Mutual Influence of Electrode Processes during Electrodeposition of Layered Structures by a Single-Bath Method: Effect of Nickel Deposition and Hydrogen Evolution on the Mass Transfer of Copper in a Sulfosalicylate Electrolyte

The work justifies the selection of a sulfosalicylate copper–nickel electrolyte and its composition for obtaining nanostructures comprising alternate magnetic and nonmagnetic layers by a single-bath method. According to calculations of an equilibrium composition of the electrolyte and electrodiffusion fluxes of discharging species, in a neutral region of pH copper exists in the form of multicharged anions CuSSA^3–, and the migration effects must reduce the rate of the mass transfer of copper-containing species with increasing current of the parallel reaction of discharge of nickel ions. Dependences of the partial current density of copper deposition on the electrode potential are studied at various values of pH of the copper and copper–nickel electrolytes. Experimental results are analyzed on the basis of modeling concepts. It is shown that the drop of the partial current density of copper deposition below its limiting value at potentials of deposition of a magnetic layer is connected with the emergence of migration effects.     

Effect of Chloride Ions on the Behavior of Saccharin, N-Methylsaccharin, and 2-Butyne-1,4-diol during Electrodeposition of Nickel from Acid Electrolytes

Rates of transformation of organic additives (saccharin, N-methylsaccharin, 2-butyne-1,4-diol) and accumulation of products of their cathodic reactions are studied during nickel electrodeposition from the chloride and Watts electrolytes. A large concentration of chloride ions accelerates the saccharine and N-methylsaccharin consumption due accelerated synthesis of o-toluenesulfamide, N-methyl-o-toluenesulfamide, and N-methylbenzylsultam, thus facilitating adsorption of additives on the nickel cathode via the carbonyl group. An inhibition of adsorption via the sulfonyl group is accompanied by a decrease in the accumulation of corresponding benzamides. An increase in the concentration of chloride ions in electrolytes containing 2-butyne-1,4-diol promotes accumulation of 2-buten-1,4-diol and inhibits hydrogenation of the double bond to a saturated bond. Differences in the behavior of the additives are due to (i) competition of chloride ions with the additives in the electrolyte or with their electroreduction products during adsorption on the nickel cathode, (ii) a change in the deposit potential, and (iii) a change in the concentration of inclusions in the deposits, which determine the catalytic activity of the cathode.     

Effect of Transition Element Ions on the Catalytic Activity of Titanium Dioxide during Chemical Deposition of Metallic Copper

We have established the high catalytic activity of TiO₂, modified by Pd²⁺, Cu²⁺, Fe³⁺, and Co²⁺ ions, in reduction of Cu²⁺ ions by formaldehyde in solution. We propose a likely scheme for the electronic processes that occur, including injection of electrons from the reducing agent into the conduction band and formation of metallic nanoparticles on the surface that effectively catalyze deposition of metallic copper.     

直流电电化学沉积镍制备原位生长碳纳米管化学修饰电极

利用直流电电化学沉积法将生长碳纳米管(CNT)的催化剂镍均匀地附着在石墨电极(GE)表面,再通过化学气相沉积法制备得到原位生长碳纳米管化学修饰电极(GSCNT-CME).电化学沉积的金属镍和所制备的修饰电极分别用光学显微镜、扫描电子显微镜(SEM)和电子能谱(EDX)进行表征,所得修饰电极的电化学性能用[Fe(CN)6]3-/[Fe(CN)6]4-溶液进行表征.结果表明:经直流电电化学沉积,可以在石墨电极表面沉积一层致密的金属镍,能生长出管径均匀的碳纳米管,所制得的修饰电极具有良好的电化学响应灵敏性和准确性,可在电化学检测领域发挥重要的应用.     

Mo对脱合金制备的Ni-Mo电极骨架结构与析氢性能的影响

采用快速凝固结合脱合金化方法制备了不同Mo含量的纳米多孔Ni-Mo合金,通过X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）和N₂吸附-脱附分析等对多孔合金的物相、形貌结构及孔径分布进行了表征,并通过线性扫描伏安、Tafel斜率、交流阻抗和循环伏安等方法测试了多孔合金电极的电催化析氢性能.结果显示,多孔合金电极材料在50 mA/cm²电流密度下析氢过电位随着Mo含量的增加先降低后升高,Ni_2.5Mo_2.5合金析氢活性最强,过电位为218 mV,析氢过程由Volmer-Heyrovsky步骤控制,交换电流密度为0.29 mA/cm²,经1000周循环后的极化曲线基本保持原状,50 mA/cm²电流密度下过电位增加3.67%,表现出优良的析氢稳定性.     

