Electrochemical reactivity of Li–Mn–O and Li–Fe–Mn–O spinels

Electrochemical reductive dissolution of Li–Mn–O and Li–Fe–Mn–O spinels and Li⁺ extraction/insertion in these oxides were performed using voltammetry of microparticles. Both electrochemical reactions are sensitive to the Fe/(Fe+Mn) ratio, specific surface area, Li content in tetrahedral positions, and Mn valence, and can be used for electrochemical analysis of the homogeneity of the elemental and phase composition of synthetic samples. The peak potential (E _P) of the reductive dissolution of the Li–Mn–O spinel is directly proportional to the logarithm of the specific surface area. E _P of Li–Fe–Mn–O spinels is mainly controlled by the Fe/(Fe+Mn) ratio. Li⁺ insertion/extraction can be performed with Mn-rich Li–Fe–Mn–O spinels in aqueous solution under an ambient atmosphere and it is sensitive to the regularity of the spinel structure, in particularly to the amount of Li in tetrahedral positions and the Mn valence. Electronic Publication     

Structural relaxation of PbO–WO3–P2O5 glasses

The structural relaxation of three compositional series of PbO–WO₃–P₂O₅ glasses with composition (0.5 ? x/2)PbO·xWO₃·(0.5 ? x/2)P₂O₅, x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5; 0.5PbO·xWO₃·(0.5 ? x)P₂O₅, x = 0, 0.1, 0.2, and 0.3; and (0.5 ? x)PbO·xWO₃·0.5P₂O₅, x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5 was studied by thermomechanical analysis. The structural relaxation was studied in the transformation region using the Tool–Narayanaswamy–Moynihan’s and Tool–Narayanaswamy–Mazurin’s models. The relaxation function of Kohlrausch Williams and Watts was used. The parameters of both models were calculated by nonlinear regression analysis of thermodilatometric curves measured by thermomechanical analyzer under the constant load. Both models very well describe the experimental data. It was found that the modulus is increasing with increasing amount of WO₃ in all glasses. On the contrary, the width of the spectrum of relaxation times is decreasing with increasing amount of WO₃ in all studied glasses. Both models possess the values of metastable melt thermal expansion coefficient equal to their experimental value.     

Kinetics of nonisothermal crystallization of Cs2O–Fe2O3–P2O5 glasses

The crystallization kinetics of Cs₂O–Fe₂O₃–P₂O₅ glasses containing 12.5–27 mol% Cs₂O were studied by using differential scanning calorimetry under nonisothermal conditions. Strong dependence of activation energy with temperature was observed, indicating the complex nature of the crystallization process. The various crystallization products were identified by X-ray diffraction technique. CsFeP₂O₇ was found to be the major crystalline phase in all cases. The overall activation energy obtained by classical model-free kinetic method was compared with that of isoconversional method; and from the results, the dependence of activation energy on extent of reaction and average temperature was delineated.     

Specific features of phase equilibriums in Ln–Ba–Fe–O systems

Formation of five-layered Ln_2–εBa_3+εFe₅O_15–δ phases [exhibiting nanoscale ordering with layer-by-layer location of the cations in the Ln–Ba–(Ln,Ba)–(Ln,Ba)–Ba–Ln perovskite-type structure] has occurred in the Ln–Ba–Fe–O (Ln = Y, Pr, Nd, Sm, Eu, and Gd) systems at 1100°С in air. Partial substitution of iron with cobalt (Ln_2–εBa_3+εFe_5–yCo_yO_15–δ, Ln = Nd, Sm, Eu) has stabilized formation of the ordered structure. The oxygen content in the complex oxides has been determined in air over a wide temperature range by means of high-temperature thermogravimetry and iodometric titration. The change in oxygen content with temperature for the phases with five-layered ordering was significantly smaller than for the disordered phases.     

Thermal properties of Na2O–P2O5–Fe2O3 polyphosphate glasses

Journal of Thermal Analysis and Calorimetry - Iron phosphate glasses are materials that can have many applications like durable matrixes in waste immobilization techniques, biomaterials,...     

Fuel Combustion Reactions and Catalysts: XXI. Synthesis and Characterization of Modified Mn–Al–O Catalysts for High-Temperature Oxidation

The phase composition of supported Mn–Al–O catalysts and their activity in the reaction of methane oxidation were studied depending on the composition of aluminum oxide supports (-Al₂O₃ with different -Al₂O₃ contents modified with individual Mg, La, and Ce oxides or Mg + La and Mg + Ce oxide mixtures) and calcination temperatures (500, 900, and 1300°C). It was found that the Mn–Al–O catalysts based on -alumina containing -Al₂O₃ and modified with Mg, La, or Ce additives are more active and thermally stable (up to 1300°C) than the samples based on pure -Al₂O₃. A conclusion was drawn that a higher degree of disorder of the structure of -Al₂O₃, compared to that of -Al₂O₃, is favorable for a deeper interaction of manganese and modifying additives with the support at the early stages of the synthesis and for the formation of Mn–Al compounds with complex composition (solid solutions and/or hexaaluminates) at 1300°C. These compounds are responsible for the stability and high activity of the catalysts in methane oxidation.     

