Exploring more efficient and low-cost electrocatalysts to replace platinum (Pt) is highly desired to promote the practical hydrogen production through water splitting. Herein, a facile and effective strategy is proposed to fabricate self-standing Al3Ni2/Ni electrode with controlled phase composition and surface morphology, which is obtained by one-step electrochemical reduction of Al3+ on commercially available nickel in eutectic NaCl-KCl melt. Different from previously reported approaches, uniform Al3Ni2 monolith catalyst can directly grow onto Ni substrate. The deposit possesses unique three-dimensional (3D) cauliflower-like morphology comprising of nano- and microparticles due to the rapid nucleation rate during molten salt electrolysis. The as-fabricated Al3Ni2/Ni electrode can be directly used as the cathode to catalyze Hydrogen evolution reaction (HER). Impressively, it exhibits remarkable HER activity comparable to commercial Pt, including a low overpotential of 83.4 mV for a current density of 10 mA cm−2, a small Tafel slope of 40.7 mV dec-1, and excellent long-term stability over 36 h of continuous HER operation in 0.5 M H2SO4 solution. The intrinsic catalytic ability of Al3Ni2 with the unique hierarchical structure of nano/microsized grains can offer multiple effects, including massive exposed active sites, enhanced charge transfer and mass transport, and fast gas releasing that synergistically contribute to improving the electrocatalytic performance of HER. This work represents a highly promising approach to the design and one-step controllable fabrication of efficient and self-standing base metal electrode for electrocatalytic hydrogen production.@en

The electrochemical behavior of Nd(III) and its coreduction with Mg(II) were investigated on a molybdenum electrode at 1023 K in eutectic NaCl-KCl melts. The results indicate that the reduction of NdCl3 in NaCl-KCl melts is a one-step process with three electrons exchanged, and the reaction is an irreversible diffusion-controlled process at low scan rate with the calculated diffusion coefficient of about 6.8 × 10-5 cm2 s-1. After MgCl2 is introduced to the melts, the reduction of Nd(III) takes place at a more positive potential value due to the formation of Mg-Nd intermetallic compounds through electrochemical co-deposition and chemical reduction of Nd(III) ions by preferentially deposited Mg. The solid intermetallic compounds of Mg3Nd, Mg2Nd, and MgNd observed in open circuit chronopotentiometry curves are transformed to thermodynamically more stable Mg-rich phases of Mg12Nd and Mg41Nd5 when potentiostatic electrolysis at -2.10 V. It has been confirmed by X-ray diffraction and SEM-EDS microscopy that the cathodic deposits are composed of Mg, Mg12Nd, Mg41Nd5, and Nd. The present results confirm that it is an effective method for recycling of neodymium from waste NdFeB magnets by means of electrochemical formation of Mg-Nd alloys from NaCl-KCl-MgCl2-NdCl3 melts.@en

The electrochemical behavior of yttrium and its co-deposition with aluminum were investigated by several transient electrochemical techniques on a tungsten electrode at 973K in NaCl-KCl eutectic melts. The results reveal that the reduction of Y(III) in NaCl-KCl-YCl3 melts is a one-step process with three-electron exchanged and the reaction is a quasi-reversible diffusion-controlled process at low scan rates (0.05∼0.5 V/s). The calculated diffusion coefficient is approximately 2.8 × 10−5cm2/s. After AlCl3 was introduced into the melts, cyclic voltammetry and open circuit chronopotentiometry showed the formation of two Y-Al intermetallic compounds, indicating that under-potential deposition of yttrium occurred on tungsten electrode covered with liquid Al. The electromotive force was measured at 973K to determine the thermodynamic properties of Y-Al intermetallic compounds, such as the activity of Y in the two-phase coexistence state, relative partial molar Gibbs energies, as well as the standard Gibbs energies of Y-Al intermetallic compounds. Finally, potentiostatic electrolysis was conducted to prepare Y-Al alloys from molten NaCl-KCl-YCl3 (1.5 mol%)-AlCl3 (1.5 mol%) by the co-reduction method. The cathodic alloys were characterized using X-ray diffraction (XRD) and scan electron micrograph (SEM)-energy dispersive spectrometry (EDS) and the results indicated that the obtained alloys were mainly composed of YAl2, as well as YAl3 and YAl phases. The Y-rich phase intermetallic compound YAl, formed in the later period of electrolysis just when the concentration of AlCl3 is fairly low.@en