Structural, optical, and magnetic properties of NiMoO4 nanorods prepared by microwave sintering

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Theoretical and experimental studies on the electronic, optical, and structural properties of poly-pyrrole-2-carboxylic acid films

A theoretical approach is used here to explain experimental results obtained from the electrosynthesis of polypyrrole-2-carboxylic acid (PPY-2-COOH) films in nonaqueous medium. An analysis of the Fukui function (reactivity index) indicates that the monomer (pyrrole-2-carboxylic acid, PY-2-COOH), and dimers and trimers are oxidized in the C4 or C5 positions of the heterocyclic ring of the PY-2-COOH structure. After calculating the heat of formation using semiempirical Austin Model 1 post-Hartree-Fock parameterization for dimer species, both C4 and C5 positions adjacent to the aromatic rings of PPY-2-COOH were considered the most susceptible ones to oxidative coupling reactions. The ZINDO-S/CI semiempirical method was used to simulate the electronic transitions typically seen in the UV-VIS-NIR range in monomer and oligomers with different conjugation lengths. The use of an electrochemical quartz crystal microbalance provides sufficient information to propose a polymerization mechanism of PY-2-COOH based on molecular modeling and experimental results.

Supramolecular coordination complexes as building blocks for porous and magnetic materials

In this work, new coordination polymers based on two different classes of synthons are presented. In addition, manganese-based metallacrowns of magnetic interest are studied, both in the solid state and in solution. Firstly, functionalized bispyrazolylmethane derivatives are employed as bridging ligands for the establishment of silver-based coordination polymers; the influence of the substituent groups and of the counterions on the supramolecular packing is also investigated. Secondly, the use of metallacrown (MC) complexes as building blocks for porous coordination polymers is discussed. The design of a new metallacrown species is presented, which shows the tendency of aggregating in the solid state to form coordination polymers. Two new coordination polymers are indeed reported, of which one is the first MC-based permanently porous coordination network ever presented. The solid resists solvent evacuation and exhibits gas uptake ability. Furthermore, the isolation and characterization of a new metallacryptate species based on manganese ions is described. The metal-rich structure comprises nine Mn(II)/Mn(III) ions and presents an inverse metallacrown core subunit that binds a μ3-O2- ion. The metallacryptate is isolated in high yields and stable in solution. Lastly, a family of 3d-4f heterometallic metallacrowns is characterized in solution by means of UV-Vis spectrophotometry and of paramagnetically shifted 1H-NMR. The lanthanide-induced shifts observed in the spectra are employed to describe the molecules behaviour in solution and are qualitatively related to the magnetic properties of the compounds.

Fabrication and evaluation of NiO/Y2O3-stabilized-ZrO2 hollow fibers for anode-supported micro-tubular solid oxide fuel cells

In this work NiO/3mol% Y₂O₃-ZrO₂ (3YSZ) and NiO/8mol% Y₂O₃-ZrO₂ (8YSZ) hollow fibers were prepared by phase-inversion. The effect of different kinds of YSZ (3YSZ and 8YSZ) on the porosity, electrical conductivity, shrinkage and flexural strength of the hollow fibers were systematically evaluated. When compared with Ni-8YSZ the porosity and shrinkage of Ni-3YSZ hollow fibers increases while the electrical conductivity decreases, while at the same time also exhibiting enhanced flexural strength. Single cells with Ni-3YSZ and Ni-8YSZ hollow fibers as the supported anode were successfully fabricated showing maximum power densities of 0.53 and 0.67Wcm^-2 at 800°C, respectively. Furthermore, in order to improve the cell performance, a Ni-8YSZ anode functional layer was added between the electrolyte and Ni-YSZ hollow fiber. Here enhanced peak power densities of 0.79 and 0.73Wcm^-2 were achieved at 800°C for single cells with Ni-3YSZ and Ni-8YSZ hollow fibers, respectively.

Preparation and characterization of Pr0.6Sr0.4FeO3-δ-Ce0.9Pr0.1O2-δ nanofiber structured composite cathode for IT-SOFCs

In this work, Pr_0.6Sr_0.4FeO_3-δ -Ce_0.9Pr_0.1O_2-δ (PSFO-CPO) nanofibers were synthesized by a one-step electrospin technique for use in intermediate-temperature solid oxide fuel cell (IT-SOFC) applications. PSFO-CPO nanofibers were produced with a diameter of about 100nm and lengths exceeding tens of microns. The thermal expansion coefficient (TEC) matches with standard GDC electrolytes and the resulting conductivity also satisfies the needs of IT-SOFCs cathodes. EIS analysis of the nanofiber structured electrode gives a polarization resistance of 0.072Ωcm² at 800°C, smaller than that from the powdered cathode with the same composition. The excellent electrochemical performance can be attributed to the well-constructed microstructure of the nanofiber structured cathode, which promotes surface oxygen diffusion and charge transfer processes. All the results imply that the one-step electrospin method is a facile and practical way of improving the cathode properties and that PSFO-CPO is a promising cathode material for IT-SOFCs.

