The cathodic reduction mechanism of Hf(Ⅳ)ions in a fused Na Cl–KCl–Na F–K_(2) HfF_(6) salt system was studied in various Na F concentrations at 1073 K to obtain a purified dendritic Hf metal.The results of cyclic ...The cathodic reduction mechanism of Hf(Ⅳ)ions in a fused Na Cl–KCl–Na F–K_(2) HfF_(6) salt system was studied in various Na F concentrations at 1073 K to obtain a purified dendritic Hf metal.The results of cyclic voltammetry and square wave voltammetry indicated that the reduction process comprised two steps of Hf(Ⅳ)→Hf(Ⅱ)and Hf(Ⅱ)→Hf at low Na F concentrations(0<molar ratio of[F-/Hf 4+]≤17.39)and one step of Hf(Ⅳ)→Hf at high Na F concentrations(17.39<molar ratio of[F-/Hf 4+]<23.27).The structure and morphology of the deposits obtained in potentiostatic electrolysis in the one-step reduction process were analyzed and verified by X-ray diffraction,scanning electron microscopy,and energy dispersive X-ray spectrometry.In the one-step reduction process,the disproportionation reaction between the Hf metal and Hf complex ions was inhibited,and a large dendrite Hf metal was achieved in molten salt electrorefining.展开更多
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 electro...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,Na_(2)SiO_(3)-SiO_(2)-Fe_(2)O_(3),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 Na_(2)SiO_(3)-SiO_(2)-Fe_(2)O_(3)in the temperature range of 1248–1278 K are between 1.86×10^(−6)cm^(2)/s and 1.58×10^(−4)cm^(2)/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.O_(2)/O_(complex)^(2-))for 6 h produces metallic iron on the cathode.展开更多
The work concerned the electrochemical behaviors of Y（Ⅲ） on W and Ni electrodes in molten LiCl-KCl salts by a series of electrochemical techniques. The electrochemical reaction of Y（Ⅲ） to Y（0） proceeded in a o...The work concerned the electrochemical behaviors of Y（Ⅲ） on W and Ni electrodes in molten LiCl-KCl salts by a series of electrochemical techniques. The electrochemical reaction of Y（Ⅲ） to Y（0） proceeded in a one-step reduction process with the exchange of three electrons, Y（Ⅲ）＋3e^–→Y（0）. Compared with the cyclic voltammogram and square wave voltammogram obtained on W electrode, the reduction potential of Y（Ⅲ） on Ni electrode was observed at less negative potential than the one of Y（Ⅲ） to give pure Y metal on W electrode, which revealed the occurrence of underpotential deposition of Y（Ⅲ） on Ni electrode. Electromotive force（emf） measurements were performed to calculate the relative partial molar Gibbs energies and activities of Y in Y-Ni alloys. The standard Gibbs energies of formation for different Y-Ni intermetallic compounds were also estimated. The different Y-Ni alloys were formed by potentiostatic electrolysis at different potentials and characterized by X-ray diffraction（XRD）, scanning electron microscopy（SEM）, and energy dispersive spectrometry（EDS）. It was found that four intermetallic compounds, YNi5, Y2Ni7, YNi3 and YNi2, were selectively produced by controlling applied potential.展开更多
基金the National Natural Science Foundation of China(No.51204021)。
文摘The cathodic reduction mechanism of Hf(Ⅳ)ions in a fused Na Cl–KCl–Na F–K_(2) HfF_(6) salt system was studied in various Na F concentrations at 1073 K to obtain a purified dendritic Hf metal.The results of cyclic voltammetry and square wave voltammetry indicated that the reduction process comprised two steps of Hf(Ⅳ)→Hf(Ⅱ)and Hf(Ⅱ)→Hf at low Na F concentrations(0<molar ratio of[F-/Hf 4+]≤17.39)and one step of Hf(Ⅳ)→Hf at high Na F concentrations(17.39<molar ratio of[F-/Hf 4+]<23.27).The structure and morphology of the deposits obtained in potentiostatic electrolysis in the one-step reduction process were analyzed and verified by X-ray diffraction,scanning electron microscopy,and energy dispersive X-ray spectrometry.In the one-step reduction process,the disproportionation reaction between the Hf metal and Hf complex ions was inhibited,and a large dendrite Hf metal was achieved in molten salt electrorefining.
基金Project(52074084)supported by the National Natural Science Foundation of China。
文摘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,Na_(2)SiO_(3)-SiO_(2)-Fe_(2)O_(3),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 Na_(2)SiO_(3)-SiO_(2)-Fe_(2)O_(3)in the temperature range of 1248–1278 K are between 1.86×10^(−6)cm^(2)/s and 1.58×10^(−4)cm^(2)/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.O_(2)/O_(complex)^(2-))for 6 h produces metallic iron on the cathode.
基金Project supported by the National Natural Science Foundation of China(21271054,11575047,21173060,11675044),the Major Research Plan of the National Natural Science Foundation of China(91326113,91226201)the Fundamental Research Funds for the Central Universities(HEUCF2016012)
文摘The work concerned the electrochemical behaviors of Y（Ⅲ） on W and Ni electrodes in molten LiCl-KCl salts by a series of electrochemical techniques. The electrochemical reaction of Y（Ⅲ） to Y（0） proceeded in a one-step reduction process with the exchange of three electrons, Y（Ⅲ）＋3e^–→Y（0）. Compared with the cyclic voltammogram and square wave voltammogram obtained on W electrode, the reduction potential of Y（Ⅲ） on Ni electrode was observed at less negative potential than the one of Y（Ⅲ） to give pure Y metal on W electrode, which revealed the occurrence of underpotential deposition of Y（Ⅲ） on Ni electrode. Electromotive force（emf） measurements were performed to calculate the relative partial molar Gibbs energies and activities of Y in Y-Ni alloys. The standard Gibbs energies of formation for different Y-Ni intermetallic compounds were also estimated. The different Y-Ni alloys were formed by potentiostatic electrolysis at different potentials and characterized by X-ray diffraction（XRD）, scanning electron microscopy（SEM）, and energy dispersive spectrometry（EDS）. It was found that four intermetallic compounds, YNi5, Y2Ni7, YNi3 and YNi2, were selectively produced by controlling applied potential.
