Direct-hydrothermal synthesis of LiFe<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>PO<Subscript>4</Subscript> cathode materials

Carbon free LiFe_1−x Mn _x PO₄ (x = 0, 0.05, 0.1, 0.2, 0.4) cathode materials were prepared by a direct-hydrothermal process at 170 °C for 10 h. The structural and electrochemical properties of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), charge–discharge experiments, cyclic voltammetry (CV) and alternating current (AC) impedance spectroscopy. The electrochemical performance of LiFePO₄ prepared in this manner showed to be positively affected by Mn²⁺-substitution. Among the Mn²⁺-substitution samples, the LiFe_0.9Mn_0.1PO₄ exhibited an initial discharge capacity of 141.4 mA h g⁻¹ at 0.1 C, and the capacity fading is only 2.7% after 50 cycles.     

Spatial localization of holes in La<Subscript>2 − <Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>CuO<Subscript>4</Subscript>

The parameters of the tensor of the electric field gradient (EFG) in cation sites of the La_{2 ? x} Sr _x CuO₄ lattice have been determined by the method of emission Mössbauer spectroscopy on ⁵⁷Co(^57m Fe), ⁶⁷Cu(⁶⁷Zn), ⁶⁷Ga(⁶⁷Zn), and ¹⁵⁵Eu(¹⁵⁵Gd) isotopes. There is no quantitative agreement between the calculated (the pointcharge model) and experimental values of the main component of the tensor EFG V _zz , which is explained by the absence of the reliable data on the Sternheimer coefficients for Fe³⁺, Zn²⁺, and Gd³⁺ ions. Based on the comparison of the calculated and experimental dependences of V _zz on x it was shown that the holes appearing during the substitution of La³⁺ for Sr²⁺ are localized preferably on the oxygen atoms that are in the same plane as the copper atoms, which is in agreement with the model discussed in the literature and assumes that the mechanism responsible for the high-temperature superconductivity of solid solutions La_{2 ? x} Sr _x CuO₄ is the interaction between the conductivity electrons and two-atomic two-electron centers with negative correlation energy.     

Synthesis of La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3 + δ</Subscript> manganites by pyrohydrolysis of nitrates

Single-phase finely dispersed perovskite-like manganites La_{1 ? x} Sr _x MnO_{3 + δ} (0 ≤ x ≤ 0.33) with an average particle size of approximately 3μm were synthesized by the pyrohydrolytic method from a stoichiometric mixture of the corresponding metal nitrates at a temperature of 500°C in a water vapor atmosphere. The parameter δ was changed as a result of the subsequent heat treatment. It was established that the manganite La_0.67Sr_0.33MnO_{3 + δ} synthesized by the pyrohydrolytic method is characterized by a more pronounced change in the magnetoresistance as compared to the manganite that had the same composition but was synthesized according to the conventional ceramic technique.     

Investigation of the Meyer-Neldel rule for AC conduction in glassy Se<Subscript>100 − <Emphasis Type="Italic">x</Emphasis></Subscript>Te<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> alloys

In many amorphous and liquid semiconductors and other class of materials, the Meyer-Neldel rule is observed in the dc conductivity, where the preexponential factor (σ₀) is found to increase exponentially with the activation energy (ΔE). In the present paper, we report on the observation of the Meyer-Neldel rule in case of ac conductivity at high temperatures (300–350 K) in bulk samples of glassy Se_{100 − x} Te _x (x = 10, 20, 30) alloys. In this temperature range, the approximate variation in ac conductivity with temperature is found to be exponential and the activation energy is found to vary with frequency. The observation of the Meyer-Neldel rule in the present study is explained in terms of the compensation effect in the relaxation time. The text was submitted by the authors in English.     

Rh<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Pd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Nanoparticle Composition Dependence in CO Oxidation by NO

Abstract  

Bimetallic 15 nm Pd-core Rh-shell Rh_1−x Pd _x nanoparticle catalysts have been synthesized and studied in CO oxidation by NO. The catalysts exhibited composition-dependent activity enhancement (synergy) in CO oxidation in high NO pressures. The observed synergetic effect is attributed to the favorable adsorption of CO on Pd in NO-rich conditions. The Pd-rich bimetallic catalysts deactivated after many hours of oxidation of CO by NO. After catalyst deactivation, product formation was proportional to the Rh molar fraction within the bimetallic nanoparticles. The deactivated catalysts were regenerated by heating the sample in UHV. This regeneration suggests that the deactivation was caused by the adsorption of nitrogen atoms on Pd sites.     

