced Electrocatalytic Oxidation of Small Organic Molecules on Platinum-Gold Nanowires: Influence of the Surface Structure and Pt-Pt/Pt-Au Pair Site Density.

The electrochemical oxidation of small organic molecules (SOMs) such as methanol and glucose is a critical process and has relevant applications in fuel cells and sensors. A key challenge in SOM oxidation is the poisoning of the surface by carbon monoxide (CO) and other partially oxidized intermediates, which is attributed to the presence of Pt-Pt pair sites. A promising pathway for overcoming this challenge is to develop catalysts that selectively oxidize SOMs via "direct" pathways that do not form CO as a primary intermediate. In this report, we utilize an ambient, template-based approach to prepare PtAu alloy nanowires with tunable compositions. X-ray photoelectron spectroscopy measurements reveal that the surface composition matches that of the bulk composition after synthesis. Monte Carlo method simulations of the surface structure of PtAu alloys with varying coverage of oxygen adsorbates and varying degrees of oxygen adsorption strength reveal that oxygen adsorption under electrochemical conditions enriches the surface with Pt and a large fraction of Pt-Pt sites remain on the surface even with the Au content of up to 50%. Electrochemical properties and the catalytic performance measurements of the PtAu nanowires for the oxidation of methanol and glucose reveal that the mechanistic pathways that produce CO are suppressed by the addition of relatively small quantities of Au (∼10%), and CO formation can be completely suppressed by 50% Au. The suppression of CO formation with small quantities of Au suggests that the presence of Pt-Au pair sites may be more important in determining the mechanism of SOM oxidation rather than Pt-Pt pair site density.

Surfactant-Free Synthesis of Three-Dimensional Perovskite Titania-Based Micron-Scale Motifs Used as Catalytic Supports for the Methanol Oxidation Reaction.

We synthesized and subsequently rationalized the formation of a series of 3D hierarchical metal oxide spherical motifs. Specifically, we varied the chemical composition within a family of ATiO3 (wherein "A" = Ca, Sr, and Ba) perovskites, using a two-step, surfactant-free synthesis procedure to generate structures with average diameters of ~3 microns. In terms of demonstrating the practicality of these perovskite materials, we have explored their use as supports for the methanol oxidation reaction (MOR) as a function of their size, morphology, and chemical composition. The MOR activity of our target systems was found to increase with decreasing ionic radius of the "A" site cation, in order of Pt/CaTiO3 (CTO) > Pt/SrTiO3 (STO) > Pt/BaTiO3 (BTO). With respect to morphology, we observed an MOR enhancement of our 3D spherical motifs, as compared with either ultra-small or cubic control samples. Moreover, the Pt/CTO sample yielded not only improved mass and specific activity values but also a greater stability and durability, as compared with both commercial TiO2 nanoparticle standards and precursor TiO2 templates.

Synthesis, decomposition studies and crystal structure of a three-dimensional CuCN network structure with protonated N-methylethanolamine as the guest cation.

The compound poly[2-hydroxy-N-methylethan-1-aminium [µ3-cyanido-κ3C:C:N-di-µ-cyanido-κ4C:N-dicuprate(I)]], {(C3H10NO)[Cu2(CN)3]}n or [meoenH]Cu2(CN)3, crystallizes in the tetragonal space group P43. The structure consists of a three-dimensional (3D) anionic CuICN network with noncoordinated protonated N-methylethanolamine cations providing charge neutrality. Pairs of cuprophilic Cu atoms are bridged by the C atoms of µ3-cyanide ligands, which link these units into a 43 spiral along the c axis. The spirals are linked together into a 3D anionic network by the two other cyanide groups. The cationic moieties are linked into their own 43 spiral via N-H...O and O-H...O hydrogen bonds, and the cations interact with the 3D network via an unusual pair of N-H...N hydrogen bonds to one of the µ2-cyanide groups. Thermogravimetric analysis indicates an initial loss of the base cation and one cyanide as HCN at temperatures in the range 130-250 °C to form CuCN. We show how loss of a specific cyanide group from the 3D CuCN structure could form the linear CuCN structure. Further heating leaves a residue of elemental copper, isolated as the oxide.

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.

Controlling the rectification properties of molecular junctions through molecule-electrode coupling.

The development of molecular components functioning as switches, rectifiers or amplifiers is a great challenge in molecular electronics. A desirable property of such components is functional robustness, meaning that the intrinsic functionality of components must be preserved regardless of the strategy used to integrate them into the final assemblies. Here, this issue is investigated for molecular diodes based on N-phenylbenzamide (NPBA) backbones. The transport properties of molecular junctions derived from NPBA are characterized while varying the nature of the functional groups interfacing the backbone and the gold electrodes required for break-junction measurements. Combining experimental and theoretical methods, it is shown that at low bias (<0.85 V) transport is determined by the same frontier molecular orbital originating from the NPBA core, regardless of the anchoring group employed. The magnitude of rectification, however, is strongly dependent on the strength of the electronic coupling at the gold-NPBA interface and on the spatial distribution of the local density of states of the dominant transport channel of the molecular junction.

