A Computational and Experimental Approach Linking Disorder, High-Pressure Behavior, and Mechanical Properties in UiO Frameworks.
A Computational and Experimental Approach Linking Disorder, High-Pressure Behavior, and Mechanical Properties in UiO Frameworks.
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DOI：
10.1002/anie.201509352
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发表时间：
2016-02-12
影响因子：
16.6
通讯作者：
Bennett, Thomas D.
中科院分区：
文献类型：
--
作者：
Hobday, Claire L.;Marshall, Ross J.;Murphie, Colin F.;Sotelo, Jorge;Richards, Tom;Allan, David R.;Dueren, Tina;Coudert, Francois-Xavier;Forgan, Ross S.;Morrison, Carole A.;Moggach, Stephen A.;Bennett, Thomas D.
关键词：
虽然许多金属有机框架具有用作功能材料所需的化学稳定性，但它们通常缺乏工业应用所需的物理强度。在此，我们通过单晶纳米压痕、高压X射线衍射、密度泛函理论计算和第一性原理分子动力学研究了两种UiO拓扑结构的Zr-MOFs，平面UiO-67（[Zr 6 O 4（OH）4（bpdc）6]，bpdc：4，4 ′-联苯二羧酸酯）和UiO-abdc（[Zr 6 O 4（OH）4（abdc）6]，abdc：4，4 ′-偶氮苯二羧酸酯）的力学性能。随着压力的增加，发现UiO-67和UiO-abdc在金刚石对顶砧单元内填充甲醇分子时是不可压缩的。在这两种情况下的稳定是由于动态链接器的障碍。UiO-abdc的重氮连接体具有局部位点无序性，这与其较长的性质相结合，也降低了骨架压缩的能力，并使其稳定以抵抗直接压缩，与UiO-67相比，其特征在于大的弹性模量。因此，在UiO-M0 F的合成中使用非线性连接体产生了在更大的压力范围内具有更刚性的机械性能的M0 F。
Whilst many metal–organic frameworks possess the chemical stability needed to be used as functional materials, they often lack the physical strength required for industrial applications. Herein, we have investigated the mechanical properties of two UiO‐topology Zr‐MOFs, the planar UiO‐67 ([Zr6O4(OH)4(bpdc)6], bpdc: 4,4′‐biphenyl dicarboxylate) and UiO‐abdc ([Zr6O4(OH)4(abdc)6], abdc: 4,4′‐azobenzene dicarboxylate) by single‐crystal nanoindentation, high‐pressure X‐ray diffraction, density functional theory calculations, and first‐principles molecular dynamics. On increasing pressure, both UiO‐67 and UiO‐abdc were found to be incompressible when filled with methanol molecules within a diamond anvil cell. Stabilization in both cases is attributed to dynamical linker disorder. The diazo‐linker of UiO‐abdc possesses local site disorder, which, in conjunction with its longer nature, also decreases the capacity of the framework to compress and stabilizes it against direct compression, compared to UiO‐67, characterized by a large elastic modulus. The use of non‐linear linkers in the synthesis of UiO‐MOFs therefore creates MOFs that have more rigid mechanical properties over a larger pressure range.
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DOI：
10.1039/c0cc02990d
发表时间：
2010-11-07
期刊：
Chemical communications (Cambridge, England)
影响因子：
--
作者：
Garibay SJ;Cohen SM
通讯作者：
Cohen SM
影响因子：
8.6
作者：
Coudert, Francois-Xavier
通讯作者：
Coudert, Francois-Xavier
影响因子：
15
作者：
Li, Zheng;Zeng, Hua Chun
通讯作者：
Zeng, Hua Chun
影响因子：
3.1
作者：
Bon, Volodymyr;Senkovska, Irena;Kaskel, Stefan
通讯作者：
Kaskel, Stefan
影响因子：
15
作者：
Cavka, Jasmina Hafizovic;Jakobsen, Soren;Lillerud, Karl Petter
通讯作者：
Lillerud, Karl Petter