摘要
NaCl-KCl-K_(2)TiF_(6)体系是熔盐电解制备金属钛及其合金的常用电解质体系,熔盐的离子结构与其物理化学性质及电极反应机理密切相关,然而熔融K_(2)TiF_(6)在空气中会氧化从而影响其离子结构。本文通过Raman光谱法和量子化学计算探究了空气氧化对不同K_(2)TiF_(6)含量NaCl-KCl-K_(2)TiF_(6)熔盐离子结构的影响。结果表明:空气中,熔融状态下NaCl-KCl-K_(2)TiF_(6)体系中的TiF_(2)^(6-)被氧化为TiOF_(3)^(-)和TiO_(4)F_(2)^(6-),二者所属空间点群为C1和D4h点群,二者的主Raman特征峰分别位于940和320 cm^(−1)处;随着体系中K_(2)TiF_(6)含量的增加,熔盐中TiOF_(3)_(-)的相对含量增加,TiO_(4)F_(2)^(6-)的含量相对减少。
The molten NaCl-KCl-K_(2)TiF_(6)was used as the electrolyte for the production of titanium and alloys by molten salt electrolysis process.The ionic structure of the molten salt is essential to its physicochemical property and mechanism of electrode reaction.However,molten K_(2)TiF_(6)will be oxidized in air and this will have an influence on the ionic structure of molten NaCl-KCl-K_(2)TiF_(6)system.In the present study,the influence of air oxidization on the ionic structure of molten NaCl-KCl-K_(2)TiF_(6)with different K_(2)TiF_(6)content was studied by Raman spectroscopy and quantum chemical calculation.The results show that TiF_(6)^(2-)is oxidized to TiOF-3 and TiO_(4)F_(2)^(6-)in the molten NaCl-KCl-K_(2)TiF_(6)system in air,and they belong to C1 and D4h point group,respectively.Furthermore,the main Raman characteristic bands of TiOF_(3)^(-)and TiO_(4)F_(2)^(6-)are located at 940 and 320 cm^(−1),respectively.With the increase of K_(2)TiF_(6)content in the system,the relative content of TiOF_(3)^(-)increases while that of TiO_(4)F_(2)^(6-)decreases.
作者
汤帅
胡宪伟
于江玉
刘爱民
石忠宁
王兆文
纪武仁
TANG Shuai;HU Xian-wei;YU Jiang-yu;LIU Ai-min;SHI Zhong-ning;WANG Zhao-wen;JI Wu-ren(Key Laboratory Ecological Metallurgy of Multimetallic Mineral,Ministry of Education,School of Metallurgy,Northeastern University,Shenyang 110819,China;Northwest Research Institute of Mining and Metallurgy,Baiyin 730900,China)
出处
《中国有色金属学报》
EI
CAS
CSCD
北大核心
2023年第2期590-597,共8页
The Chinese Journal of Nonferrous Metals
基金
国家自然科学基金资助项目(51974081)
辽宁省自然科学基金资助项目(2019-MS-129)。
