Effect of praseodymium oxide and cerium–praseodymium mixed oxide in the Pt electrocatalyst performance for the oxygen reduction reaction in PAFCs

The effect of praseodymium oxide and cerium–praseodymium mixed oxide in the Pt electrocatalyst performance for oxygen reduction reaction (ORR) in Phosphoric Acid Fuel Cells (PAFCs) has been studied. Three electrocatalysts (Pt/C, PtPrO _x /C and PtCe_0.9Pr_0.1O _y /C, where x and y are ≤2) have been prepared and tested by cyclic voltammetry (CV) and long term chronoamperometry (CA) experiments. The fresh and tested electrocatalysts have been characterized by X-ray diffraction (XRD) and Transmission Electron Microscopy–Energy Dispersion Spectroscopy (TEM–EDS). The Pr and Ce–Pr oxides improved Pt dispersion in the fresh electrocatalysts with regard to the Pt-only catalyst, and the PtPrO _x /C and PtCe_0.9Pr_0.1O _y /C electrocatalysts presented a slightly improved catalytic activity towards ORR in comparison to the reference Pt/C electrocatalyst. The activity decay during the long term CA tests was slower for PtPrO _x /C and PtCe_0.9Pr_0.1O _y /C than for Pt/C. Although the Pr and Ce–Pr oxides were dissolved during the CA measurements, the Pt sintering was prevented.     

Investigation of the mechanism for the separation of nitrogen—oxygen mixtures on carbon molecular sieves

Sorption separation of nitrogen-oxygen mixtures by carbon molecular sieves, e.g. to produce nitrogen using the pressure swing adsorption principle, proceeds under the condition of non-equilibrium. Experimental data based upon measurements of sorption equilibria and kinetics for nitrogen and oxygen on several samples of carbon molecular sieve particles in the temperature range 0–50°C suggest the existence of a surface barrier in the pore mouths of slit-like micropores for these particular samples. The conclusion on this phenomenon is supported by the results of canonical and grand canonical Monte Carlo simulations. Both types of analysis give a deeper insight into the complex non-equilibrium separation process.     

The reactivity of titanium–vanadium containing groups in the synthesis of two-component monolayers on silica surfaces

The coating of silica surfaces with two-component VOCl₃ and TiCl₄ monolayers was studied with respect to the composition of the products and the kinetics of interaction. The titanium and vanadium-containing groups were found to be able to replace each other equivalently. Surface sites were found to determine reactivity, as were lateral interactions in the monolayer. The results found the presence of two kinds of active center; with the estimated ratio of such groups correlating with data from chemical analyses of the concentrations of groups covalently linked to the surface by different numbers of bonds.     

Experimental investigation and thermodynamic simulation of the uranium oxide–zirconium oxide–iron oxide system in air

The behavior of melts and the phase composition of crystallization products of six compositions in the uranium oxide-zirconium oxide-iron oxide system in air have been investigated. It has been revealed that crystallized samples containing 20–50 wt % uranium oxide and 25–80 wt % iron oxide (the rest is zirconium oxide) consist of five crystalline phases and involve two types of eutectic structures. The possible factors responsible for this phenomenon have been considered.     

The effect of the change of the structure on oxidative dehydrogenation of propane over cerium–zirconium catalysts

A series of pure CeO₂, ZrO₂, and CeZrO_x mixed metal oxide catalysts were prepared by a wetness impregnation method and were applied to the dehydrogenation of propane to propylene at 500°C and 0.1 MPa. The prepared catalysts were characterized by thermal gravimetric analysis (TGA), Brunauer, Emmett, and Teller (BET), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopes (TEM), Raman spectroscopy, and H₂-TPR. It was observed that the zirconium content of the solid solution of the mixed metal oxide catalyst was 5%–25%, while the zirconium content of the material with phase segregation was higher (50%). The addition of zirconium was proven to decrease the oxygen vacancy concentration on the catalyst surface and change the intensity of (111) crystal of cerium oxide in the catalysts. Among the prepared catalysts, the Ce_0.90Zr_0.10O_x catalyst with the maximum strength of the (111) crystal plane of cerium oxide exhibited the better catalytic oxidation performance for the dehydrogenation of propane to propylene. Compared with ZrO₂ in the blank experiment, the average propane conversion and propylene selectivity of the Ce_0.90Zr_0.10O_x catalyst were increased by 10.78% and 17.95%, respectively.     

