Yuan Ye, Yang Yajie, Meihaus Katie R, Zhang Shenli, Ge Xin, Zhang Wei, Faller Roland, Long Jeffrey R, Zhu Guangshan
Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun, China.
Department of Chemistry, University of California, Berkeley, CA, USA.
Nat Chem. 2023 Nov;15(11):1599-1606. doi: 10.1038/s41557-023-01273-3. Epub 2023 Jul 3.
The use of coordination complexes within covalent organic frameworks can significantly diversify the structures and properties of this class of materials. Here we combined coordination chemistry and reticular chemistry by preparing frameworks that consist of a ditopic (p-phenylenediamine) and mixed tritopic moieties-an organic ligand and a scandium coordination complex of similar sizes and geometries, both bearing terminal phenylamine groups. Changing the ratio of organic ligand to scandium complex enabled the preparation of a series of crystalline covalent organic frameworks with tunable levels of scandium incorporation. Removal of scandium from the material with the highest metal content subsequently resulted in a 'metal-imprinted' covalent organic framework that exhibits a high affinity and capacity for Sc ions in acidic environments and in the presence of competing metal ions. In particular, the selectivity of this framework for Sc over common impurity ions such as La and Fe surpasses that of existing scandium adsorbents.
在共价有机框架中使用配位络合物可显著使这类材料的结构和性质多样化。在此，我们通过制备由双齿（对苯二胺）和混合三齿部分组成的框架，将配位化学与网状化学相结合——一种有机配体和具有相似尺寸和几何形状的钪配位络合物，二者均带有末端苯胺基团。改变有机配体与钪络合物的比例能够制备出一系列具有可调钪掺入水平的结晶共价有机框架。随后从金属含量最高的材料中去除钪，得到了一种“金属印迹”共价有机框架，该框架在酸性环境以及存在竞争金属离子的情况下对钪离子表现出高亲和力和容量。特别地，该框架对钪相对于常见杂质离子（如镧和铁）的选择性超过了现有的钪吸附剂。
