Qian Hai-Long, Meng Fan-Lin, Yang Cheng-Xiong, Yan Xiu-Ping
State Key Laboratory of Food Science and Technology, Jiangnan University, Wuxi, 214122, China.
Institute of Analytical Food Safety, School of Food Science and Technology, Jiangnan University, Wuxi, 214122, China.
Angew Chem Int Ed Engl. 2020 Sep 28;59(40):17607-17613. doi: 10.1002/anie.202006535. Epub 2020 Aug 11.
Design of stable adsorbents for selective gold recovery with large capacity and fast adsorption kinetics is of great challenge, but significant for the economy and the environment. Herein, we show the design and preparation of an irreversible amide-linked covalent organic framework (COF) JNU-1 via a building block exchange strategy for efficient recovery of gold. JNU-1 was synthesized through the exchange of 4,4'-biphenyldicarboxaldehyde (BA) in mother COF TzBA consisting of 4,4',4''-(1,3,5-triazine-2,4,6-triyl)trianiline (Tz) and BA with terephthaloyl chloride. The irreversible amide linked JNU-1 gave good stability, unprecedented fast kinetics, excellent selectivity and outstanding adsorption capacity for gold recovery. X-ray photoelectron spectroscopy along with thermodynamic study and quantum mechanics calculation reveals that the excellent performance of JNU-1 for gold recovery results from the formation of hydrogen bonds C(N)-H⋅⋅⋅Cl and coordinate interaction of O and Au. The rational design of irreversible bonds as both inherent linkage and functional groups in COFs is a promising way to prepare stable COFs for diverse applications.
设计具有大容量和快速吸附动力学的用于选择性回收金的稳定吸附剂极具挑战性,但对经济和环境意义重大。在此,我们展示了通过构建单元交换策略设计和制备不可逆酰胺连接的共价有机框架(COF)JNU-1以高效回收金。JNU-1是通过在由4,4',4''-(1,3,5-三嗪-2,4,6-三基)三苯胺(Tz)和4,4'-联苯二甲醛(BA)组成的母体COF TzBA中,将4,4'-联苯二甲醛(BA)与对苯二甲酰氯进行交换而合成的。不可逆酰胺连接的JNU-1在金回收方面具有良好的稳定性、前所未有的快速动力学、优异的选择性和出色的吸附容量。X射线光电子能谱以及热力学研究和量子力学计算表明,JNU-1在金回收方面的优异性能源于氢键C(N)-H⋅⋅⋅Cl的形成以及O与Au的配位相互作用。在COF中合理设计作为固有连接和官能团的不可逆键是制备用于多种应用的稳定COF的一种有前途的方法。