电沉积法制备铂纳米粒子过程中卤素阴离子对粒子形貌及电催化性质的影响

在电化学沉积铂纳米粒子的过程中, 通过添加卤素阴离子, 可以显著地改变纳米粒子的形貌. 通过添加氯离子、溴离子和碘离子, 可以在导电基底上分别获得球形、片状及立方结构的铂纳米粒子. 对卤素阴离子影响电沉积铂纳米粒子形貌的原因进行了探讨. 研究了铂纳米粒子的电催化活性, 发现通过添加卤素阴离子制备得到的铂纳米粒子对于甲醇的电化学催化氧化表现出较低的电化学催化活性. 通过电化学氧化法全部或部分除去铂表面吸附的卤素阴离子后, 纳米粒子对甲醇的电化学催化氧化活性显著提高.     

Effect of Lanthanide Additives to a Nickel Oxide Electrode of a Sealed Nickel-Zinc Battery on the Self-Discharge and Hydrogen Pressure

The influence exerted by addition of a nickel-based alloy containing lanthanides (La, Ce, Nd, Pr) to the active paste of a nickel oxide electrode on the self-discharge and hydrogen pressure in a sealed nickel-zinc battery was studied.     

Electrolytic Synthesis of Complex Oxide Systems by Cathodic Deposition of Molybdenum Oxide from Aqueous Solutions in the Presence of Nickel(II) and Thiosulfate Ions

Cathodic processes occurring in electrolytic deposition of molybdenum oxide from aqueous solutions of sodium molybdate in the presence of nickel(II) and thiosulfate ions were studied. Conditions for formation of cathodic deposits in the form of complex oxide systems Mo-Ni and Mo₄O_{1 1}-MoS₂ were determined.     

The Structure of Nickel(Ii) and Copper(Ii) Complexes with 1,4,8,11-Tetraazacyclotetradecanein Aqueous Solution as Studied by the X-Ray Diffraction Method

The structure of 1,4,8,11-tetraazacyclotetradecane (cyclam) complexes with nickel(II) and copper(II) ions in aqueous solution has been determined by the x-ray diffraction method at 25°C. The [Ni-(cyclam)]²⁺ complex has a square-planar structure with four nitrogen atoms of the cyclam, and the Ni-N bond length has been determined to be 198 pm. Upon the addition of ammonia, the color of the nickel(II)-cyclam solution turns to deep purple and the [Ni(NH₃)₂(cyclam)]²⁺ complex is formed. The complex has a regular octahedral structure with an additional two NH₃ molecules along the axis vertical of the cyclam plane, and the Ni-N (NH₃ and cyclam) bond lengths are 209 pm. The copper(II)-cyclam complex in the aqueous solution is a distorted octahedron with two water molecules along the elongated axis. The axial Cu—O and equatorial Cu—N bond lengths are 277 and 210 pm, respectively.     

Effect of Sulfur Compounds and Higher Homologues of Methane on Hydrogen Cyanide Production by the Andrussow Method

The influence of sulfur compounds, higher homologues of methane on the parameters ofoxidative ammonolysis of methane was studied.     

Part II: NiMoO4 Nanostructures Synthesized by the Solution Combustion Method: A Parametric Study on the Influence of Material Synthesis and Electrode-Fabrication Parameters on the Electrocatalytic Activity in the Hydrogen Evolution Reaction

Earth-abundant NiMo-oxide nanostructures were investigated as efficient electrocatalytic materials for the hydrogen evolution reaction (HER) in acidic media. Synthesis and non-synthesis parameters were thoroughly studied. For the non-synthesis parameters, the variation in Nafion loading resulted in a volcano-like trend, while the change in the electrocatalyst loading showed that the marginal benefit of high loadings attenuates due to mass-transfer limitations. The addition of carbon black to the electrocatalyst layer improved the HER performance at low loadings. Different carbon black grades showed a varying influence on the HER performance. Regarding the synthesis parameters, a calcination temperature of 500 °C, a calcination time between 20 and 720 min, a stoichiometric composition (Ni/Mo = 1), an acidic precursor solution, and a fuel-lean system were conditions that yielded the highest HER activity. The in-house NiMoO₄/CB/Nafion electrocatalyst layer was found to offer a better long-term performance than the commercial Pt/C.     

