Application of a deep eutectic solvent to prepare nanocrystalline Ni and Ni/TiO2 coatings as electrocatalysts for the hydrogen evolution reaction

The paper reports the electrochemical deposition of nanocrystalline nickel and composite nickel-titania films as effective electrocatalysts for the hydrogen evolution reaction. To produce the composite Ni/TiO₂ electrodeposits, a plating bath based on a deep eutectic solvent, a novel kind of ionic liquids, was used for the first time. The electrolyte contained ethaline (a eutectic mixture of choline chloride and ethylene glycol), 1 M NiCl₂⋅6H₂O and the addition of extra water (3, 6, 9 mol dm⁻³). Titania dispersed phase was introduced into the electrolyte as nanopowder Degussa P 25 (0–10 g dm⁻³). It was shown that the introduction of extra water to the plating bath allowed appreciably increasing the content of TiO₂ phase in the coating (from ca. 2 to 10 wt%). The effects of electrolysis conditions on the TiO₂ content in the coatings, surface morphology and microstructure were determined. The results of voltammetry measurements showed that the Ni and composite Ni/TiO₂ coatings electrodeposited from the plating electrolyte based on a deep eutectic solvent exhibit improved electrocatalytic properties towards the hydrogen evolution reaction as compared with deposits obtained from commonly used aqueous electrolytes. The mechanism of the hydrogen evolution reaction on the Ni and composite Ni/TiO₂ coatings is a combination of Volmer-Heyrovsky reactions. The introduction of TiO₂ particles into the nickel matrix results in the acceleration of the hydrogen evolution reaction. An improved catalytic activity of Ni/TiO₂ composites towards the hydrogen evolution reaction can be associated with the presence of titanium-containing redox couples on the surface.     

Accelerated oxygen evolution kinetics on NiFeAl-layered double hydroxide electrocatalysts with defect sites prepared by electrodeposition

NiFe layered double hydroxides (LDHs) is considered to be one of the LDHs electrocatalyst materials with the best electrocatalytic oxygen evolution properties. However, its poor conductivity and inherently poor electrocatalytic activity are considered to be the limiting factors inhibiting the electrocatalytic properties for oxygen evolution reaction (OER). The amorphous NiFeAl-LDHs electrocatalysts were prepared by electrodeposition with nickel foam as the support, and the D-NiFeAl-LDHs electrocatalyst with defect sites was then obtained by alkali etching. The mechanism of catalysts with defect sites in OER was analyzed. The ingenious defects can selectively accelerate the adsorption of OH⁻, thus enhancing the electrochemical activity. The D-NiFeAl-LDHs electrocatalyst had higher OER electrocatalytic activity than NiFe-LDHs electrocatalyst: its accelerated OER kinetics were mainly due to the introduction of iron and nickel defects in NiFeAl-LDHs nanosheets, which effectively adjusted the surface electronic structure and improved OER electrocatalytic performance. There was only a low overpotential of 262 mV with the current density of 10 mA cm⁻², and the Tafel slope was as low as 41.67 mV dec⁻¹. The OER electrocatalytic performance of D-NiFeAl-LDHs was even better than those of most of the reported NiFe-LDHs electrocatalysts.     

Preparation of the TiB2 coatings by electroplating in molten salts

The improvement of titanium diboride (TiB₂) coatings over the molybdenum substrate was investigated by comparing the electrochemical techniques of continuous current plating (CCP) and periodically interrupted current (PIC). The solvent used was a eutectic Flinak mixture (LiF-NaF-KF, 46.5:11.5:42 molar ratio) with solutes K₂TiF₆ and KBF₄ with the electrochemically-active components in the molar ratio of one to five. The coatings produced by PIC show improvements in morphology and microstructure for the suitable conditions: i = 0.5 A/cm², frequency = 100 Hz, the time ratio t_c/t_off (current on/current off) = 4/1. X-ray diffraction (XRD) analyses indicated that the coatings are composed of the relatively pure TiB₂ and the preferred orientation is [001] + [110], which is in accordance with the prediction of the two-dimensional crystal nuclei theory.     

Application of artificial neural networks for prediction of coercivity of highly ordered cobalt nanowires synthesized by pulse electrodeposition

This study aims to predict the coercivity of cobalt nanowires fabricated by Alternating Current (AC) pulse. Coercivity is one of the most important properties of magnetic materials and its value shows the needed magnetic field in a way that magnetization of system is decreased to zero. There are many parameters such as pH of solution, oxidative and reductive times, oxidative and reductive voltages, interval between pulses (off-time), and concentration of deposition solution that have direct effect on materials magnetic properties of. Change of initial conditions to obtain the best results is very time consuming, therefore employing a method which can save both the time and cost is necessary. Hence, it this study Artificial Neural Network (ANN), which has numerous applications and has attracted many attentions in various fields, was applied. Through this study, an ANN was designed to present a template that is capable for predicting output data (coercivity) according to input data (pH, oxidative and reductive times, oxidative and reductive voltages, and off-time). Besides, in this research, the results for pH = 4 and 6 were investigated and the effect of off-time as well as the deposition time on coercivity were studied.     

Thermal optimization and supercapacitive application of electrodeposited Fe2O3 thin films

In the present work, thin films of Fe₂O₃ were deposited onto stainless steel substrates by electrodeposition method. All deposited electrodes were annealed for 1 h within the temperature range of 423–673 K with an interval of 50 K. These were further characterized for their structural and morphological measurements by means of X-ray diffraction and scanning electron microscopy techniques, respectively. The supercapacitive characteristics of as-deposited and annealed electrodes were carried out in 1 M KOH electrolyte to confirm the variation in specific capacitance, specific energy, specific power and columbic efficiency, etc., with annealing temperatures.     