The influence of oxide–oxide interaction on the catalytic properties of Co/Al2O3 in CO hydrogenation

The influence of oxide–oxide interaction on the catalytic properties of cobalt in CO hydrogenation is investigated on the example of a Co/Al₂O₃ catalyst. Oxide–oxide interaction was prevented by modification of the alumina surface with magnesia. It has been shown that oxide–oxide interaction affects catalytic activity and the amount of carbon deposited on the catalyst surface. This revised version was published online in July 2006 with corrections to the Cover Date.     

Spectroscopic Study on the Nature of Active Entities in Copper–Ceria CO-PROX Catalysts

A series of oxidised copper-ceria catalysts with varying copper loadings and prepared by two different methods (impregnation of ceria and coprecipitation of the two components within reverse microemulsions) have been examined with the aim of determining the nature of active entities for the two main (CO and H₂) competing oxidation reactions that take place during preferential oxidation of CO in H₂-rich streams over this type of catalysts. The analysis is mainly based on operando spectroscopic exploration by DRIFTS and XANES as well as in situ analysis by Raman. The results allow establishing a model of the catalytic behaviour of this type of catalysts which can provide keys to control their CO-PROX catalytic properties.     

Influence of petrographic and mineral matter composition of coal particles on their combustion reactivity☆

Combustion at programmed temperature in a thermobalance is a rapid technique, which monitors coal burning characteristics and has shown its utility to classify coals according to their combustion performance. However, combustion profiles are affected by different coal properties and characteristics such as particle size, rank, maceral composition and mineral matter content, whose separate effects are difficult to determine. The objective of this work was to ascertain the influence of coaly and mineral matter composition and distribution on burning profiles as determined by thermogravimetric analysis, by using coals of different rank, and fractions of these coals obtained by density separation. Five coals ranging in rank from lignite to anthracite and with variable mineral matter content and composition were used in this study. Density fractions were separated from each coal to obtain samples with different organic/mineral matter proportions. Some of the factors influencing coal combustion profiles are widely recognised as the negative effect of increasing both rank and inertinite content on the reactivity. The favorable effect of mineral matter content on the reactivity has shown to be related to the maceral size within the density fractions and the intimate association organic/mineral matter that favors the diffusion of the reacting gas. Catalytic effects of the mineral matter could not be demonstrated.     

The influence of aluminum oxide on the heat resistance of the coatings based on the zirconium boride–silicon composite

The process of the formation of coatings based on zirconium boride, silicon, and aluminum oxide on graphite by the thermal treatment of the mixtures of the initial components in air has been studied. During the chemical reactions, a vitreous melt encapsulating the particles of zirconium boride and silicon is formed, which provides high heat resistance of the material. The effect of the composition, temperature, and mode of heating on the kinetics of oxidation of graphite samples with the coatings during their thermal treatment at 1400°C has been studied via the methods of thermogravimetric, thermal, and X-ray phase (XPA) analyses. The compositions of the coatings that effectively protect graphite from oxidation in air at temperatures of up to 1400°C have been proposed based on the results of the study.     

Mesoporous copper–cerium–oxygen hybrid nanostructures for low temperature catalytic oxidation of carbon monoxide

Mesoporous copper–cerium–oxygen hybrid nanostructures were prepared by one-pot cetyltrimethylammonium bromide surfactant-assisted method, and were characterized by thermogravimetry, X-ray diffraction, transmission electron microscopy, nitrogen adsorption–desorption, X-ray photoelectron spectroscopy and temperature-programmed reduction techniques. Low temperature carbon monoxide oxidation was used as probe reaction to investigate the application of the prepared mesoporous copper–cerium–oxygen hybrid nanostructures in catalysis. The product calcined at 400 °C, with disordered wormlike mesoporous structure, high specific surface area (SSA) of 117.4 m²/g and small catalyst particle size of 8.3 nm, shows high catalytic activity with the 100 % CO conversion at 110 °C, indicating its potential application in catalysis. Catalytic activity results from the samples calcinied at different temperature suggested that high SSA, small catalyst particle size, finely dispersed CuO species and synergistic effect between CuO and CeO₂ were responsible for the high catalytic activity of the catalysts.     

