Surfactant-Free Monodispersed Pd Nanoparticles Template for Core-Shell Pd@PdPt Nanoparticles as Electrocatalyst towards Methanol Oxidation Reaction (MOR)

An eco-friendly two-step synthetic method for synthesizing Pd@PdPt/CNTs nanoparticles was introduced and studied for the methanol oxidation reaction. The Pd@PdPt alloy core-shell structure was synthesized by preparing a surfactant-free monodispersed Pd/CNTs precursor through the hydrolysis of tetrachloropalladate (II) ion ([PdCl4]2−) in the presence of carbon nanotubes (CNTs) and the subsequent hydrogen reduction and followed by a galvanic replacement reaction. This method opens up an eco-friendly, practical, and straightforward route for synthesizing monometallic or bimetallic nanoparticles with a clean surfactant-free electrocatalytic surface. It is quite promising for large-scale preparation. The Pd@PdPt/CNTs electrocatalyst demonstrated a high specific mass activity for methanol oxidation (400.2 mAmgPt−1) and excellent stability towards direct methanol oxidation compared to its monometallic counterparts.

Improvement of Mechanical Properties of Hard Metals Using Solid Solution Strengthened Metallic Binder (Co1-xWx)

The metallic binder in WC-Co hard metals was effectively strengthened using the solid solution phases of Co and W. These metallic phases of Co and W (Co1-xWx, x<1), which consist of two kinds of structures (FCC and HCP), were successfully formed by hydrogen reduction of milled oxides mixtures (Co3O4 and WO3) at over 1000 oC. When hard metals are fabricated by pressureless sintering of mixed WC and Co1-xWx, the hard metals containing the WC2 and M6C phases (Co2W4C and Co4W2C) have brittleness, which degrades their mechanical properties, like hard metals fabricated from mixtures of WC, Co, and W. By rapidly sintering the WC-Co1-xWx hard metals for 5 min the WC2 and M6C phases were eliminated, and a two-phase (WC and the metallic phase of Co and W) region was successfully obtained. The mechanical properties of the WC-Co1-xWx hard metals showed higher values for both hardness (max. 18.8 GPa) and fracture toughness (8.5 MPa·m1/2) than conventional WC-Co hard metal (HV: 15.9 GPa, KIC: 6.9 MPa·m1/2). The enhancement in toughness was attributed to the solid solution strengthening of the metallic binder and the elimination of the WC2 and M6C phases. The suppression of grain growth due to the short duration of sintering also played a positive role in improving the hardness of the WC-Co1-xWx hard metals. The phase-controlled solid solution metallic binder could be the key material to enhance the hardness and toughness of hard metals.

Sintering Behavior and Hardness of Tungsten Prepared by Hard Metal Sludge Recycling Process without Ammonium Paratungstate

In this paper, we suggest a novel recycling process for hard metal sludge that does not use ammonium paratungstate. Ammonia, which in the conventional recycling process is essential for removing sodium and crystallized tungstate, was not used in the novel process. Instead of ammonia, acid was used to remove the sodium and crystallized tungstate resulting in the formation of tungstic acid (H2WO4). Tungsten powders were successfully synthesized by hydrogen reduction of the tungstic acid through H2O decomposition, WO3 to WO2 reduction, and tungsten metal formation. The tungsten powders prepared from tungstic acid were spherical in shape and had a higher sintering density than the facet-shaped tungsten powders prepared from tungsten oxide. The spherical shape of the tungsten powders enhanced their sinterability and resulted in an increase in the size of grains. This is a result of the high diffusion rate of the atoms along the particle surfaces. Despite having a higher density, the hardness of the sintered tungsten was lower than that of tungsten from tungsten oxide. High energy milling effectively reduced grain size and improved hardness. The hardness of the tungsten prepared from milled tungstic acid was enhanced to a value (max. 471 HV) higher than the best previously reported value (389 HV). In sum, tungsten can be hardened, thereby improving its sinterability and reducing grain size, with tungstic acid prepared using the proposed recycling process.

ELECTROCATALYTIC COBALT-VANADIUM COATINGS FOR THE HYDROGEN EVOLUTION REACTION

The study of existing energy-saving materials and obtaining the new ones for reducing the cost of the hydrogen production, is relevant for modern hydrogen energy industry. Such properties can be predicted for materials containing vanadium, molybdenum, tungsten and exhibiting catalytic activity for the hydrogen evolution reaction Aforementioned metals can be co-deposited from aqueous solutions with iron subgroup metal-catalysts through the formation of cluster intermetallic compounds with Me-V bond adsorbed on the cathode surface. The induced co-deposition of cobalt with vanadium from the complex citrate electrolyte was investigated in the current work. As a result of the research, it was found that the uniform microcrystalline light-gray high-quality cobalt-vanadium alloy coating is possible to precipitate from a citrate electrolyte with content of 20 g/dm3 vanadium (in terms of metal) as a citrate complex The process was carried out at a current density of 5–10 A/dm2, at a temperature of 30–40°С, pH = 2,8–3,2. The content of vanadium in the coating is 0,37–0,53 % by weight. The maximum vanadium content in the coating is observed at current densities 8–9 А/dm2. The catalytic activity study of the coating that was obtained using cobalt-vanadium alloy in the reaction of hydrogen reduction at the cathode was performed in solution of 2,5М NaOH + 0,02 M NaCl. By increasing the vanadium content in the coating from 0,37 to 0,53% the hydrogen evolution overvoltage is reduced by 0,5 V. It was found that the overvoltage of the hydrogen ion evolution reaction on cathodes from steel 20 with cobalt-vanadium coating is 0.08–0,1 V lower, and the exchange current is higher than on electrodes made of steel 20, which are used in industrial water-alkali electrolysis. This indicates the electrocatalytic activity of the investigated materials for the hydrogen evolution reaction. Electrodes with coating, obtained by cobalt-vanadium alloy can be recommended as a cathode material for the hydrogen electrochemical production. Hydrogen evolution overvoltage reduction also decrease the energy consumption for this process by 15–20 %.

Hydrogen Diffusion and Adsorption on WO3 (001) based on First Principles Calculation

Hydrogen reduction of tungsten oxide is currently the most widely applied ultrafine tungsten powder production process. The process has the advantage of short, pollution free and simple production equipment. But it is difficult to effectively control the morphology and particle size of the tungsten powder because of lacking in-depth understanding of the dynamic mechanism of the process. The first-principles calculations are carried out to explore the diffusion and internal adsorption of hydrogen on the WO-terminated surface of WO3 based on the density functional theory. The results show that hydrogen can diffuse from the WO terminal surface to the inside of WO3, the activation energy of diffusion is 46.682 Kcal/mol. It’s preferable for hydrogen to diffuse from the surface to the inside than diffuse within the WO3 lattice. The adsorption energy of hydrogen on the WO termination surface of WO3 is 15.093 Kcal/mol, the adsorption energy of hydrogen inside the WO termination surface of WO3 is 14.116 Kcal/mol, which means the hydrogen is easier to adsorb inside the WO3 lattice.