Reversible Structural Transformations of Metal–Organic Frameworks as Artificial Switchable Catalysts for Dynamic Control of Selectively Cyanation Reaction

The synthesis of molecular-level artificial switchable catalysts, of which activity in different chemical processes can be switched by controlling different stimuli, has provided a new paradigm to perform mechanical tasks and measurable work. In this work, to obtain highly effective and regioselective artificial switchable catalysts, a hierarchical anion-pillared framework {(H₃O)[Cu(CPCDC)(4,4′-bpy)]}_n ( 1 ; H₃CPCDC=9-(4-carboxyphenyl)-9H-carbazole-3,6-dicarboxylic acid, 4,4′-bpy=4,4′-bipyridine), including free [H₃O]⁺ ions as guest molecules, was constructed. Upon dissolve–exchange–crystallization behavior, fascinating reversible structural transformations proceeded between anion framework 1 and neutral 2D stair-stepping framework {[Cu(CPCDC)(4,4′-bpe)]}_n ( 2 ; 4,4′-bpe=4,4′-vinylenedipyridine). Moreover, frameworks 1 and 2 can act as heterogeneous artificial switchable catalysts to selectively promote the direct cyanation reaction of terminal alkynes and azobisisobutyronitrile. The results indicated that 1 and 2 exhibited excellent selectivity to generate vinyl isobutyronitrile skeletons or propiolonitrile frameworks, respectively, as unique products. Furthermore, indicating paper, GC-MS, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy analysis demonstrated that the reversible structural transformations endowed 1 and 2 with well-defined platforms to stabilize the isobutyronitrile and CN sources through the different catalytic pathways.     

Electrodeposition and lithium storage performance of novel three-dimensional porous Fe–Sb–P amorphous alloy electrode

The three-dimensional porous Fe–Sb–P amorphous alloy electrodes were prepared by electroplating on porous copper current collector. The structure and electrochemical performance of the electroplated Fe–Sb–P amorphous alloy electrodes have been investigated in detail. XRD results showed that the as-deposited Fe–Sb–P alloy electrode exhibits an amorphous nature. Electrochemical tests indicated that at the 50th cycle, the Fe–Sb–P amorphous alloy electrodes can deliver a discharge capacity of 448 mAh g^?1. The porous and amorphous structure of electrode of Fe–Sb–P alloy was beneficial in relaxing the volume expansion during cycling, which improved the cycle ability of Fe–Sb–P alloy electrode.     

Synthesis and some properties of a new compound in the Al–Sb–V–O system

A new compound in the Al?CSb?CV?CO system of the composition AlSbVO₆ was successfully synthesized by a solid-state reaction and characterized by powder XRD diffraction. The structural and thermal properties of AlSbVO₆ were investigated. The infra-red spectrum of the new phase is presented.     

Mixed Platinum–Nickel Catalysts of Oxygen Reduction

Russian Journal of Electrochemistry - A mixed catalyst based on platinum and nickel oxide was obtained as a result of the synthesis and subsequent alkaline hydrolysis of thin polymer films of...     

In vitro biological evaluations of Fe3O4 compared with core–shell structures of chitosan-coated Fe3O4 and polyacrylic acid-coated Fe3O4 nanoparticles

Research on Chemical Intermediates - Today the use of magnetic nanoparticles (MNPs) is widely investigated because of their biocompatibility and nontoxicity. The objective of this study was to...     

Experimental study of Fe–C–O based system above 1,000 °C

The paper deals with the study of phase transformation temperatures of the model Fe–C–O based metallic alloys in the high temperature region (above 1,000 °C). Six model alloys with graded carbon and oxygen content were prepared and studied. Temperatures of phase transitions were obtained using DTA method (differential thermal analysis). The Setaram SETSYS 18? (TG/DTA/DSC/TMA) modular experimental system was used for measurements. Influence of composition change (carbon and oxygen content) on shift of phase transformation temperatures is investigated in this paper. New original data (phase transformation temperatures) were obtained in this study. Controlled heating of the alloys was conducted at the rates of 2, 4, 7, 10, 15 and 20 °C min^?1. Comparison of the obtained experimental data with the data presented in the literature was also carried out. It follows from comparison of the obtained results with the data accessible in the literature that a lack of experimental data exists, and these available data significantly differ.     