Detection and characterization of molybdenum oxides formed during the initial stages of cobalt–molybdenum electrodeposition

The initial stages of cobalt–molybdenum electrodeposition on a vitreous carbon electrode were studied to obtain information about the mechanism of cobalt–molybdenum induced codeposition. Solutions containing cobalt sulphate, sodium molybdate and sodium citrate at pH 6.6 were used. A first step in the mechanism of alloy deposition is proposed. This step takes into account the formation of molybdenum(IV) oxides over which Co–Mo alloy may be only deposited if sufficient potential is applied. Co–Mo electrodeposition occurs through an early stage involving low reduction current, related to the formation of molybdenum oxides, followed by a later stage in which the reduction current suddenly increases, corresponding to alloy codeposition. When a low potential is applied, a continuous coloured molybdenum oxide film is formed on the electrode and Co–Mo is not deposited. To induce the alloy deposition on the oxide film it is necessary to apply more negative potentials than a threshold value, which depends on the composition of the electrolytic bath. By increasing molybdate concentration in solution, the threshold potential shifts to more negative values. Intermediate molybdenum oxides were characterized using scanning electron microscopy (SEM), compositional analysis, Raman measurements and Auger and X-ray photoelectron spectroscopies.     

Prediction of breakthrough curves of oxygen—nitrogen coadsorption system on molecular sieves

The coadsorption breakthrough curves of oxygen—nitrogen on 5A zeolite molecular sieve (MSZ-5A) and carbon molecular sieve (MSC) are predicted theoretically and compared with experimental data. According to the binary equilibrium isotherms, the theoretical isothermal model for coadsorption fixed bed has been established under consideration of the effect of the solid phase mass transfer resistance. The breakthrough curves are obtained by solving the above model numerically for oxygen—nitrogen system in fixed beds of MSZ-5A and MSC at 293.15 K and 392 kPa. The data of pure component isotherms are used to obtain the numerical solution. The predicted curves are in good agreement with the experimental data.     

Studying the efficiency of the diesel fuel isodewaxing process on a zeolite-containing nickel–molybdenum catalyst

A GIP-14 diesel fuel isodewaxing catalyst based on a mixture of zeolites with different pore structures and entrance sizes and transition metals Ni and Mo as hydrogenating components is developed. Its stability during operation is studied. It is shown that the cold filter plugging point (CFPP) of the diesel fuel reaches values below–38°C at its yield of 92–93 wt %, temperatures of 305–310°C, and a feedstock hourly space velocity (FHSV) of 3 h^?1. A pilot diesel fuel sample is tested according to GOST (Russian State Standard) R 55475–2013. Comparative tests of domestic and foreign catalysts show that the developed GIP-14 catalyst conforms to international standards and allows the production of diesel fuel with required cold flow properties under milder conditions (300°C against 320–325°C for the foreign catalyst) at a higher FHSV (3 h^?1 against 2 h^?1). The production of GIP-14 catalyst is planned to be launched in 2017.     

Effect of the dimensions of carbon nanotube channels on copper–cobalt–cerium catalysts for higher alcohols synthesis

A series of carbon nanotube (CNT)-supported copper–cobalt–cerium catalysts were prepared and investigated for higher alcohols synthesis. The superior selectivity for the formation of ethanol and C_2 + alcohols achieved using the CuCoCe/CNT(8) catalyst was 39.0% and 67.9%, respectively. The diameters of CNTs considerably influence the distribution of metal particles and the electronic interaction between the tube surface and the active species. The electronic effect between the encapsulated Co species and the inner surface is greatly improved in the narrowest CNT channel, which is expected to facilitate the reduction of cobaltous oxide and promote the alcohols yield remarkably (291.9 mg/g_cath).     

Effects of nanosilica and titanium oxide on the performance of epoxy–amine nanocoatings

Different types of composite coatings were prepared by the blending of colloidal nanosilica (SiO₂) and titanium dioxide (TiO₂) in epoxy resin to investigate their coating performances. A fixed amount of silica nanoparticles (20 wt %) and different amounts (5, 10, and 15 wt %) of microsized TiO₂ particles were used in the coatings. The functional groups of the formulated coatings were confirmed by Fourier transform infrared spectroscopy. These results indicate that the SiO₂–TiO₂ particles interacted well with epoxy. Scanning electron microscopy images of the composite coatings revealed a good dispersion of TiO₂ particles at a lower amount of loading; this improved the adhesiveness, glass-transition temperature, thermal stability, and chemical resistance properties. At higher loadings, the performances decreased. The composite coatings were also characterized by their UV radiation-absorption properties with an ultraviolet–visible spectrophotometer. Interestingly, this property was found to be enhanced at higher loadings. An impressive result was noticed in the nanocomposites in terms of oxygen transmission rate performance compared to that of the neat epoxy. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47901.     

