采用循环伏安法,研究了0.25 mol/L Ta Cl5在离子液体1-丁基-3-甲基咪唑六氟磷酸盐([Bmim]PF6)中的电化学行为。实验结果表明,电沉积钽是受扩散控制、两步骤的不可逆电极反应过程,首先是Ta(Ⅴ)还原为Ta(Ⅲ),其次是Ta(Ⅲ)还原为金属钽和...采用循环伏安法,研究了0.25 mol/L Ta Cl5在离子液体1-丁基-3-甲基咪唑六氟磷酸盐([Bmim]PF6)中的电化学行为。实验结果表明,电沉积钽是受扩散控制、两步骤的不可逆电极反应过程,首先是Ta(Ⅴ)还原为Ta(Ⅲ),其次是Ta(Ⅲ)还原为金属钽和形成其它低价钽氯化物。Ta(Ⅴ)/Ta(Ⅲ)和Ta(Ⅲ)/Ta在离子液体[Bmim]PF6中的阴极传递系数分别为0.155和0.406。Ta(Ⅴ)在离子液体[Bmim]PF6中的扩散系数为1.629×10-9cm2/s。在100℃和-1.25 V条件下,采用恒电势法在铂片上电沉积钽,扫描电子显微镜照片和EDS分析表明,沉积物为钽和钽的低价氯化物。展开更多
To investigate the electrochemical reduction mechanism of Ta(Ⅴ)in ethylene carbonate and aluminum chloride(EC-AlCl3)solvate ionic liquid,cyclic voltammetry experiments were conducted on a tungsten working electrode.F...To investigate the electrochemical reduction mechanism of Ta(Ⅴ)in ethylene carbonate and aluminum chloride(EC-AlCl3)solvate ionic liquid,cyclic voltammetry experiments were conducted on a tungsten working electrode.Four reduction peaks were observed in the cyclic voltammogram of the EC-AlCl3-TaCl5 ionic liquid.The reduction peaks at-0.55,-0.72,and-1.12 V(vs Al)were related to the reduction of Ta(Ⅴ)to tantalum metal by three stages including the formation of Ta(Ⅳ)and Ta(Ⅲ)complex ions.The reduction of Ta(Ⅲ)to tantalum metal was an irreversible diffusion-controlled reaction with a diffusion coefficient of 3.7×10^-7 cm^2/s at 323 K,and the diffusion activation energy was 77 k J/mol.Moreover,the cathode products at 323 K were characterized by scanning electron microscopy,energy-dispersive spectroscopy,and X-ray photoelectron spectroscopy.The results showed that tantalum metal and tantalum oxides were obtained by potentiostatic electrodeposition at-0.8 V for 2 h.展开更多
文摘采用循环伏安法,研究了0.25 mol/L Ta Cl5在离子液体1-丁基-3-甲基咪唑六氟磷酸盐([Bmim]PF6)中的电化学行为。实验结果表明,电沉积钽是受扩散控制、两步骤的不可逆电极反应过程,首先是Ta(Ⅴ)还原为Ta(Ⅲ),其次是Ta(Ⅲ)还原为金属钽和形成其它低价钽氯化物。Ta(Ⅴ)/Ta(Ⅲ)和Ta(Ⅲ)/Ta在离子液体[Bmim]PF6中的阴极传递系数分别为0.155和0.406。Ta(Ⅴ)在离子液体[Bmim]PF6中的扩散系数为1.629×10-9cm2/s。在100℃和-1.25 V条件下,采用恒电势法在铂片上电沉积钽,扫描电子显微镜照片和EDS分析表明,沉积物为钽和钽的低价氯化物。
基金Projects(N182503033N172502003)supported by the Fundamental Research Funds for the Central Universities,China+1 种基金Project(2018M640258)supported by Postdoctoral Research Foundation of ChinaProject(GUIKE AA18118030)supported by Guangxi Innovation-driven Development Program,China。
文摘To investigate the electrochemical reduction mechanism of Ta(Ⅴ)in ethylene carbonate and aluminum chloride(EC-AlCl3)solvate ionic liquid,cyclic voltammetry experiments were conducted on a tungsten working electrode.Four reduction peaks were observed in the cyclic voltammogram of the EC-AlCl3-TaCl5 ionic liquid.The reduction peaks at-0.55,-0.72,and-1.12 V(vs Al)were related to the reduction of Ta(Ⅴ)to tantalum metal by three stages including the formation of Ta(Ⅳ)and Ta(Ⅲ)complex ions.The reduction of Ta(Ⅲ)to tantalum metal was an irreversible diffusion-controlled reaction with a diffusion coefficient of 3.7×10^-7 cm^2/s at 323 K,and the diffusion activation energy was 77 k J/mol.Moreover,the cathode products at 323 K were characterized by scanning electron microscopy,energy-dispersive spectroscopy,and X-ray photoelectron spectroscopy.The results showed that tantalum metal and tantalum oxides were obtained by potentiostatic electrodeposition at-0.8 V for 2 h.
