Electrochemical behavior of Fe(III) in Na₂SiO₃-SiO₂-Fe₂O₃ molten salt

The high-temperature requirement for liquid iron smelting via molten oxide electrolysis presents significant challenges. This study investigates the electrochemical reduction of Fe(III) in a novel low-temperature electrolyte, Na₂SiO₃-SiO₂-Fe₂O₃, utilizing cyclic voltammetry and square wave voltammetry techniques. The results show that Fe(III) reduction occurs in two steps: Fe(III)+e⁻→Fe(II), Fe(II)+2e⁻→Fe, and that the redox process of Fe(III)/Fe(II) at the tungsten electrode is an irreversible reaction controlled by diffusion. The diffusion coefficients of Fe(III) in the molten Na₂SiO₃-SiO₂-Fe₂O₃ in the temperature range of 1248–1278 K are between 1.86×10⁻⁶ cm²/s and 1.58×10⁻⁴ cm²/s. The diffusion activation energy of Fe(III) in the molten salt is 1825.41 kJ/mol. As confirmed by XRD analysis, potentiostatic electrolysis at −0.857 V (vs. \(\mathrm{O}_{2}/\mathrm{O}_{(\text{complex})}^{2-}\) $${\mathrm{O}}_2/{\mathrm{O}}_{(\text{complex})}^{2-}$$ ) for 6 h produces metallic iron on the cathode.