A bimetallic catalyst on a dual component support for low temperature total methane oxidation

Palladium, platinum bimetallic catalysts supported on η-Al₂O₃, ZSM-5(23) and ZSM-5(80), with and without the addition of TiO₂, were prepared and used for low temperature total methane oxidation (TMO). The catalysts were tested under reaction temperatures of 200-500 °C with a GHSV of 100,000 mL g^-1 h^-1. It was found that all four components, palladium, platinum, an acidic support and oxygen carrier were needed to achieve a highly active and stable catalyst. The optimum support being 17.5% TiO₂ on ZSM-5(80) where the T_10% was observed at only 200 °C. On addition of platinum, longer time on stream experiments showed no decrease in the catalyst activity over 50 h at 250 °C.

Ordered arrays of multiferroic epitaxial nanostructures

Epitaxial heterostructures combining ferroelectric (FE) and ferromagnetic (FiM) oxides are a possible route to explore coupling mechanisms between the two independent order parameters, polarization and magnetization of the component phases. We report on the fabrication and properties of arrays of hybrid epitaxial nanostructures of FiM NiFe(2)O(4) (NFO) and FE PbZr(0.52)Ti(0.48)O(3) or PbZr(0.2)Ti(0.8)O(3), with large range order and lateral dimensions from 200 nm to 1 micron. METHODS: The structures were fabricated by pulsed-laser deposition. High resolution transmission electron microscopy and high angle annular dark-field scanning transmission electron microscopy were employed to investigate the microstructure and the epitaxial growth of the structures. Room temperature ferroelectric and ferrimagnetic domains of the heterostructures were imaged by piezoresponse force microscopy (PFM) and magnetic force microscopy (MFM), respectively. RESULTS: PFM and MFM investigations proved that the hybrid epitaxial nanostructures show ferroelectric and magnetic order at room temperature. Dielectric effects occurring after repeated switching of the polarization in large planar capacitors, comprising ferrimagnetic NiFe2O4 dots embedded in ferroelectric PbZr0.52Ti0.48O3 matrix, were studied. CONCLUSION: These hybrid multiferroic structures with clean and well defined epitaxial interfaces hold promise for reliable investigations of magnetoelectric coupling between the ferrimagnetic / magnetostrictive and ferroelectric / piezoelectric phases.

First-Principles Study of the Electronic and Magnetic Properties of Defects in Carbon Nanostructures

Understanding the magnetic properties of graphenic nanostructures is instrumental in future spintronics applications. These magnetic properties are known to depend crucially on the presence of defects. Here we review our recent theoretical studies using density functional calculations on two types of defects in carbon nanostructures: Substitutional doping with transition metals, and sp$^3$-type defects created by covalent functionalization with organic and inorganic molecules. We focus on such defects because they can be used to create and control magnetism in graphene-based materials. Our main results are summarized as follows: i)Substitutional metal impurities are fully understood using a model based on the hybridization between the $d$ states of the metal atom and the defect levels associated with an unreconstructed D$_{3h}$ carbon vacancy. We identify three different regimes, associated with the occupation of distinct hybridization levels, which determine the magnetic properties obtained with this type of doping; ii) A spin moment of 1.0 $\mu_B$ is always induced by chemical functionalization when a molecule chemisorbs on a graphene layer via a single C-C (or other weakly polar) covalent bond. The magnetic coupling between adsorbates shows a key dependence on the sublattice adsorption site. This effect is similar to that of H adsorption, however, with universal character; iii) The spin moment of substitutional metal impurities can be controlled using strain. In particular, we show that although Ni substitutionals are non-magnetic in flat and unstrained graphene, the magnetism of these defects can be activated by applying either uniaxial strain or curvature to the graphene layer. All these results provide key information about formation and control of defect-induced magnetism in graphene and related materials.

Biobutanol as Fuel for Direct Alcohol Fuel Cells-Investigation of Sn-Modified Pt Catalyst for Butanol Electro-oxidation