Magnetic and structural inhomogeneities of the La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3 + δ</Subscript> manganites

The specific features revealed in the behavior of the parameters of the crystal structure and the lattice dynamics of the La_{1 ? x} Ca _x MnO_{3 + δ} manganites upon the transition to a magnetically ordered state are investigated using X-ray powder diffraction and inelastic neutron scattering. The results obtained are explained in terms of an inhomogeneous state of the samples. This state manifests itself in the form of local regions that are enriched or depleted in charge carriers, with the former regions characterized by the highest temperature of ferromagnetic ordering in the system under investigation. A comparison of the evolution of the crystal structure with variations in the temperature both in the presence and in the absence of a magnetic field has demonstrated that the inhomogeneities are eliminated by an external magnetic field and that the regions enriched in charge carriers become predominant in the system.     

Fabrication of Coaxial Si<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ge<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Heterostructure Nanowires by O<Subscript>2</Subscript> Flow-Induced Bifurcate Reactions

We report on bifurcate reactions on the surface of well-aligned Si_1−x Ge _x nanowires that enable fabrication of two different coaxial heterostructure nanowires. The Si_1−x Ge _x nanowires were grown in a chemical vapor transport process using SiCl₄ gas and Ge powder as a source. After the growth of nanowires, SiCl₄ flow was terminated while O₂ gas flow was introduced under vacuum. On the surface of nanowires was deposited Ge by the vapor from the Ge powder or oxidized into SiO₂ by the O₂ gas. The transition from deposition to oxidation occurred abruptly at 2 torr of O₂ pressure without any intermediate region and enables selectively fabricated Ge/Si_1−x Ge _x or SiO₂/Si_1−x Ge _x coaxial heterostructure nanowires. The rate of deposition and oxidation was dominated by interfacial reaction and diffusion of oxygen through the oxide layer, respectively.     

Synthesis and proton incorporation in BaCe<Subscript>0.9−<Emphasis Type="Italic">x</Emphasis></Subscript>Zr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Y<Subscript>0.1</Subscript>O<Subscript>3−δ</Subscript>

BaCe_0.9−x Zr _x Y_0.1O_3−δ powders were synthesized by a solid-state method at 1,400 °C. Two compositions were studied (x = 0.3 and x = 0.7). Pellets were prepared and conventionally sintered in air at 1,700 °C. Then, the samples were heated at 600 °C for 3 h in different reducing atmospheres: dry hydrogen, wet hydrogen and wet deuterium. After each treatment, the proton diffusion depth profile was obtained using Secondary Ion Mass Spectroscopy (SIMS). Protons were not incorporated in the material when the gas was not wet, and the isotope effect suggests that protons present in the pellet come from water and not from hydrogen.     

Kinetics of stepwise bulk crystallization of AsSe<Subscript>1.5</Subscript>Sn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> (<Emphasis Type="Italic">x</Emphasis> ≤ 0.28) glasses

The kinetics of stepwise transformations during bulk isothermal crystallization of semiconducting AsSe_1.5Sn _x (x = 0.13, 0.20, 0.28) glasses has been studied in the temperature range of 210?310°С using ¹¹⁹Sn Mössbauer spectroscopy, XPA, and the density and microhardness measurements of the quenched specimens. The kinetics of the gross bulk crystallization of glasses have been analyzed according to the data on density measurement using the Kolmogorov–Avrami equation, which was generalized on stepwise and incomplete isothermal transformations.     