Preparation of the stable core–shell latex particles containing organic-siloxane in the shell

In this study, the latex particles with a polyacrylate core and a polydimethylsiloxane shell via 3-(methacryloxypropyl)-trimethoxysilane as the space arm to link the core and shell have been prepared by semi continuous seeded emulsion polymerization. And several key polymerization reaction conditions such as the emulsifier concentration, 3-(methacryloxypropyl)-trimethoxysilane dosages, feeding sequence and the acrylates/siloxanes ratio were detailedly discussed. Then, the optimal condition to prepare stable core/shell particles was selected and a proper preparation process has been established. The as-synthesized particles were characterized by TEM and XPS. The clear core/shell structure of the particles could be observed through analysis TEM. In addition, the results of XPS analyses manifested that siloxanes had been grafted on the surface of the polyacrylate particles and they distributed on the outmost layer of the particles. Finally, the surface hydrophobicity of the film formed by latex particles was investigated by the water absorption ratio measurement. The results indicated the developed latex particle provided with a fair water-repellency property.     

Effect of oxide ion donors on the corrosion and dechromization of stainless steels in KCl–NaCl–BaCl2 melt

The corrosion behaviour of several austenitic and ferritic stainless steels was studied in the KCl–NaCl–BaCl₂ melt (molar ratio 1:1:1) at 600°C in the absence and presence of 0.1 molal sodium salts with different oxyanions, namely, Na₂CO₃, Na₂O₂, Na₂SO₃, Na₂SO₄, Na₃PO₄ and Na₄P₂O₇. The corrosion rate, determined from analysis of the melt by atomic absorption, was found to agree well with that determined from anodic polarization and decreased with increasing percentage Cr in the alloy. The presence of the oxyanions led to a decrease in the corrosion rate in the order: P₂O ₇ ^4– 4 ^3– 3 ^2– 4 ^2– 2 ^2– 3 ^2– which runs parallel to the order of increasing ability of O^2– ion donation and indicates that the inhibition process involves the formation of a passivating film on the surface. All stainless steels were found to suffer a significant selective leaching of chromium and among all the oxyanions tested, only CO ₃ ^2– anions suppressed the dechromization in the KCl–NaCl–BaCl₂ melt significantly.     

Study on Shrinkage Deformation of Food in Microwave–Vacuum Drying

Drying shrinkage is an important problem in the food industry. Focusing on microwave–vacuum drying, we study the mechanism of deformation due to shrinkage of the food structure. A relationship between the strain and the water content is introduced for a finite element analysis. The temperature and water distributions are obtained by a finite difference method with the use of a variable permeability and diffusion coefficient depending on the water content. Comparisons with experimental data on radishes, carrots, and tofu indicate that the present model can express the deformation as well as the water content inside the materials.     

The multifunctional mesoporous Sn–Cu–Ti catalysts for the B–V oxidation of cyclohexanone by molecular oxygen

The multifunctional three-component mesoporous Sn–Cu–Ti samples were successfully prepared by a facile one-pot AcHE method and characterized by XRD, N₂ sorption, ICP, FT-IR, UV–vis, SEM and TEM techniques, and their catalytic performances were carried out in the B–V oxidation of cyclohexanone by molecular oxygen. The results show that both tin and copper species can homogeneously incorporated in the crystalline framework of mesoporous anatase TiO₂, where tin species as the active sites would increase the Lewis acidity and the oxidation of benzaldehyde as pro-oxygenic agent would be promoted by the introduction of little copper species resulting in the improving catalytic performance. The prepared 15Sn–3Cu–Ti catalyst shows higher yield of ε-caprolactone than other catalysts and exhibits excellent catalytic stability even after repeated reaction for five times without any further treatment. The outstanding catalytic performance for Sn–Cu–Ti catalysts could offer a valuable reference for the industrial development of B–V oxidation of cyclohexanone.