在水溶液中通过两步过程结晶Keggin异质聚离子
Mrinal K Bera1, Mark R Antonio1
1Chemical Sciences and Engineering Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
Journal of the American Chemical Society
|June 2, 2016
概括
异多酸盐的结晶包括在结晶核形成之前形成的密集的液态结构,支持两步过程. 这些结构和晶体形成取决于异构电荷,与奥斯瓦尔德对齐
科学领域:
- 材料科学
- 化学物理
- 晶体学
背景情况:
- 经典的核化理论假定一个步骤,但许多结晶涉及多个阶段.
- 两个阶段的核化理论提出密集的液态结构先于晶体形成.
- 异多聚离子是复杂的无机离子,在催化和材料科学中具有潜在的应用.
研究的目的:
- 在水溶液中研究异聚酸盐结晶的早期阶段.
- 在结晶之前观察溶液结构的形成和演变.
- 了解异聚离子电荷对核和晶体形成的影响.
主要方法:
- 在现场依赖时间的小角度X射线散射 (SAXS) 测量.
- 在干燥酸盐溶液上进行的实验.
- 在溶液蒸发和结晶过程中监测结构顺序.
主要成果:
- 在结晶之前,在水溶液中观察到密集的液态相关结构.
- 随着溶液体积的减少,这些相关结构的密度不断增加.
- 相关结构的形成和随后的结晶取决于异质聚离子的电荷.
- 在干燥过程中形成的多态晶体结构不同于最终的稳定结构.
结论:
- 这些发现支持溶液中异多酸盐的两步核化机制.
- 结果与奥斯瓦尔德的阶段规则一致, 表明连续形成的转移稳定阶段.
- 异多聚离子的电荷在核和结晶路径中起着关键作用.
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