A Salt-Templated Synthesis Method for Porous Platinum-based Macrobeams and Macrotubes.

The synthesis of high surface area porous noble metal nanomaterials generally relies on time consuming coalescence of pre-formed nanoparticles, followed by rinsing and supercritical drying steps, often resulting in mechanically fragile materials. Here, a method to synthesize nanostructured porous platinum-based macrotubes and macrobeams with a square cross section from insoluble salt needle templates is presented. The combination of oppositely charged platinum, palladium, and copper square planar ions results in the rapid formation of insoluble salt needles. Depending on the stoichiometric ratio of metal ions present in the salt-template and the choice of chemical reducing agent, either macrotubes or macrobeams form with a porous nanostructure comprised of either fused nanoparticles or nanofibrils. Elemental composition of the macrotubes and macrobeams, determined with x-ray diffractometry and x-ray photoelectron spectroscopy, is controlled by the stoichiometric ratio of metal ions present in the salt-template. Macrotubes and macrobeams may be pressed into free standing films, and the electrochemically active surface area is determined with electrochemical impedance spectroscopy and cyclic voltammetry. This synthesis method demonstrates a simple, relatively fast approach to achieve high-surface area platinum-based macrotubes and macrobeams with tunable nanostructure and elemental composition that may be pressed into free-standing films with no required binding materials.

Boosted Oxygen Evolution Reactivity by Igniting Double Exchange Interaction in Spinel Oxides.

A double-exchange interaction (DEI) was demonstrated to boost the oxygen evolution reaction (OER) in spinel oxides. DEI was ignited by synergistic actions of constructing nanoheterojunctions and creating oxygen vacancy (VO) in spinel NiCo2O4. DEI between octahedrally coordinated Ni and Co resulted in the generation of superior OER active centers Co(3-δ)+ and Ni3+. The multiple synergistic effects empower the electrocatalyst with exceptional OER activity, with an overpotential of 270 ± 3 mV at 10 mA/cm2 and a Tafel slope of 39 mV/dec, both of which are among the best values for NiCo2O4-based nanostructures, and even better than those for IrO2 and RuO2.

Harvesting resonantly-trapped light for small molecule oxidation reactions at the Au/α-Fe2O3 interface.

Plasmonic metal nanoparticles (NPs) extend the overall light absorption of semiconductor materials. However, it is not well understood how coupling metal NPs to semiconductors alters the photo-electrochemical activity of small molecule oxidation (SMO) reactions. Different photo-anode electrodes comprised of Au NPs and α-Fe2O3 are designed to elucidate how the coupling plays not only a role in the water oxidation reaction (WO) but also performs for different SMO reactions. In this regard, Au NPs are inserted at specific regions within and/or on α-Fe2O3 layers created with a sequential electron beam evaporation method and multiple annealing treatments. The SMO and WO reactions are probed with broad-spectrum irradiation experiments with an emphasis on light-driven enhancements above and below the α-Fe2O3 band gap. Thin films of α-Fe2O3 supported on a gold back reflective layer resonantly-traps incident light leading to enhanced SMO/WO conversion efficiencies at high overpotential (η) for above band-gap excitations with no SMO activity observed at low η. In contrast, a substantial increase in the light-driven SMO activity is observed at low η, as well as for below band-gap excitations when sufficiently thin α-Fe2O3 films are decorated with Au NPs at the solution-electrode interface. The enhanced photo-catalytic activity is correlated with increased surface oxygen content (hydroxyl groups) at the Au/α-Fe2O3 interface, as well as simulated volume-integrated near-field enhancements over select regions of the Au/α-Fe2O3 interface providing an important platform for future SMO/WO photo-electrocatalyst development.

Photoelectrochemical overall water splitting with textured CuBi2O4 as a photocathode.

Nanotextured CuBi2O4 photocathodes have been developed for applications toward solar water splitting. Tailoring the CuBi2O4 photocathodes to yield a high photocurrent and a positively large onset potential demonstrates their applicability in a photoelectrochemical tandem cell for entirely solar-driven overall water splitting.

Nano-Structured Bio-Inorganic Hybrid Material for High Performing Oxygen Reduction Catalyst.

In this study, we demonstrate a non-Pt nanostructured bioinorganic hybrid (BIH) catalyst for catalytic oxygen reduction in alkaline media. This catalyst was synthesized through biomaterial hemin, nanostructured Ag-Co alloy, and graphene nano platelets (GNP) by heat-treatment and ultrasonically processing. This hybrid catalyst has the advantages of the combined features of these bio and inorganic materials. A 10-fold improvement in catalytic activity (at 0.8 V vs RHE) is achieved in comparison of pure Ag nanoparticles (20-40 nm). The hybrid catalyst reaches 80% activity (at 0.8 V vs RHE) of the state-of-the-art catalyst (containing 40% Pt and 60% active carbon). Comparable catalytic stability for the hybrid catalyst with the Pt catalyst is observed by chronoamperometric experiment. The hybrid catalyst catalyzes 4-electron oxygen reduction to produce water with fast kinetic rate. The rate constant obtained from the hybrid catalyst (at 0.6 V vs RHE) is 4 times higher than that of pure Ag/GNP catalyst. A catalytic model is proposed to explain the oxygen reduction reaction at the BIH catalyst.

