节点扭曲作为金属有机框架中负热膨胀的调节机制
Zhihengyu Chen1, Gautam D Stroscio2, Jian Liu3
1Department of Chemistry, Stony Brook University, Stony Brook, New York 11794, United States.
金属有机框架 (MOF) 由于其节点的温度引起的局部扭曲而表现出负热膨胀 (NTE). 通过封闭连接体控制这些节点扭曲提供了调整MOF动态结构和功能的一种新方法.
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) 提供了具有多样性特性的可调结构.
- 了解局部化学和远程框架行为之间的关系对于MOF设计至关重要.
研究的目的:
- 研究基于NU-1000的MOF的局部和远程结构变化.
- 阐明这些MOF中负热膨胀 (NTE) 的机制.
- 探索封闭连接体在控制MOF结构和NTE中的作用.
主要方法:
- 在现场同步X射线总散射.
- 粉末衍射和对分布函数分析 (PDF)
- 多变量数据分析 (非负矩阵分解 - NMF).
- 密度函数理论 (DFT) 的计算.
主要成果:
- Zr6O8节点的局部扭曲受限联体可变性的影响,并导致NTE.
- 发现了一种新的NTE机制:温度上升会导致较小,扭曲的节点状态,导致框架收缩.
- 节点状态之间的转换发生在非合作的固体溶液中,而不是有序的相位过渡.
- DFT的计算证实了配体去除会导致与实验PDF数据相一致的扭曲.
结论:
- 可以通过调整节点的局部化学来控制MOF的动态结构和NTE行为.
- 局部节点扭曲,受封闭连接体的影响,是控制宏观负热膨胀的关键因素.
- 这项研究揭示了通过局部化学修饰来控制MOF的基本机制.
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