Effect of Pd, Cu, and Ni additions on the kinetics of NiCl2 reduction by hydrogen

Abstract

Differnetial thermal analysis (DTA) and thermal gravimetric analysis (TGA), at a heating rate of 10 °C/min, revealed a complete reduction of NiCl2 by hydrogen in a temperature interval of 375 °C to 450 °C. However, addition of 0.1 mass pct of Pd, Cu, or Ni to the sample caused the reduction to occur at considerably lower temperatures, in the rather narrow range of 315 °C to 370 °C. The activation energy of NiCl2 reduction by hydrogen (between 300 °C and 550 °C) without additives is 54 kJ/mol, and with Pd and Cu or Ni added, under isothermal conditions (from 260 °C to 380 °C), is 33 and 50 kJ/mol, respectively. These values confirm a positive effect of additives on the reduction kinetics. The positive effect of Pd is a consequence of the dissociation and spillover of hydrogen, whereas in the case of Cu and Ni(HCOO)2, it is manifested in a decrease in bonds energy in the nickel lattice because of good Cu solubility, and in the formation of artificial nickel nuclei that intensify the reduction, respectively. Scanning electron microscopy (SEM) analysis of nickel powders obtained under isothermal conditions shows relatively rounded spherical particles (0.321 to 0.780 µm in size) of powder samples with additives, and particles of irregular shape (2.085 µm mean size) of the sample without additives. This illustrates the positive effect of Pd, Cu, or Ni added in the reduction process, in decreasing the size of nickel particles and in the production of a more uniform particle shape.