Experimental study of Fe–C–O based system below 1000 °C

The paper deals with the study of phase transformation temperatures of Fe (Fe–C–O) based metallic alloys. Six model alloys with graded carbon and oxygen content were used for experimental investigation. Low-temperature region (<1000 °C) was the investigated area. Phase transformation temperatures were obtained using Differential thermal analysis and Setaram Setsys 18_TM laboratory system. Controlled heating was conducted at the rates of 2, 4, 7, 10, 15, 20 °C min^?1. Region of eutectoid transformation (Fe_α(C) + Fe₃C → Fe_γ(C)), alpha–gamma (Fe_α(C) → Fe_γ(C)) and transformation Fe_α(O) + Fe_0.92O → Fe_γ(O) + Fe_0.92O was studied. New original data (phase transformation temperatures) were obtained in this study. The relationship between shift of phase transformation temperatures and chemical composition (mainly carbon and oxygen content) is investigated in this paper. To achieve good approximation to the equilibrium conditions, the extrapolation of the obtained phase transformation temperatures to the zero heating rate was performed. The influence of experimental conditions (heating rate) on temperatures of phase transformations was studied as well. Comparison of the obtained experimental data with the data presented in the accessible literature and IDS calculations (Solidification Analysis Package) was carried out. It follows from literature search that there is a lack of thermo-physical and thermo-dynamical data on Fe–C–O system.     

Structural Properties of Glass-Forming Ethanol and Glycerol From O–H Vibrational Spectra

The O–H stretching vibrations of hydrogen-bonded glass formers (ethanol and glycerol) are studied by Raman scattering in a temperature range where the liquid state changes from low-viscous to solid. Several characteristic bands exhibiting different temperature behavior can be distinguished in the O–H vibrational spectrum of ethanol. The appearance of an additional band on cooling ethanol below 220 K is related to the appearance of locally favored structures. No notable manifestations of these features are detected in the spectra of glycerol.     

Structural studies of copper-containing multicomponent glasses from the SiO2–P2O5–K2O–CaO–MgO system

Multicomponent glasses from the SiO₂–P₂O₅–K₂O–MgO–CaO–CuO system acting as slow release fertilizers were synthesized by the melt-quenching technique. The influence of CuO and P₂O₅ addition on the structure of glasses was evaluated by FTIR, Raman, ³¹P, and ²⁹Si MAS NMR spectroscopies. The studies showed that the Cu²⁺ ions displacing Ca²⁺ ions and Mg²⁺ ions in the structure of glass prefer to associate with the phosphorus Q¹ species, forming the Q⁰ species with chemically stable POCu bonds. This is accompanied by the reduction of the degree of polymerization of the phospho-oxygen sub-network, with a simultaneous increased degree of polymerization of the silico-oxygen sub-network of the silicate–phosphate glasses.     

In Situ X-Ray Absorption Spectroscopy Studies of Carbon Monoxide Oxidation in the Presence of Nanocomposite Cu–Fe–Al Oxide Catalysts

Kinetics and Catalysis - Nanocomposite Fe–Al and Cu–Fe–Al oxide catalysts are studied in the CO oxidation reaction. It is shown that the introduction of copper leads to a more...     

Preparation and electrocatalytic performance of Fe–N–C for electroreduction of H2O2

Fe–N–C catalysts were prepared through metal-assisted polymerization method. Effects of carbon treatment, Fe loading, nitrogen source, and calcination temperature on the catalytic performance of the Fe–N–C for H₂O₂ electroreduction were measured by voltammetry and chronoamperometry. The Fe–N–C catalyst shows optimal performance when prepared with pretreated active carbon, 0.2 wt.% Fe, paranitroaniline (4-NA) and one-time calcination. The Fe–N–C catalyst displayed good performance and stability for electroreduction of H₂O₂ in alkaline solution. An Al–H₂O₂ semi-fuel cell was set up with Fe–N–C catalyst as cathode and Al as anode. The cell exhibits an open-circuit voltage of 1.3 V and its power density reached 51.4 mW cm⁻² at 65 mA cm⁻².     

The effect of mechanical activation on the thermal reactions of P2O5–Al2O3–Fe2O3–Na2O phosphate glasses

The effect of mechanical activation on the structure and thermal reactions of glasses has been studied on the example of Na–Al–Fe phosphate glasses. These glasses are used in nuclear technology for immobilization of radioactive waste. The glasses were activated by grinding in a planetary mill. Mechanical activation causes a decrease of the T _g temperature as well as of the glass crystallization temperature. The type of crystalline phases formed and the quantitative proportions between them are changing. Analysis of inter-atomic interactions in the structure of glass was applied to explain the observed regularities governing the crystallization of the activated glasses.