Dissolution reaction of TiO2 in molten 6.58NaF-AlF3:A Raman spectroscopy and computational simulation study
Dissolution reaction of TiO2 in molten 6.58NaF-AlF3:A Raman spectroscopy and computational simulation study
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DOI：
10.1016/j.molliq.2022.120431
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发表时间：
2022-09
影响因子：
6
通讯作者：
Shuai Tang;Xianwei Hu;Jiang-yu Yu;Aimin Liu;Zhongning Shi;Zhuo Li;Yifan Zhang;Zhaowen Wang
中科院分区：
文献类型：
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作者：
Shuai Tang;Xianwei Hu;Jiang-yu Yu;Aimin Liu;Zhongning Shi;Zhuo Li;Yifan Zhang;Zhaowen Wang
NaF-AlF 3-TiO 2三元系是熔盐电解法生产Al-Ti合金的常用体系。为了探索TiO 2在NaF-AlF 3熔盐中的溶解反应，采用拉曼光谱结合计算机模拟研究了（6. 58 NaF-AlF 3）-TiO 2熔盐的离子结构。结果表明，在6. 58 NaF-AlF 3熔盐中加入TiO 2，首先与F-或AlF 63-反应，反应式为：2F-+2TiO2= Ti 2 O 4F 22-，4AlF 63-+6TiO2= 2Al 2 O3 + 3 Ti 2 O2 F62-+6F-，生成的Al 2 O3再与TiO 2和F-或AlF 63-反应，反应式为：Al2O3+ 3TiO2+ 21F-=3TiO3F35-+2AlF63-，Al2O3+ 4AlF63-=3Al2OF84-，Al2O3+ 4AlF63-=3Al2OF62-+6F-。此外，Ti 2 O2 F62-、TiO 3F 35-和Ti 2 O 4F 22-团簇分别属于Cs、C2 v和C1点群，其主要特征拉曼谱带分别来自O 1-Ti 3-O2-Ti4、Ti 1-O 7和O 6-Ti 2-O 5和/或O 7-Ti 1-O 8的伸缩振动。此外，Ti 2 O2 F62-、TiO 3F 35-和Ti 2 O 4F 22-的主要特征拉曼谱带分别位于790、850和900 cm−1处。
The NaF-AlF3-TiO2ternary system is often used in the molten salt electrolysis process to produce Al-Ti alloys. In order to explore the dissolution reaction of TiO2in NaF-AlF3melts, the ionic structure of (6.58NaF-AlF3)-TiO2molten salts was examined by Raman spectroscopy combined with computational simulation in the present study. The results indicated that when TiO2was added to 6.58NaF-AlF3molten salt, it first reacted with F-or AlF63-with the following reactions: 2F-+2TiO2= Ti2O4F22-, 4AlF63-+6TiO2= 2Al2O3+ 3Ti2O2F62-+6F-, and then the generated Al2O3reacted with TiO2and F-or AlF63-with the following reactions: Al2O3+ 3TiO2+ 21F-=3TiO3F35-+2AlF63-, Al2O3+ 4AlF63-=3Al2OF84-, Al2O3+ 4AlF63-=3Al2OF62-+6F-. In addition, Ti2O2F62-, TiO3F35-and Ti2O4F22-clusters belonged to Cs, C2v and C1 point group, and the main characteristic Raman bands of these clusters were due to the stretching vibration of O1-Ti3-O2-Ti4, Ti1-O7and O6-Ti2-O5and/or O7-Ti1-O8, respectively. What’ more, the main characteristic Raman bands of Ti2O2F62-, TiO3F35-and Ti2O4F22-were located at 790, 850 and 900 cm−1, respectively.