Structural Complexity in Metal-Organic Frameworks: Simultaneous Modification of Open Metal Sites and Hierarchical Porosity by Systematic Doping with Defective Linkers
Structural Complexity in Metal-Organic Frameworks: Simultaneous Modification of Open Metal Sites and Hierarchical Porosity by Systematic Doping with Defective Linkers
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DOI：
10.1021/ja503218j
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发表时间：
2014-07-09
影响因子：
15
通讯作者：
Fischer, Roland A.
中科院分区：
文献类型：
--
作者：
Fang, Zhenlan;Duerholt, Johannes P.;Fischer, Roland A.
在母体微孔MOFs的基础上，通过在合成过程中系统掺杂缺陷连接剂，获得了一系列缺陷工程金属有机骨架（DEMOFs），从而同时可控地修饰了配位不饱和金属位点（CUS）并引入了功能化介孔。在超高真空条件下，利用傅里叶红外光谱（FTIR）对CO的温度依赖性吸附/解吸进行了研究。通过对实验数据与理论模拟结果的匹配，推导出了精确的点缺陷结构模型。结果显示了CUS的电子和空间性质的多元多样性，证明了MOP缺陷结构在两个长度尺度上的单步调节，以克服CUS有限的活性位点特异性和有限的配位空间。此外，demof表现出有希望的改进物理性质，包括带隙、磁性和孔隙率，其分层微孔/中孔结构与框架中缺陷连接剂的性质和程度相关。
A series of defect-engineered metal-organic frameworks (DEMOFs) derived from parent microporous MOFs was obtained by systematic doping with defective linkers during synthesis, leading to the simultaneous and controllable modification of coordinatively unsaturated metal sites (CUS) and introduction of functionalized mesopores. These materials were investigated via temperature-dependent adsorption/desorption of CO monitored by FTIR spectroscopy under ultra-high-vacuum conditions. Accurate structural models for the generated point defects at CUS were deduced by matching experimental data with theoretical simulation. The results reveal multivariate diversity of electronic and steric properties at CUS, demonstrating the MOP defect structure modulation at two length scales in a single step to overcome restricted active site specificity and confined coordination space at CUS. Moreover, the DEMOFs exhibit promising modified physical properties, including band gap, magnetism, and porosity, with hierarchical micro/mesopore structures correlated with the nature and the degree of defective linker incorporation into the framework.