Electrodeposited Copper Nanocatalysts for CO2 Electroreduction: Effect of Electrodeposition Conditions on Catalysts’ Morphology and Selectivity

Catalytic electroreduction of carbon dioxide represents a promising technology both to reduce CO2 emissions and to store electrical energy from discontinuous sources. In this work, electrochemical deposition of copper on to a gas-diffusion support was tested as a scalable and versatile nanosynthesis technique for the production of catalytic electrodes for CO2 electroreduction. The effect of deposition current density and additives (DAT, DTAB, PEG) on the catalysts’ structure was evaluated. The selectivity of the synthesized catalysts towards the production of CO was evaluated by analyzing the gaseous products obtained using the catalysts as cathodes in electroreduction tests. Catalyst morphology was deeply influenced by the deposition additives. Copper nanospheres, hemispherical microaggregates of nanowires, and shapeless structures were electrodeposited in the presence of dodecyltrimethylammonium bromide (DTAB), 3,5-diamino-1,2,4-triazole (DAT) and polyethylene glycol (PEG), respectively. The effect of the deposition current density on catalyst morphology was also observed and it was found to be additive-specific. DTAB nanostructured electrodes showed the highest selectivity towards CO production, probably attributable to a higher specific surface area. EDX and XPS analysis disclosed the presence of residual DAT and DTAB uniformly distributed onto the catalysts structure. No significant effects of electrodeposition current density and Cu(I)/Cu(II) ratio on the selectivity towards CO were found. In particular, DTAB and DAT electrodes yielded comparable selectivity, although they were characterized by the highest and lowest Cu(I)/Cu(II) ratio, respectively.

Efficient Preparation of Nanoparticle-Reinforced Nickel-based Composite Coating with Highly Preferred (220) Orientation

Nanoparticle-reinforced metal matrix composite coatings have significant potential in mechanical part surface strengthening owing their excellent mechanical properties. This paper reports a phenomenon in which the grain orientation gradually evolves to (220) as the deposition current density increases when preparing nanoparticle-reinforced nickel-based composite coatings through jet electrodeposition (JED). During the preparation of the Ni-SiC composite coatings, the deposition current density increased from 180 A/dm2 to 220 A/dm2, and TC(220) gradually increase from 41.4% to 97.7%. With an increase of TC(220), the self-corrosion potential increases from −0.575 to −0.477 V, the corrosion current density decreases from 9.52 μA/cm2 to 2.76 μA/cm2, the diameter of the corrosion pits that after 10 days of immersion in a 3.5 wt% NaCl solution decreases from 278–944 nm to 153–260 nm, and the adhesion of the coating increases from 24.9 N to 61.6 N. Compared a conventional electrodeposition (CED), the Ni-SiC composite coating using JED has the advantages of a smooth surface morphology, high corrosion resistance, and strong adhesion, which are more obvious with an increase in TC(220).

ELECTROCATALYSIS OF THE HYDROGEN EVOLUTION REACTION ON CoRe, CoWRe SUPERALLOYS DEPOSITED FROM CITRATE ELECTROLYTE

The reaction of electroreduction of hydrogen ions on binary CoRe and ternary CoWRe alloys electrodeposited from a citrate electrolyte with different amount of potassium perrhenate (0.01 and 0.05 mol·L-1) depending on the deposition current density (5–40 A·cm-2) has been investigated by the method of stationary voltammetry. The kinetic parameters of the reaction have been calculated, and it is shown that the use of ternary alloys allows one to increase the value of exchange current density by almost an order of magnitude and significantly reduce the overvoltage of hydrogen reduction in comparison with cobalt. It is shown that the best electrocatalysts for the reduction of hydrogen in alkaline solution can be ternary CoWRe alloys with a rhenium content of 15–20 at. %.

Efficient Preparation of Nanoparticles Reinforced Nickel-based Composite Coating with Highly Preferred (220) Orientation

Nanoparticles reinforced metal matrix composite coatings have great application potential in mechanical parts surface strengthening due to their excellent mechanical properties. This paper reports a phenomenon that the grain orientation gradually evolves to (220) with the deposition current density increasing when preparing nanoparticles reinforced nickel-based composite coatings by jet electrodeposition (JED). During the preparation of Ni-SiC composite coatings, the deposition current density increases from 180 A/dm2 to 220 A/dm2, and TC(220) gradually increases from 41.4% to 97.7% correspondingly. With the increase of TC(220), the self-corrosion potential increases from -0.575 V to -0.477 V, the corrosion current density decreases from 9.52 μA·cm2 to 2.76 μA·cm2, the diameter of corrosion pits that after 10 days of immersion in 3.5 wt% NaCl solution decreases from 278~944 nm to 153~260 nm, and the adhesion of the coating is increased from 24.9 N to 61.6 N. Compared with conventional electrodeposition (CED), the Ni-SiC composite coating prepared by JED has the advantages of smooth surface morphology, corrosion resistance and strong adhesion, which is more obvious with the increase of TC (220).