Optical absorption and disorder in the As<Subscript>40</Subscript>S<Subscript>60 − <Emphasis Type="Italic">x</Emphasis></Subscript>Se<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> vitreous alloys

The absorption edge spectra of vitreous alloys in the As-S-Se system are measured in the temperature range 77–300 K. The parameters of the fundamental absorption edge and the electron-phonon interaction in As₄₀S_{60 ? x} Se _x (x = 0–40) glasses are determined, and the influence of the compositional disorder on these parameters is investigated. The contributions of the static structural and temperature disorders to the smearing of the fundamental absorption edge of the alloys under study are evaluated.     

Photoelectrochemical Properties of NiO Coupled with TiO<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>N<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Thin Film Prepared by Magnetron Sputtering Method

TiO_2−x N _x films were deposited on ITO glass by reactive dc magnetron sputtering method under different O₂/N₂ flow ratios. A NiO film was deposited by chemical bath deposition onto the as-prepared ITO/TiO_2−x N _x film to form an ITO/TiO_2−x N _x /NiO composite electrode. The morphology, crystal structure and composition of the TiO_2−x N _x films were characterized by SEM, XRD and XPS. The photoelectrochemical properties of the TiO_2−x N _x films were investigated by means of UV–Vis absorption spectra and photocurrent measurements. The results showed that the TiO_2−x N _x film sputtered under O₂/N₂ flow ratio of 1:2 exhibited a higher photocurrent response than the others. Correspondingly, the TiO_2−x N _x /NiO electrode consisting of the sputtered TiO_2−x N _x film under O₂/N₂ flow ratio of 1:2 also showed the best photoelectrochromic feature.     

Effect of oxidation states of Mn in Ca<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Li<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> on chemical-looping combustion reactions

We investigated the effect of the oxidation state of Mn in CaMnO₃ perovskite particles to improve their oxygen transfer performance for chemical-looping combustion (CLC). Li was introduced in the Ca site of CaMnO₃ to increase the Mn oxidation state. Ca_1?x Li _x MnO₃ particles were synthesized by the solid-state method, and the amount of Li added ranged from 0 to 0.015 mol. The structure of the synthesized Ca_1?x Li _x MnO₃ particles was examined using XRD, and all particles were confirmed to have a CaMnO₃ perovskite structure. The shape and chemical properties of the prepared particles were characterized by using SEM and CH₄-TPD. The binding energy and oxidation state of the different elements in the Ca_1?x Li _x MnO₃ particles were measured by XPS. When Li was added, the oxidation state of Mn in Ca_1?x Li _x MnO₃ was higher than that of Mn in CaMnO₃. The oxygen transfer performance of the particles was determined by an isothermal H₂-N₂/air and CH₄-CO₂/air redox cycle at 850 °C, repeated ten times, using TGA. All particles showed an oxygen transfer capacity of about 8.0 to 9.0 wt%. Among them, Ca_0.99Li_0.01MnO₃ particles had the best performance and the oxygen transfer capacity under H₂-N₂/air and CH₄-CO₂/air atmosphere was 8.47 and 8.75 wt%, respectively.     

Solid Solution (AlN)<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>(SiC)<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript> (<Emphasis Type="Italic">x</Emphasis> ≈ 0.7) by SHS under High Pressure of Nitrogen Gas

Solid solution (AlN) _x (SiC)_1–x (x = 0.7) was prepared from Al–SiC mixtures by SHS under high pressure of nitrogen gas (50, 70 MPa) and characterized by XRD and SEM. Combustion product was found to have a wurtzite 2H structure with lattice parameters a = 3.10889 ± 0.00022 Å and c = 5.00741 ± 0.00080 Å.     

Thermal expansion and phase transitions in K<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Cs<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>BSi<Subscript>2</Subscript>O<Subscript>6</Subscript> borosilicate solid solutions