Fabrication and characterization of SSZ tape cast electrolyte-supported solid oxide fuel cells

A 10 mol%Sc₂O₃, 1 mol%CeO₂ stabilized-ZrO₂ (SSZ) powder was successfully prepared using the sol-gel method. Subsequent SSZ electrolyte pellets were prepared by tape casting technique and sintered at 1400 °C, 1450 °C, 1500 °C, 1550 °C and 1600 °C. These were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). SSZ showed a pure cubic phase after sintering, the grain size of SSZ increased with the increase of sintering temperature. The SSZ sintered at 1550 °C showed the highest ion conductivity. The maximum power densities of Ni-SSZ/SSZ/La_0.8Sr_0.2MnO_3-δ (LSM)-SSZ single cells sintered at 1550 °C were 0.18, 0.36, 0.51 and 0.72 W cm^-2 at 650, 700, 750 and 800 °C, respectively. The polarization resistance (R_p) of the single cell attained 0.201 Ω cm² at 800 °C.

Design and Flux-Weakening Control of an Interior Permanent Magnet Synchronous Motor for Electric Vehicles

Permanent magnet synchronous motors (PMSMs) provide a competitive technology for EV traction drives owing to their high power density and high efficiency. In this paper, three types of interior PMSMs with different PM arrangements are modeled by the finite element method (FEM). For a given amount of permanent magnet materials, the V-shape interior PMSM is found better than the U-shape and the conventional rotor topologies for EV traction drives. Then the V-shape interior PMSM is further analyzed with the effects of stator slot opening and the permanent magnet pole chamfering on cogging torque and output torque performance. A vector-controlled flux-weakening method is developed and simulated in Matlab to expand the motor speed range for EV drive system. The results show good dynamic and steady-state performance with a capability of expanding speed up to four times of the rated. A prototype of the V-shape interior PMSM is also manufactured and tested to validate the numerical models built by the FEM.

Fibrillar Elastomeric Micropatterns Create Tunable Adhesion Even to Rough Surfaces

Acknowledgements V.B., N.K.G., and E.A. contributed with conception and experimental design. V.B. performed the experiments. V.B., R.H., A.G., and R.M.M. carried out analysis and interpretation of data. V.B., R.H., A.G., and E.A. wrote the manuscript. V.B. and R.H. contributed equally to this work. V.B. acknowledges funding by SPP 1420 of the German Science Foundation DFG. E.A., N.K.G., and R.H. acknowledge funding from the European Research Council under the European Union/ERC Advanced Grant “Switch2Stick,” Agreement No. 340929.

Highlights from Faraday Discussion: Designing New Heterogeneous Catalysts, London, UK, April 2016

The Faraday Discussion on the design of new heterogeneous catalysts took place from 4-6 April 2016 in London, United Kingdom. It brought together world leading scientists actively involved in the synthesis, characterisation, modelling and testing of solid catalysts, attracting more than one hundred delegates from a broad spectrum of backgrounds and experience levels-academic and industrial researchers, experimentalists and theoreticians, and students. The meeting was a reflection of how big of an impact the ability to control and design catalysts with specific properties for particular processes can potentially have on the chemical industry, environment, economy and society as a whole. In the following, we give an overview of the topics covered during this meeting and briefly highlight the content of each presentation.

Acid-mediated topological control in a functionalized foldamer

Induced conformational change provides a powerful mechanism to modulate the structure and function of molecules. Here we describe the synthesis of chiral, surface-functionalized oligomeric pyridine/imidazolidin-2-one foldamers, and interrogate their acid-mediated transition between linear and helical topologies.

The infared optical properties of Sr2RuO4 and SmTiO3 including an object-oriented resistivity interface /

The perovskite crystal structure is host to many different materials from insulating to superconducting providing a diverse range of intrinsic character and complexity. A better fundamental description of these materials in terms of their electronic, optical and magnetic properties undoubtedly precedes an effective realization of their application potential. SmTiOa, a distorted perovskite has a strongly localized electronic structure and undergoes an antiferromagnetic transition at 50 K in its nominally stoichiometric form. Sr2Ru04 is a layered perovskite superconductor (ie. Tc % 1 K) bearing the same structure as the high-tem|>erature superconductor La2_xSrrCu04. Polarized reflectance measurements were carried out on both of these materials revealing several interesting features in the far-infrared range of the spectrum. In the case of SmTiOa, although insulating, evidence indicates the presence of a finite background optical conductivity. As the temperature is lowered through the ordering temperature a resonance feature appears to narrow and strengthen near 120 cm~^ A nearby phonon mode appears to also couple to this magnetic transition as revealed by a growing asymmetry in the optica] conductivity. Experiments on a doped sample with a greater itinerant character and lower Neel temperature = 40 K also indicate the presence of this strongly temperature dependent mode even at twice the ordering temperature. Although the mode appears to be sensitive to the magnetic transition it is unclear whether a magnon assignment is appropriate. At very least, evidence suggests an interesting interaction between magnetic and electronic excitations. Although Sr2Ru04 is highly anisotropic it is metallic in three-dimensions at low temperatures and reveals its coherent transport in an inter-plane Drude-like component to the highest temperatures measured (ie. 90 K). An extended Drude analysis is used to probe the frequency dependent scattering character revealing a peak in both the mass enhancement and scattering rate near 80 cm~* and 100 cm~* respectively. All of these experimental observations appear relatively consistent with a Fermi-liquid picture of charge transport. To supplement the optical measurements a resistivity station was set up with an event driven object oriented user interface. The program controls a Keithley Current Source, HP Nano-Voltmeter and Switching Unit as well as a LakeShore Temperature Controller in order to obtain a plot of the Resistivity as a function of temperature. The system allows for resistivity measurements ranging from 4 K to 290 K using an external probe or between 0.4 K to 295 K using a Helium - 3 Cryostat. Several materials of known resistivity have confirmed the system to be robust and capable of measuring metallic samples distinguishing features of several fiQ-cm.