Efficient Preparation of Nanoparticles Reinforced Nickel-based Composite Coating with Highly Preferred (220) Orientation

This paper reports a phenomenon that the grain orientation gradually evolves to (220) with the deposition current density increasing when preparing nanoparticles reinforced nickel-based composite coatings by jet electrodeposition (JED). During the preparation of Ni-SiC composite coatings, the deposition current density increases from 180 A/dm2 to 220 A/dm2, and TC(220) gradually increases from 41.4% to 97.7% correspondingly.The Ni-SiC composite coating with highly preferred (220) orientation has superior corrosion resistance and adhesion force. With the increase of TC(220), the surface roughness is reduced from Ra1.210 μm to Ra0.119 μm, the self-corrosion potential increases from -0.747 V to -0.477 V, the corrosion current density decreases from 54.52 μA·cm2 to 2.76 μA·cm2, the diameter of corrosion pits that after 10 days of immersion in 3.5 wt% NaCl solution decreases from 3.3~22.2 μm to 153~260 nm, and the adhesion of the coating is increased from 20.5 N to 61.6 N.The research results can provide theoretical and technical support for the preparation of new composite coatings with high efficiency, low cost, high adhesion and strong corrosion resistance.

PECULIARITIES OF ELECTRODEPOSITION OF COBALT—WOLFRAM—RENIUM ALLOY

The methods of stationary voltammetry and chronovoltammetry have been used to study deposition processes of ternary CoWRe alloys at different rhenium content of the electrolyte and deposition current density. It has been found that the limiting currents have a diffusive nature and are proportional to the concentration of perrhenate ions in the electrolyte. The CoWRe alloys should be formed by the discharge of bimetallic citrate complexes of the following composition [(Co)(WO4)(H)(Cit)]2- and rhenium electrodeposition. Rhenium does not form complexes with citrate ions and deposits better in an alloy with iron group metals than in the form of an individual metal from a perrhenate solution. It can be assumed that the discharge of rhenium into the alloy occurs from a surface complex, the nature of which has not yet been established. The alloy current efficiency reaches 93% due to the high overpotential of hydrogen evolution on the alloy surface. According to the results of investigations of the catalytic properties of alloys in the hydrogen reduction reaction, it has been found that with increasing the rhenium content of the electrolyte and alloy, an increase in hydrogen overpotential is observed. Based on the Tafel coefficients found, it was found that in an acidic and neutral medium, the limiting stage of the cathodic and anodic reaction is the transfer of the first electron. In an alkaline medium, the anode process is complicated by the simultaneous transport of two electrons. The found values of corrosion resistance are 1-2 kOm·cm-2 in solutions of 0.01 M H2SO4; 20-110 kOm·cm-2 in 2.5% NaCl; 10-30 kOm·cm-2 in 1.0 M KOH. Based on the dependence of corrosion resistance on the refractory metals content of the alloy and the electrodeposition conditions, the optimum deposition current density of 10 mA·cm-2 has been found.

Effect of deposition current density and annealing temperature on the microstructure and magnetic properties of nanostructured Ni-Fe-W-Cu alloys

Ni-Fe-W-Cu alloy powders were obtained by electrodeposition from an ammonium citrate bath at current densities ranging between 70 and 600 mA cm-2. As the deposition current density increased, the contents of Fe and W in the alloy increased, and those of Ni and Cu decreased. The total cathodic polarization curve was recorded, and partial polarization curves for Ni, Fe and W deposition and hydrogen evolution were determined. The current efficiency of alloy deposition was measured. The powders contained an amorphous matrix and FCC nanocrystals of the solid solution of Fe, W and Cu in Ni. At high current densities, small-sized nanocrystals exhibiting high internal microstrain values were formed. Powder particles were dendrite- and cauliflower-shaped. The dendrites had a large number of secondary branches and higher-order branches containing interconnected globules. The density of branches was higher in particles formed at high current densities. The powders formed at high current densities exhibited higher magnetization. Annealing at temperatures up to 460?C resulted in structural relaxation, accompanied by an increase in magnetization. At temperatures above 460?C, amorphous matrix crystallization and FCC crystal growth took place, accompanied by a decrease in magnetization.

Electrodeposition process and composition of Zn-Cr alloy coatings

In the present work, the electrodeposition process of Zn-Cr alloy coatings under the conditions of direct and pulse current was discussed. Changes in the Cr content in the obtained alloy coatings, current efficiency of the process, surface morphology, structure and microhardness as a function of chromium(III) concentration in the bath to deposition, current density (direct and pulse) and solution mixing were determined. Surface morphology, structure and hardness of the obtained coatings were investigated. The Zn-Cr alloy coatings of good quality contained up to 0.25 %Cr (for direct current) and up to 9% Cr (for pulse current). The tested Zn-Cr alloy coatings obtained under pulse current conditions showed higher microhardness than the Zn-Cr coatings obtained under direct current conditions and than zinc coatings.