Defect Creation by Linker Fragmentation in Metal-Organic Frameworks and Its Effects on Gas Uptake Properties
Defect Creation by Linker Fragmentation in Metal-Organic Frameworks and Its Effects on Gas Uptake Properties
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DOI：
10.1021/ic500722n
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发表时间：
2014-07-07
影响因子：
4.6
通讯作者：
Farha, Omar K.
中科院分区：
文献类型：
--
作者：
Barin, Gokhan;Krungleviciute, Vaiva;Farha, Omar K.
我们成功地展示了一种基于连接体断裂的方法，可以产生缺陷并调整两种金属有机框架NU-125和HKUST-1的孔体积和表面积，这两种框架都具有铜桨轮节点。取决于接头片段组成，缺陷可以是空位或原始接头不具有的官能团。在第一种情况下，我们表明，表面积和孔体积增加，而在第二种情况下，它们减少。还研究了不同气体在大的温度和压力范围内缺陷对高压气体吸收的影响。我们发现，尽管增加了孔体积和表面积的结构与空位，绝对吸附甲烷HKUST-1和NU-125略有增加。然而，由于在低压下较低的吸收，这两种情况下的工作能力（可输送量在65至5巴之间）与母框架保持相似。在NU-125的情况下，缺陷的影响在较低的温度下变得更加明显，反映了改变形式的更大的表面积和孔体积。
We successfully demonstrate an approach based on linker fragmentation to create defects and tune the pore volumes and surface areas of two metal-organic frameworks, NU-125 and HKUST-1, both of which feature copper paddlewheel nodes. Depending on the linker fragment composition, the defect can be either a vacant site or a functional group that the original linker does not have. In the first case, we show that both surface area and pore volume increase, while in the second case they decrease. The effect of defects on the high-pressure gas uptake is also studied over a large temperature and pressure range for different gases. We found that despite an increase in pore volume and surface area in structures with vacant sites, the absolute adsorption for methane decreases for HKUST-1 and slightly increases for NU-125. However, the working capacity (deliverable amount between 65 and 5 bar) in both cases remains similar to parent frameworks due to lower uptakes at low pressures. In the case of NU-125, the effect of defects became more pronounced at lower temperatures, reflecting the greater surface areas and pore volumes of the altered forms.