Solid solutions K_{1 − x} Cs _x BSi₂O₆ (x (atomic fraction) = 0.00, 0.20, 0.30, 0.35, 0.40, 0.80, 0.90,1.00) have been prepared by solid-phase synthesis and crystallization of glasses in the KBSi₂O₆-CsBSi₂O₆ borosilicate series. The thermal behavior of the solid solutions has been investigated using the annealing and quenching techniques, dilatometry, and high-temperature X-ray powder diffraction. It has been shown that solid solutions with x = 0.00–0.35 and 0.40–1.00 correspond to space groups I $ \bar 4 $ \bar 4 3d and I a $ \bar 3 $ \bar 3 d, respectively. The cubic-cubic phase transition I $ \bar 4 $ \bar 4 3d ai Ia $ \bar 3 $ \bar 3 d occurs in the composition range x = 0.35−0.40 at room temperature. In the series of solid solutions with x = 0−0.30, the reversible cubic-cubic polymorphic transition I $ \bar 4 $ \bar 4 3d ai ia $ \bar 3 $ \bar 3 d with an increase in the temperature has been revealed, the temperature of the polymorphic transition has been determined, and the thermal expansion in both polymorphic modifications has been studied using high-temperature X-ray diffraction and dilatometry. The solid solutions belonging to the space group Ia $ \bar 3 $ \bar 3 d are characterized by a lower thermal expansion than the solid solution belonging to the space group I $ \bar 4 $ \bar 4 3d. According to the calculations, the equivalents α/γ for the space groups I $ \bar 4 $ \bar 4 3d and Ia $ \bar 3 $ \bar 3 d are 0.03 and 0.02 (in cesium atomic fractions per degree Celsius), respectively.     

Sol-Gel Synthesis,Thermal Behavior of Nanopowders and Chemical Stability of La<Subscript>1 – <Emphasis Type="Italic">x</Emphasis></Subscript>Ho<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>PO<Subscript>4</Subscript> Ceramic Matrices

Nanosized powders of orthophosphates in the LaPO₄–HoPO₄–H₂O system have been synthesized to determine the mutual solubility of LaPO₄ · nH₂O and HoPO₄ · nH₂O initial components and to obtain ceramic matrices by sintering them. Formation of hexagonal, monoclinic or tetragonal solid solutions was revealed, and their limits and thermal stability were determined. A series of limited hexagonal LaPO₄ · nH₂O-based solid solutions was observed within the 0 ≤ x ≤ 0.6 concentration range up to 600°C. Further they transformed to monoclinic LaPO₄-based form within the 0 ≤ x ≤ 0.3 concentration range. Solubility of LaPO₄ · nH₂O and LaPO₄ in tetragonal HoPO₄(· nH₂O) is lower (≤10 mol %). Specific surface area of La_1–xHo_xPO₄ · nH₂O powders was in the range of 90.5–165.0 m²/g depending on x. Leaching rate of La³⁺ and Ho³⁺ from La_1–xHo_xPO₄ matrices in nitric acid solution (pH 1–2) was determined to be 10^–5–10^–2 g/(cm² day) for both ions.     

Electrochemical properties of amorphous Li<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>V<Subscript>2</Subscript>O<Subscript>5−<Emphasis Type="Italic">y</Emphasis></Subscript> thin film deposited by r.f.-sputtering

The electrochemical properties of amorphous vanadium pentoxide (V₂O₅) thin films deposited by reactive r.f.-sputtering were investigated using galvanostatic charge/discharge cycling and galvanostatic intermittent titration technique (GITT). As x in Li _x V₂O_5−y increased (x = 0–2.0), the electromotive force of the lithium (Li)∣1 M LiClO₄–propylene carbonate∣Li _x V₂O_5−y cell decreased gradually without a potential plateau or an abrupt potential reduction, demonstrating that an irreversible structural change did not occur in the entire Li content. Chemical diffusivity of the Li ion in the Li _x V₂O_5−y thin film measured using GITT was determined to be 4 × 10⁻¹³–7 × 10⁻¹⁴ cm² s⁻¹ in the Li content range investigated.     

Thermal expansion and phase transitions in K<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Rb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>BSi<Subscript>2</Subscript>O<Subscript>6</Subscript> leucite borosilicate solid solutions

