Electrochemistry and the mechanisms of nucleation and growth of neodymium during electroreduction from LiCl–KCl eutectic salts on Mo substrate

Abstract

The electrochemical behavior of NdCl3 was studied on a Mo electrode in molten LiCl–KCl eutectic salts. The electroreduction of Nd(III)/Nd(0) involved two reaction steps, as confirmed by three different electrochemical techniques. In the first reaction step, Nd(III) is converted into soluble Nd(II), which undergoes further reduction into metallic Nd(0) in the second reaction step. The standard reaction rate constants for each reaction step were determined by Nicholson method. The rate constant values were used in Matsuda-Ayabe’s criteria for testing the electrochemical reversibility. Accordingly, both reaction steps were quasi-reversible redox reactions.The nucleation mechanisms of neodymium metal deposited on a Mo substrate were predicted by using Scharifker–Hill model, and tested for the first time by scanning electron microscopy (SEM) studies of the electrode surface. The SEM studies confirmed that for the low initial concentration of NdCl3, neodymium nucleates and grows progressively, while for higher NdCl3 concentrations, the related mechanism is instantaneous. Both are governed by the aggregative growth mechanisms based on surface mobility of formed nanoclusters.