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Orlovskaya, Nina

Publications and source records attributed to Orlovskaya, Nina.

Interface synergism and engineering of Pd/Co@N-C for direct ethanol fuel cells

Direct ethanol fuel cells have been widely investigated as nontoxic and low-corrosive energy conversion devices with high energy and power densities. It is still challenging to develop high-activity and durable catalysts for a complete ethanol oxidation reaction on the anode and accelerated oxygen reduction reaction on the cathode. The materials’ physics and chemistry at the catalytic interface play a vital role in determining the overall performance of the catalysts. Herein, we propose a Pd/Co@N-C catalyst that can be used as a model system to study the synergism and engineering at the solid-solid interface. Particularly, the transformation of amorphous carbon to highly graphitic carbon promoted by cobalt nanoparticles helps achieve the spatial confinement effect, which prevents structural degradation of the catalysts. The strong catalyst-support and electronic effects at the interface between palladium and Co@N-C endow the electron-deficient state of palladium, which enhances the electron transfer and improved activity/durability. The Pd/Co@N-C delivers a maximum power density of 438 mW cm -2 in direct ethanol fuel cells and can be operated stably for more than 1000 hours. This work presents a strategy for the ingenious catalyst structural design that will promote the development of fuel cells and other sustainable energy-related technologies.

25 ENERGY STORAGE↗

Time and frequency dependent mechanical properties of LaCoO 3 -based perovskites: Neutron diffraction and domain mobility

The study of domain wall movement and texture formation in ferroelastic LaCoO 3 perovskite under constant applied compressive stress has been performed using in situ neutron diffraction. Additionally, it was established that under constant applied compressive stress the domain walls show mobility that may lead both to the shrinkage (creep strain) and to the expansion (negative creep strain) of LaCoO 3 perovskite. The domain wall movement and texture formation can be explained by the availability, mobility, and interaction of twins, stacking faults, antiphase boundaries, dislocations, and point defects, such as oxygen vacancies and their complexes as well as impurity atoms. Lastly, the equation of motion was used to describe the possible mechanisms of domain wall movement under applied stress, and it was determined that the available solutions of this equation allow both for the shrinkage (creep strain) and for the expansion (negative creep strain) of LaCoO 3 perovskite to occur.

36 MATERIALS SCIENCE↗

Non-congruence of high-temperature mechanical and structural behaviors of LaCoO 3 based perovskites

Our paper presents the mechanical behavior of LaCoO 3 and La 0.8 Ca 0.2 CoO3 ceramics under four-point bending in which the two cobaltites are subjected to a low stress of ~8 MPa at temperatures ranging from room temperature to 1000 °C. Unexpected stiffening is observed in pure LaCoO 3 in the 700–900 °C temperature range, leading to a significant increase in the measured Young’s modulus, whereas La 0.8 Ca 0.2 CoO 3 exhibits softening from 100 °C to 1000 °C, as expected for most materials upon heating. we use neutron diffraction, X-ray diffraction and micro-Raman spectroscopy to study the crystal structure of the two materials in the RT–1000 °C temperature range. Despite a detailed study, there is no conclusive evidence to explain the stiffening behavior observed in pure LaCoO 3 as opposed to the softening behavior in La 0.8 Ca 0.2 CoO 3 at high temperatures (above 500 °C).

36 MATERIALS SCIENCE↗

Oxygen interaction with hexagonal OsB 2 at high temperature

The stability of ReB 2 -type hexagonal OsB 2 powder at high temperature with oxygen presence has been studied by thermogravimetric analysis, differential scanning calorimetry, SEM, EDS, and high-temperature scanning transmission electron microscopy and XRD. Results of the study revealed that OsB 2 ceramics interact readily with oxygen present in reducing atmosphere, especially at high temperature and produces boric acid, which decomposes on the surface of the powder resulting in the formation of boron vacancies in the hexagonal OsB 2 lattice as well as changes in the stoichiometry of the compound. It was also found that under low oxygen partial pressure, sintering of OsB 2 powders occurred at a relatively low temperature (900°C). Finally, hexagonal OsB 2 ceramic is prone to oxidation and it is very sensitive to oxygen partial pressures, especially at high temperatures.

36 MATERIALS SCIENCE↗

In search of the elusive IrB{sub 2}: Can mechanochemistry help?

The previously unknown hexagonal ReB{sub 2}-type IrB{sub 2} diboride and orthorhombic IrB monoboride phases were produced by mechanochemical syntheses. High energy ball milling of elemental Ir and B powder for 30 h, followed by annealing of the powder at 1050 °C for 48 h, resulted in the formation of the desired phases. Both traditional laboratory and high resolution synchrotron X-ray diffraction (XRD) analyses were used for phase identification of the synthesized powder. In addition to XRD, scanning electron microscopy and transmission electron microscopy were employed to further characterize the microstructure of the phases produced. - Graphical abstract: ReB{sub 2}-type IrB{sub 2} and a new IrB have been successfully synthesized for the first time using mechanochemical method. Crystal structures of IrB{sub 2} and IrB were studied by synchrotron X-ray diffraction. Microstructures of the new phases were characterized by SEM and TEM. - Highlights: • ReB{sub 2}-type IrB{sub 2} and a new IrB have been synthesized by mechanochemical method. • Crystal structures of IrB{sub 2} and IrB were studied by synchrotron XRD. • Microstructures of the new phases were characterized by SEM and TEM.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High temperature Ir segregation in Ir-B ceramics: Effect of oxygen presence on stability of IrB 2 and other Ir-B phases

The formation of IrB 2 , IrB 1.35 , IrB 1.1 and IrB monoboride phases in the Ir–B ceramic nanopowder was confirmed during mechanochemical reaction between metallic Ir and elemental B powders. The Ir–B phases were analysed after 90 h of high energy ball milling and after annealing of the powder for 72 h at 1050°C in vacuo . The iridium monoboride (IrB) orthorhombic phase was synthesised experimentally for the first time and identified by powder X-ray diffraction. Additionally, the ReB 2 type IrB 2 hexagonal phase was also produced for the first time and identified by high resolution transmission electron microscope. Ir segregation along disordered domains of the boron lattice was found to occur during high temperature annealing. Furthermore, these nanodomains may have useful catalytic properties.

36 MATERIALS SCIENCE↗

Hexagonal OsB 2 : Sintering, microstructure and mechanical properties

In this study, the metastable high pressure ReB 2 -type hexagonal OsB 2 bulk ceramics was produced by spark plasma sintering. The phase composition, microstructure, and mechanical behavior of the sintered OsB 2 were studied by X-ray diffraction, optical microscopy, TEM, SEM, EDS, and nanoindentation. The produced ceramics was rather porous and contained a mixture of hexagonal (~80 wt.%) and orthorhombic (~20 wt.%) phases as identified by X-ray diffraction and EBSD analysis. Two boron-rich phases, which do not contain Os, were also identified by TEM and SEM/EDS analysis. Nanoindentation measurements yielded a hardness of 31 ± 9 GPa and Young’s modulus of 574 ± 112 GPa, indicating that the material is rather hard and very stiff; but, it is very prone to crack formation and propagation, which is indicative of a very brittle nature of this material. Improvements in the sintering regime are required in order to produce dense, homogeneous and single phase hexagonal OsB 2 bulk ceramics.

36 MATERIALS SCIENCE↗