Direct alcohol fuel cells (DAFCs) mostly use low molecular weight alcohols such as methanol and ethanol as fuels. However, short-chain alcohol molecules have a relative high membrane crossover rate in DAFCs and a low energy density. Long chain alcohols such as butanol have a higher energy density, as well as a lower membrane crossover rate compared to methanol and ethanol. Although a significant number of studies have been dedicated to low molecular weight alcohols in DAFCs, very few studies are available for longer chain alcohols such as butanol. A significant development in the production of biobutanol and its proposed application as an alternative fuel to gasoline in the past decade makes butanol an interesting candidate fuel for fuel cells. Different butanol isomers were compared in this study on various Pt and PtSn bimetallic catalysts for their electro-oxidation activities in acidic media. Clear distinctive behaviors were observed for each of the different butanol isomers using cyclic voltammetry (CV), indicating a difference in activity and the mechanism of oxidation. The voltammograms of both n-butanol and iso-butanol showed similar characteristic features, indicating a similar reaction mechanism, whereas 2-butanol showed completely different features; for example, it did not show any indication of poisoning. Ter-butanol was found to be inactive for oxidation on Pt. In situ FTIR and CV analysis showed that OHads was essential for the oxidation of primary butanol isomers which only forms at high potentials on Pt. In order to enhance the water oxidation and produce OHads at lower potentials, Pt was modified by the oxophilic metal Sn and the bimetallic PtSn was studied for the oxidation of butanol isomers. A significant enhancement in the oxidation of the 1° butanol isomers was observed on addition of Sn to the Pt, resulting in an oxidation peak at a potential ∼520 mV lower than that found on pure Pt. The higher activity of PtSn was attributed to the bifunctional mechanism on PtSn catalyst. The positive influence of Sn was also confirmed in the PtSn nanoparticle catalyst prepared by the modification of commercial Pt/C nanoparticle and a higher activity was observed for PtSn (3:1) composition. The temperature-dependent data showed that the activation energy for butanol oxidation reaction over PtSn/C is lower than that over Pt/C.

An effective three-dimensional ordered mesoporous CuCo2O4 as electrocatalyst for Li-O2 batteries

Three-dimensional ordered mesoporous (3DOM) CuCo₂O₄ materials have been synthesized via a hard template and used as bifunctional electrocatalysts for rechargeable Li-O₂ batteries. The characterization of the catalyst by X-ray diffractometry and transmission electron microscopy confirms the formation of a single-phase, 3-dimensional, ordered mesoporous CuCo₂O₄ structure. The as-prepared CuCo₂O₄ nanoparticles possess a high specific surface area of 97.1 m² g^{- 1} and a spinel crystalline structure. Cyclic voltammetry demonstrates that mesoporous CuCo₂O₄ catalyst enhances the kinetics for either oxygen reduction reaction (ORR) or oxygen evolution reaction (OER). The Li-O₂ battery utilizing 3DOM CuCo₂O₄ shows a higher specific capacity of 7456 mAh g^{- 1} than that with pure Ketjen black (KB). Moreover, the CuCo₂O₄-based electrode enables much enhanced cyclability with a 610 mV smaller discharge-recharge voltage gap than that of the carbon-only cathode at a current rate of 100 mA g^{- 1}. Such excellent catalytic performance of CuCo₂O₄ could be associated with its larger surface area and 3D ordered mesoporous structure. The excellent electrochemical performances coupled with its facile and cost-effective way will render the 3D mesoporous CuCo₂O₄ nanostructures as attractive electrode materials for promising application in Li-O₂ batteries.

Interface-mediated ferroelectric patterning and Mn valency in nano-structured PbTiO3/La0.7Sr0.3MnO3

We employed a multitechnique approach using piezo-force response microscopy and photoemission microscopy to investigate a self-organizing polarization domain pattern in PbTiO3/La0.7Sr0.3MnO3 (PTO/LSMO) nanostructures. The polarization is correlated with the nanostructure morphology as well as with the thickness and Mn valence of the LSMO template layer. On the LSMO dots, the PTO is upwards polarized, whereas outside the nanodots, the polarization appears both strain and interface roughness dependent. The results suggest that the electronic structure and strain of the PTO/LSMO interface contribute to determining the internal bias of the ferroelectric layer.

Electric Field Effects on Graphene Materials

Understanding the effect of electric fields on the physical and chemical properties of two-dimensional (2D) nanostructures is instrumental in the design of novel electronic and optoelectronic devices. Several of those properties are characterized in terms of the dielectric constant which play an important role on capacitance, conductivity, screening, dielectric losses and refractive index. Here we review our recent theoretical studies using density functional calculations including van der Waals interactions on two types of layered materials of similar two-dimensional molecular geometry but remarkably different electronic structures, that is, graphene and molybdenum disulphide (MoS2). We focus on such two-dimensional crystals because of they complementary physical and chemical properties, and the appealing interest to incorporate them in the next generation of electronic and optoelectronic devices. We predict that the effective dielectric constant (ε) of few-layer graphene and MoS2 is tunable by external electric fields (E ext). We show that at low fields (E ext < 0.01 V/Å) ε assumes a nearly constant value ∼4 for both materials, but increases at higher fields to values that depend on the layer thickness. The thicker the structure the stronger is the modulation of ε with the electric field. Increasing of the external field perpendicular to the layer surface above a critical value can drive the systems to an unstable state where the layers are weakly coupled and can be easily separated. The observed dependence of ε on the external field is due to charge polarization driven by the bias, which show several similar characteristics despite of the layer considered. All these results provide key information about control and understanding of the screening properties in two-dimensional crystals beyond graphene and MoS2