Computational Design of Intrinsic Molecular Rectifiers Based on Asymmetric Functionalization of N-Phenylbenzamide.

We report a systematic computational search of molecular frameworks for intrinsic rectification of electron transport. The screening of molecular rectifiers includes 52 molecules and conformers spanning over 9 series of structural motifs. N-Phenylbenzamide is found to be a promising framework with both suitable conductance and rectification properties. A targeted screening performed on 30 additional derivatives and conformers of N-phenylbenzamide yielded enhanced rectification based on asymmetric functionalization. We demonstrate that electron-donating substituent groups that maintain an asymmetric distribution of charge in the dominant transport channel (e.g., HOMO) enhance rectification by raising the channel closer to the Fermi level. These findings are particularly valuable for the design of molecular assemblies that could ensure directionality of electron transport in a wide range of applications, from molecular electronics to catalytic reactions.

In Situ Probing of the Active Site Geometry of Ultrathin Nanowires for the Oxygen Reduction Reaction.

To create truly effective electrocatalysts for the cathodic reaction governing proton exchange membrane fuel cells (PEMFC), namely the oxygen reduction reaction (ORR), necessitates an accurate and detailed structural understanding of these electrocatalysts, especially at the nanoscale, and to precisely correlate that structure with demonstrable performance enhancement. To address this key issue, we have combined and interwoven theoretical calculations with experimental, spectroscopic observations in order to acquire useful structural insights into the active site geometry with implications for designing optimized nanoscale electrocatalysts with rationally predicted properties. Specifically, we have probed ultrathin (∼2 nm) core-shell Pt∼Pd9Au nanowires, which have been previously shown to be excellent candidates for ORR in terms of both activity and long-term stability, from the complementary perspectives of both DFT calculations and X-ray absorption spectroscopy (XAS). The combination and correlation of data from both experimental and theoretical studies has revealed for the first time that the catalytically active structure of our ternary nanowires can actually be ascribed to a PtAu∼Pd configuration, comprising a PtAu binary shell and a pure inner Pd core. Moreover, we have plausibly attributed the resulting structure to a specific synthesis step, namely the Cu underpotential deposition (UPD) followed by galvanic replacement with Pt. Hence, the fundamental insights gained into the performance of our ultrathin nanowires from our demonstrated approach will likely guide future directed efforts aimed at broadly improving upon the durability and stability of nanoscale electrocatalysts in general.

Facet-dependent photoelectrochemical performance of TiO2 nanostructures: an experimental and computational study.

The behavior of crystalline nanoparticles depends strongly on which facets are exposed. Some facets are more active than others, but it is difficult to selectively isolate particular facets. This study provides fundamental insights into photocatalytic and photoelectrochemical performance of three types of TiO(2) nanoparticles with predominantly exposed {101}, {010}, or {001} facets, where 86-99% of the surface area is the desired facet. Photodegradation of methyl orange reveals that {001}-TiO(2) has 1.79 and 3.22 times higher photocatalytic activity than {010} and {101}-TiO(2), respectively. This suggests that the photochemical performance is highly correlated with the surface energy and the number of under-coordinated surface atoms. In contrast, the photoelectrochemical performance of the faceted TiO(2) nanoparticles sensitized with the commercially available MK-2 dye was highest with {010}-TiO(2) which yielded an overall cell efficiency of 6.1%, compared to 3.2% for {101}-TiO(2) and 2.6% for {001}-TiO(2) prepared under analogous conditions. Measurement of desorption kinetics and accompanying computational modeling suggests a stronger covalent interaction of the dye with the {010} and {101} facets compared with the {001} facet. Time-resolved THz spectroscopy and transient absorption spectroscopy measure faster electron injection dynamics when MK-2 is bound to {010} compared to other facets, consistent with extensive computational simulations which indicate that the {010} facet provides the most efficient and direct pathway for interfacial electron transfer. Our experimental and computational results establish for the first time that photoelectrochemical performance is dependent upon the binding energy of the dye as well as the crystalline structure of the facet, as opposed to surface energy alone.

The effect of tungstate nanoparticles on reactive oxygen species and cytotoxicity in raw 264.7 mouse monocyte macrophage cells.

