真正MOF多态的稳定性的实验和理论评估解释了它们的机械化学相互转换
Zamirbek Akimbekov1, Athanassios D Katsenis2, G P Nagabhushana1
1Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California, Davis , One Shields Avenue, Davis, California 95616, United States.
Journal of the American Chemical Society
|May 19, 2017
概括
这项研究揭示了连接体结构和框架拓对金属有机框架 (MOF) 的稳定性产生重大影响. 受联体替代剂影响的密度较高的MOF多态体在热力学上更稳定.
科学领域:
- 材料科学
- 化学学
- 晶体学
背景情况:
- 金属有机框架 (MOF) 是具有调节性质的多功能多孔材料.
- 了解控制MOF多态稳定性的因素对于其有针对性的合成和应用至关重要.
- 异构MOF或真多态共享相同的化学成分,但在结构和特性上有所不同.
研究的目的:
- 通过实验和理论评估连接体结构和框架拓如何影响同构MOF的相对稳定性.
- 调查不同替代剂和拓的热力学稳定性.
- 将MOF密度和稳定性与连接体结构和框架拓相关联.
主要方法:
- 使用溶液热量计测量ZIF多态的热力学稳定性.
- 使用周期密度函数理论 (DFT) 计算进行理论评估.
- 分析了基于2-甲基和2-乙烯基胺酸结合剂的两个ZIF家族.
主要成果:
- 在测量的热力学稳定性和ZIF多态的密度之间观察到直接的相关性.
- 发现基替代剂对ZIF的稳定性有显著影响.
- 机械化学合成和ZIF的转换符合奥斯瓦尔德的阶段规则,有利于更密集,更稳定的阶段.
结论:
- 连接体结构和框架拓是MOF多态稳定的关键决定因素.
- 在MOF中增加的密度与增强的热力学稳定性相关.
- 在机械化学条件下,MOF的转化会朝着热力学上更有利,更密集的结构发展.
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