The Effect of Particle Size and the Modifier on the Properties of Palladium Catalysts in the Synthesis of Hydrogen Peroxide by the Anthraquinone Method

The effect of the composition of the catalytic system and the size of particles on the properties of palladium catalysts in 2-ethyl-9,10-anthraquinone hydrogenation was studied. It was shown that, depending on the nature of a reducing agent (H₂, AlEt₃), palladium species formed in the absence of a modifying agent catalyze various side processes to a substantial extent together with 2-ethyl-9,10-anthraquinone hydrogenation: mostly hydrogenolysis (in the case of H₂ as a reducing agent) and hydrogenation of aromatic rings in 2-ethyl-9,10-anthrahydroquinone (in the case of AlEt₃ as a reducing agent). Elementary phosphorus was found to have a promoting effect on the selectivity of palladium catalysts in the synthesis of hydrogen peroxide by the anthraquinone method. The main factors that make it possible to control the selectivity of palladium catalysts were discussed.     

The Effect of the Weak Completing Nature of NaF,NaN3, and NaC3H3O3 Supporting Electrolytes on the Electrocatalysis of Nickel(II) Reduction in the Presence of Organic Amines

Abstract

Contrary to the results obtained in essentially noncomplexing supporting electrolyte media (NaClo₄, NaN0₃, NaCl and NaBr), the kinetic limited currents of the catalytic prewaves obtained for the polarographic reduction of Ni(II) in the presence of organic amines (o-phenylenediamine, pyridine, etc.) employing weakly complexing supporting electrolytes (NaF, NaN₃, and NaC₂H₃O₂) do not correlate with ?₂ potentials as predicted by simple double layer theory. However, the limiting current does correlate with the ligand exchange rates for Ni(H₂O)₅X⁺ type complexes (where X = F^?, N₃ ^? and C₂H₃O₂ ^?) with an organic ligand. These results lead to a general mechanism for the electrocatalysis mechanism of Ni(II) reduction.     

Sorption of Zinc Ions by a Nonwoven Polypropylene Material Modified with Poly(acrylic acid) Grafted to the Fiber Surface: The Role of Grafting Density and Hydrogen Bonds

A microfiber carboxylic cationite is prepared via the photoinduced polymerization of acrylic acid on the surface of nonwoven polypropylene material. Changes in the amount of the graft polymer (grafting density) and in the strength of hydrogen bonds between its carboxyl groups, depending on the polymerization time, are investigated by attenuated total internal reflectance FTIR spectroscopy. The sorption properties of the obtained ionite in the acidic (COOH) and salt (COONa) forms with respect to Zn²⁺ ions at various grafting densities are studied. The sorption capacity of the investigated cationite in its salt form is higher than that in the acidic form, and this difference increases quickly with the grafting density. The data of IR spectroscopy showed that this behavior is caused by the formation of stronger hydrogen bonds between COOH groups of the grafted polyacrylic acid, complicating their ionization and, thus, preventing the ion exchange.     

Effect of Thiourea on the Kinetics of the Hydrogen Evolution Reaction at Iron and the Transport of Hydrogen through a Steel Membrane in Solutions of C<Subscript>2</Subscript>H<Subscript>4</Subscript>(OH)<Subscript>2</Subscript>-H<Subscript>2</Subscript>O-HCl

The effect of thiourea (0.5–10 mM) on the kinetics of the hydrogen evolution reaction (HER) at iron and the hydrogen transport through a steel membrane out of ethylene glycol (containing 2 and 10 wt % H₂O) and aqueous solutions containing HCl (0.1–0.99 M) with a constant ionic strength equal to unity is studied in parallel experiments. The presence of 0.5 mM of thiourea in the solutions raises the overvoltage of hydrogen evolution, while a subsequent increase in its concentration does not effect the HER kinetics. The dependence of the flux of hydrogen diffusion through the membrane on the thiourea content passes through a maximum.     

The Effect of Evaporation Temperature on the Structure and Conductivity of Thin Films Obtained by the Moving Meniscus Method from Nanodispersions of Silver Particles

The effect of temperature (23–58°C) on the structure and conductivity of thin films obtained by the moving meniscus method from nanodispersions of silver particles with sizes of 6.5–70 nm has been studied. It has been shown that an increase in temperature leads to an exponential decrease in the specific conductivity of the films, with their thickness varying nonmonotonically. In the case of “large” particles, an increase in temperature decreases the efficiency of their deposition onto a substrate. The reasons for the observed regularities have been discussed.     

ChemInform Abstract: Microsolvation of Hydrogen Sulfide: Exploration of H2S×(H2O)n and SH‐×H3O+× (H2O)n‐1 (n = 5—7) Cluster Structures on ab initio Potential Energy Surfaces by the Scaled Hypersphere Search Method.

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