Due to their unique size, surface area, and chemical characteristics, nanoparticles' use in consumer products has increased. However, the toxicity of nanoparticle (NP) exposure during the manufacturing process has not been fully assessed. Tungstate NP are used in numerous products, including but not limited to scintillator detectors and fluorescent lighting. As with many NP, no apparent toxicity studies have been completed with tungstate NP. The hypothesis that tungstate NP in vitro exposure results in reactive oxygen species (ROS) formation and cytotoxicity was examined. Differences in toxicity based on tungstate NP size, shape (sphere vs. wire), and chemical characteristics were determined. RAW 264.7 mouse monocyte macrophages were exposed to tungstate NP, and ROS formation was assessed via electron spin resonance (ESR), and several assays including hydrogen peroxide, intracellular ROS, and Comet. Results showed ROS production induced by tungstate nanowire exposure, but this exposure did not result in oxidative DNA damage. Nanospheres showed neither ROS nor DNA damage following cellular exposure. Cells were exposed over 72 h to assess cytotoxicity using an MTT (tetrazolium compound) assay. Results showed that differences in cell death between wires and spheres occurred at 24 h but were minimal at both 48 and 72 h. The present results indicate that tungstate nanowires are more reactive and produce cell death within 24 h of exposure, whereas nanospheres are less reactive and did not produce cell death. Results suggest that differences in shape may affect reactivity. However, regardless of the differences in reactivity, in general both shapes produced mild ROS and resulted in minimal cell death at 48 and 72 h in RAW 264.7 cells.

Ambient synthesis of high-quality ruthenium nanowires and the morphology-dependent electrocatalytic performance of platinum-decorated ruthenium nanowires and nanoparticles in the methanol oxidation reaction.

We report for the first time (a) the synthesis of elemental ruthenium nanowires (Ru NWs), (b) a method for modifying their surfaces with platinum (Pt), and (c) the morphology-dependent methanol oxidation reaction (MOR) performance of high-quality Pt-modified Ru NW electrocatalysts. The synthesis of our elemental Ru NWs has been accomplished utilizing a template-based method under ambient conditions. As-prepared Ru NWs are crystalline and elementally pure, maintain electrochemical properties analogous to elemental Ru, and can be generated with average diameters ranging from 44 to 280 nm. We rationally examine the morphology-dependent performance of the Ru NWs by comparison with commercial Ru nanoparticle (NP)/carbon (C) systems after decorating the surfaces of these structures with Pt. We have demonstrated that the deposition of Pt onto the Ru NWs (Pt~Ru NWs) results in a unique hierarchical structure, wherein the deposited Pt exists as discrete clusters on the surface. By contrast, we find that the Pt-decorated commercial Ru NP/C (Pt~Ru NP/C) results in the formation of an alloy-type NP. The Pt~Ru NPs (0.61 A/mg of Pt) possess nearly 2-fold higher Pt mass activity than analogous Pt~Ru NW electrocatalysts (0.36 A/mg of Pt). On the basis of a long-term durability test, it is apparent that both catalysts undergo significant declines in performance, potentially resulting from aggregation and ripening in the case of Pt~Ru NP/C and the effects of catalyst poisoning in the Pt~Ru NWs. At the conclusion of the test, both catalysts maintain comparable performance, despite a slightly enhanced performance in Pt~Ru NP/C. In addition, the measured mass-normalized MOR activity of the Pt~Ru NWs (0.36 A/mg of Pt) was significantly enhanced as compared with supported elemental Pt (Pt NP/C, 0.09 A/mg of Pt) and alloy-type PtRu (PtRu NP/C, 0.24 A/mg of Pt) NPs, both serving as commercial standards.

Highly enhanced electrocatalytic oxygen reduction performance observed in bimetallic palladium-based nanowires prepared under ambient, surfactantless conditions.

We have employed an ambient, template-based technique that is simple, efficient, and surfactantless to generate a series of bimetallic Pd(1-x)Au(x) and Pd(1-x)Pt(x) nanowires with control over composition and size. Our as-prepared nanowires maintain significantly enhanced activity toward oxygen reduction as compared with commercial Pt nanoparticles and other 1D nanostructures, as a result of their homogeneous alloyed structure. Specifically, Pd(9)Au and Pd(4)Pt nanowires possess oxygen reduction reaction (ORR) activities of 0.49 and 0.79 mA/cm(2), respectively, which are larger than the analogous value for commercial Pt nanoparticles (0.21 mA/cm(2)). In addition, core-shell Pt~Pd(9)Au nanowires have been prepared by electrodepositing a Pt monolayer shell and the corresponding specific, platinum mass, and platinum group metal mass activities were found to be 0.95 mA/cm(2), 2.08 A/mg(Pt), and 0.16 A/mg(PGM), respectively. The increased activity and catalytic performance is accompanied by improved durability toward ORR.

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.

Size-dependent enhancement of electrocatalytic performance in relatively defect-free, processed ultrathin platinum nanowires.

We report on the synthesis, characterization, and electrocatalytic performance of ultrathin Pt nanowires with a diameter of less than 2 nm. An acid-wash protocol was employed in order to yield highly exfoliated, crystalline nanowires with a diameter of 1.3 +/- 0.4 nm. The electrocatalytic activity of these nanowires toward the oxygen reduction reaction was studied in relation to the activity of both supported and unsupported Pt nanoparticles as well as with previously synthesized Pt nanotubes. Our ultrathin, acid-treated, unsupported nanowires displayed an electrochemical surface area activity of 1.45 mA/cm(2), which was nearly 4 times greater than that of analogous, unsupported platinum nanotubes and 7 times greater than that of commercial supported platinum nanoparticles.