Department of Chemistry and International Institute for Nanotechnology, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States.
Departments of Biomedical Engineering, Materials Science & Engineering, and Pharmacology, Simpson-Querrey Institute, Chemistry of Life Processes Institute, and Lurie Cancer Center, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States.
J Am Chem Soc. 2022 Apr 20;144(15):6674-6680. doi: 10.1021/jacs.2c01095. Epub 2022 Apr 6.
Metal-organic frameworks (MOFs) constructed from Zr nodes and tetratopic carboxylate linkers display high structural diversity and complexity in which various crystal topologies can result from identical building units. To determine correlations between MOF topologies and experimental parameters, such as solvent choice or modulator identity and concentration, we demonstrate the rapid generation of phase diagrams for Zr-MOFs with 1,4-dibromo-2,3,5,6-tetrakis(4-carboxyphenyl)benzene linkers under a variety of conditions. We have developed a full set of methods for high-throughput transmission electron microscopy (TEM), including automated sample preparation and data acquisition, to accelerate MOF characterization. The use of acetic acid as a modulator yields amorphous, NU-906, NU-600, and mixed-phase structures depending on the ratio of ,-dimethylformamide to ,-diethylformamide solvent and the quantity of the modulator. Notably, the use of formic acid as a modulator enables direct control of crystal growth along the direction through variation of the modulator quantity, thus realizing aspect ratio control of NU-1008 crystals with different catalytic hydrolysis performance toward a nerve agent simulant.
金属-有机骨架（MOFs）由 Zr 节点和四齿羧酸连接体构成，在结构上具有高度的多样性和复杂性，其中各种晶体拓扑结构可以由相同的构建单元产生。为了确定 MOF 拓扑结构与实验参数之间的相关性，例如溶剂选择或调节剂的种类和浓度，我们展示了在各种条件下，具有 1,4-二溴-2,3,5,6-四（4-羧基苯基）苯连接体的 Zr-MOFs 的相图的快速生成。我们已经开发了一套用于高通量透射电子显微镜（TEM）的全方法，包括自动化的样品制备和数据采集，以加速 MOF 的表征。使用乙酸作为调节剂会产生无定形、NU-906、NU-600 和混合相结构，这取决于 -二甲基甲酰胺与 -二乙基甲酰胺溶剂的比例以及调节剂的数量。值得注意的是，使用甲酸作为调节剂可以通过调节调节剂的数量来直接控制晶体沿着 方向的生长，从而实现 NU-1008 晶体的纵横比控制，其对神经毒剂模拟物的催化水解性能不同。