Continuous solid solutions and the reversible phase transition from the I-43d cubic phase to the Ia-3d cubic phase are revealed in the borosilicate series K_{1 ? x} Rb _x BSi₂O₆. Samples in the KBSi₂O₆-RbBSi₂O₆ system are prepared by solid-phase synthesis and crystallization of glasses and investigated using the annealing and quenching technique, high-temperature X-ray diffraction, and dilatometry. The above polymorphic phase transition is observed in all solid solutions at temperatures in the range from 330 to 430°C depending on the composition: an increase in the rubidium content in the solid solution leads to a gradual decrease in the phase transition temperature. The linear thermal expansion coefficients α are determined for solid solutions of different crystalline modifications and glasses. The linear thermal expansion coefficients α for the I-43d low-temperature phase are equal to (20–23) × 10^?6 K^?1 according to the X-ray diffraction data and (21–24) × 10^?6 K^?1 according to the dilatometric data. The values of α for the Ia-3d high-temperature phase lie in the range (4–9) × 10^?6 K^?1 according to the X-ray diffraction data and in the range (6–9) × 10^?6 K^?1 according to the dilatometric data. The linear thermal expansion coefficients for both modifications decrease with an increase in the rubidium content in the solid solutions. The linear thermal expansion coefficients for glasses α = (10–11) × 10^?6 K^?1 are close to those for the high-temperature modification and virtually independent of the sample composition. The I-43d (cubic) ai I4₁/a (tetragonal) o Ia-3d (cubic) polymorphic phase transitions in the KBSi₂O₆ compound are revealed by differential scanning calorimetry (DSC) and dilatometry. Their reversibility is confirmed by the DSC data.     

Features of the Growth of Thread-Like <Emphasis Type="Italic">x</Emphasis>InSe(1 – <Emphasis Type="Italic">x</Emphasis>)In<Subscript>2</Subscript>O<Subscript>3</Subscript> Crystals of Two-Layer PbSe and In Films

Lead and indium selenide films with an area of 3 × 3 mm² and thickness of ~1 μm each are deposited successively by thermal vacuum deposition on C-29 glass substrates. The films are heat-treated in a dry air atmosphere at a temperature of 550°С. X-ray microanalysis and scanning electron microscopy show the possibility of the formation of the thread-like nanocrystals of a xInSe(1 – x)In₂O₃ composite from two-layer PbSe and In films deposited on glass substrates in the process of heat treatment in an air atmosphere.     

Synthesis of Highly Effective CeO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>–MnO<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>–BaO Catalysts for Direct NO Decomposition

Abstract  

Ce–Mn mixed oxides with a Mn/(Ce + Mn) molar ratio of 0.25 were prepared by solvothermal (ST-1) and co-precipitation (CP) methods, and Ba was loaded on the Ce–Mn oxides. In addition, CeO₂–MnO _x –BaO catalysts with various compositions were directly prepared by the solvothermal (ST-2) method. The NO decomposition activities of these catalysts were examined. Among the catalysts examined, the ST-2 catalyst having a nominal composition of Ce_0.8Mn_0.15Ba_0.05O _x exhibited the highest activity; 77% NO conversion to N₂ was attained at 800 °C. These catalysts were characterized by X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The Raman and XPS results indicate that the CP catalyst had larger amounts of the BaMnO_3-δ and/or Mn₃O₄ phases. The ST-1 and ST-2 catalysts had highly dispersed Ba species on the surface. The ST-2 catalyst had Mn species with the lowest binding energy of Mn 2p and also had a high population of oxygen vacancies in the ceria lattice, suggesting that Mn species with a low oxidation state contributes to the formation of oxygen vacancies, which play an important role in this reaction.     

Effects of various factors on capacitive properties of VO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>·<Emphasis Type="Italic">n</Emphasis>H<Subscript>2</Subscript>O powders in aqueous electrolyte

In this work, effects of drying temperature, pH of aqueous electrolyte and current density on capacitive performance of VO _x ·nH₂O material were firstly investigated. VO _x ·nH₂O powders were prepared by a melt quenching method. The samples were characterized by X-ray diffraction analysis (XRD) and Fourier transform infrared (FTIR). The capacitive properties of VO _x ·nH₂O samples were examined by cyclic voltammetry and galvanostatic charge/discharge test. VO _x ·nH₂O sample which was obtained at the drying temperature of 80 °C, delivers a maximum specific capacitance of 227.3 F g⁻¹ and exhibits excellent capacity retention in the potential range of −0.3 to 0.7 V at a current density of 200 mA g⁻¹ in NaNO₃ solution with pH 2.