Water-Lubricated Ni-Based Composite(Ni-Al_2O_3,Ni-SiC and Ni-ZrO_2)Thin Film Coatings for Industrial Applications

In this work,pure nickel and Ni-based nanocomposite coatings(N1-Al_2O_3,Ni-SiC and Ni-ZrO_2) were produced on steel substrate by using pulse electrodeposition technique.The industrial performance tests were conducted to evaluate the wear resistance,corrosion resistance,adhesion strength and wettability behaviour of newly developed coatings.Rolling contact ball-on-disc tribometer was used to assess anti-wear behaviour of these coatings under waterlubricated contacts.The results showed that the wear- and corrosion resistance properties of nickel alumina and Ni-SiC composite coatings significantly improved than that of pure Ni and Ni-ZrO_2 coatings.The adhesion and wettability results of Ni-Al_2O_3 composite showed better performance when compared to the rest of the coatings.The effects of incorporating nanoparticles on the surface microstructure,interface adhesion and distribution of the particles were also investigated.The coatings were characterized by using scanning electron microscopy,X-ray diffraction analysis and 3D white light interferometry.The wear failure behaviour of these coatings was further examined by post-test surface observation under optical microscope.     

直流电沉积法制备纳米晶体镍镀层及其热稳定性的研究

利用直流电沉积技术,系统分析电流密度和镀液糖精浓度对纳米晶体镍性能的影响。电流密度在0.5-1.5 A/dm2 范围内时,可调节糖精浓度制备出415-603Hv的显微硬度宽分布的纳米晶镀层。小电流密度0.5 A/dm2 时,随糖精浓度增大,镀层(200) 面衍射强度增强,结构由(111), (200)双织构向(200)面转变,且镀层内应力值降低,增大到1.2g/L时,内应力降为0MPa。镀层晶粒尺寸为28~98nm时,直到600℃晶粒才开始长大,结构稳定性较好;晶粒尺寸为10nm时,晶粒在317℃异常长大,其结构稳定性显著下降。     

PB/ITO-PET柔性电致变色薄膜制备及性能研究

柔性电致变色器件具有体积小、重量轻、可弯曲等优点,在可穿戴设备、曲面显示器、节能及自适应伪装等领域具有潜在应用前景。本工作以铁氰化钾、氯化钾、无水氯化铁为原料,采用电沉积方法在ITO-PET柔性基底上沉积普鲁士蓝(PB)制得PB/ITO-PET电致变色薄膜,并利用扫描电子显微镜、紫外光谱仪、电化学工作站对PB/ITO-PET电致变色薄膜微观结构和电化学性能进行分析表征。结果表明,电沉积时间为200 s时得到的PB/ITO-PET电致变色薄膜在700 nm波长处光吸收率达到0.755,且PB/ITO-PET电致变色薄膜可在较低电压(0.6 V/-0.3 V)下实现着色和褪色。其光调制范围为68%,着色/褪色响应时间分别为9 s/8 s,着色效率为108 cm2/C。PB/ITO-PET电致变色薄膜经1000次着色-褪色循环后光调制范围为68%,着色效率为100.3 cm2/C。PB/ITO-PET电致变色薄膜500次弯曲,着色效率为105.5 cm2/C,并经1000次着色-褪色循环后着色效率为91 cm2/C,光调制范围为65%。利用ITO-PET为离子存储层(对电极)、凝胶电解质和PB/ITO-PET为工作电极组装得到柔性电致变色器件,其光调制范围为53%,着色/褪色响应时间分别为13 s/18 s。     

Electrochemical formation of Sm-Co alloys by codeposition of Sm and Co in a molten LiCl-KCl-SmCl3-CoCl2 system

Electrocodeposition of Sm and Co on a Cu substrate was investigated in a molten LiCl-KCl-SmCl₃ (0.5 mol.%)-CoCl₂ (0.1 mol.%) system at 723 K. Phase of the deposited Sm-Co alloys could be controlled by electrolysis potential. SmCo₃ was formed on a Cu substrate by potentiostatic electrolysis in the potential range of 0.20-0.90 V (vs. Li⁺/Li). Sm₂Co₁₇ was obtained in the potential range of 0.90-1.50 V.     

Kinetic models for alloy and semiconductor electrodeposition

The residence time τ of an atom in a kink site position is a characteristic property of a growing phase. For alloys kink site positions and associated residence times must be defined for the different alloy components. For instance, for an alloy AB kink site positions A^* and B^* must be distinguished. Each kink site atom can react either with ions of type A or B to form new kink site positions AA^*, AB^*, BA^* or BB^*. The selectivity of the kink site positions for either A or B can be expressed by residence times τ_AA, τ_AB, τ_BA and τ_BB. Another characterization of the selectivity is possible by the application of the finite Markov chain theory. Then selectivity constants g_A and g_B can be defined. Assuming equilibrium between the atoms in kink site positions and the respective ions in the electrolyte, the selectivity constants represent the ratios of the respective equilibrium constants between kink site positions and electrolyte concentrations g_A = K_AA/K_AB and g_B = K_BB/K_BA. If the process is rate-controlled, the selectivity constants represent the ratios of the respective rate constants of deposition. The model is applied to CoNi and SnNi alloys and to bismuth telluride. A relation is derived between selectivity constants and residence times.