Plasmon-induced photonic and energy-transfer enhancement of solar water splitting by a hematite nanorod array.

Plasmonic metal nanostructures offer a promising route to improve the solar energy conversion efficiency of semiconductors. Here we show that incorporation of a hematite nanorod array into a plasmonic gold nanohole array pattern significantly improves the photoelectrochemical water splitting performance, leading to an approximately tenfold increase in the photocurrent at a bias of 0.23 V versus Ag|AgCl under simulated solar radiation. Plasmon-induced resonant energy transfer is responsible for enhancement at the energies below the band edge, whereas above the absorption band edge of hematite, the surface plasmon polariton launches a guided wave mode inside the nanorods, with the nanorods acting as miniature optic fibres, enhancing the light absorption. In addition, the intense local plasmonic field can suppress the charge recombination in the hematite nanorod photoanode in a photoelectrochemical cell. Our results may provide a general approach to overcome the low optical absorption and spectral utilization of thin semiconductor nanostructures, while further reducing charge recombination losses.

Flame synthesis of nanosized Cu-Ce-O, Ni-Ce-O, and Fe-Ce-O catalysts for the water-gas shift (WGS) reaction.

A flame synthesis method has been used to prepare nanosized, high-surface-area Cu-Ce-O, Ni-Ce-O, and Fe-Ce-O catalysts from aqueous solutions of metal acetate precursors. The particles were formed by vaporization of the precursors followed by reaction and then gas to particle conversion. The specific surface areas of the synthesized powders ranged from 127 to 163 m(2)/g. High-resolution transmission electron microscope imaging showed that the particle diameters for the ceria materials are in the range of 3-10 nm, and a thin layer of amorphous material was observed on the surface of the particles. The presence and surface enrichment of the transition-metal oxides (CuO, NiO, and Fe(2)O(3)) on the ceria particles were detected using X-ray photoelectron spectroscopy. Electron energy-loss spectroscopic studies suggest the formation of a core-shell structure in the as-prepared particles. Extended X-ray absorption fine structure studies suggest that the dopants in all M-Ce-O systems are almost isostructural with their oxide counterparts, indicating the doping materials form separate oxide phases (CuO, Fe(2)O(3), NiO) within the host matrix (CeO(2)). Etching results confirm that most of the transition-metal oxides are present on the surface of CeO(2), easily dissolved by nitric acid. The performance of the flame-synthesized catalysts was examined toward water-gas shift (WGS) activity for fuel processing applications. The WGS activity of metal ceria catalysts decreases in the order Cu-Ce-O > Ni-Ce-O > Fe-Ce-O > CeO(2) with a feed mixture having a hydrogen to carbon monoxide (H(2)/CO) ratio of 1. There was no methane formation for these catalysts under the tested conditions.

Combinatorial approach toward high-throughput analysis of direct methanol fuel cells.

A 40-member array of direct methanol fuel cells (with stationary fuel and convective air supplies) was generated by electrically connecting the fuel cells in series. High-throughput analysis of these fuel cells was realized by fast screening of voltages between the two terminals of a fuel cell at constant current discharge. A large number of voltage-current curves (200) were obtained by screening the voltages through multiple small-current steps. Gaussian distribution was used to statistically analyze the large number of experimental data. The standard deviation (sigma) of voltages of these fuel cells increased linearly with discharge current. The voltage-current curves at various fuel concentrations were simulated with an empirical equation of voltage versus current and a linear equation of sigma versus current. The simulated voltage-current curves fitted the experimental data well. With increasing methanol concentration from 0.5 to 4.0 M, the Tafel slope of the voltage-current curves (at sigma=0.0), changed from 28 to 91 mV.dec-1, the cell resistance from 2.91 to 0.18 Omega, and the power output from 3 to 18 mW.cm-2.

Nanocrystalline sensor-grade Sn1-xInxO2 (0 < or = x < or = 0.2).

Nanocrystalline Sn1-xInxO2 (0 < or = x < or = 0.2) has been successfully prepared by a solution chemical route. High-resolution transmission electron microscopy studies show that the average grain size of Sn0.8In0.2O2 heated at 310 degrees C, 500 degrees C, and 800 degrees C for 12 h is about 3-4 nm, 5-6 nm, and 7-10 nm, respectively. The corresponding values for pure SnO2 are 3-4 nm, 7-10 nm, and 50-90 nm, respectively. Powder X-ray diffraction and electron diffraction studies confirm the existence of solid solution only in the nanocrystalline state (the average particle size is in the range of 5-10 nm) with the solubility limited to 20% of In2O3. Indium ions stabilize the nanocrystalline nature of Sn1-xInxO2 (0 < or = x < or = 0.2) and prevent the grain growth by entering the SnO2 lattice. The thermal characteristics of nanocrystalline Sn1-xInxO2 (0 < or = x < or = 0.2) investigated by thermogravimetric (TG) and differential thermal analysis (DTA) show that the solid solution decomposes at 820 degrees C into SnO2 and In2O3, which is accompanied by a rapid crystal growth. The electrical conductivity and activation energy of Sn1-xInxO2 (0 < or = x < or = 0.2) undergo significant changes when the average grain size is less than or equal to 2 x the Debye length, LD.