Zhao Jie, Chen Rui, Huang Jian, Wang Fang, Tao Cheng-An, Wang Jianfang
College of Liberal Arts and Science, National University of Defense Technology, Changsha 410073, China.
ACS Appl Mater Interfaces. 2021 Sep 1;13(34):40863-40871. doi: 10.1021/acsami.1c08365. Epub 2021 Aug 18.
Two-dimensional (2D) metal-organic layer (MOL) materials are highly desired against chemical warfare agents (CWAs). However, the rapid synthesis of 2DMOLs with open metal sites in a single step is very challenging. Herein, a facile bottom-up method for synthesizing MOLs with microwave assistance is applied to produce Zr/Hf-BTB MOLs, composed of six-connected MO(OH) and the tritopic carboxylate ligand 1,3,5-tris(4-carboxyphenyl)benzene (BTB). The synthesis and ligand exchange steps can be combined into a single step to yield MOLs with active open sites directly. The as-synthesized MOLs demonstrate excellent catalytic performance toward the degradation of a CWA simulant. The theoretical calculations confirm that the high catalytic activity is due to the formate groups coordinated to the metal nodes being replaced by hydroxyl groups. The present work not only develops a method for the fast synthesis of 2D MOLs with active open metal sites in a single step but also provides a first demonstration for the application of 2D metal coordination materials in CWA protection.
二维(2D)金属有机层(MOL)材料对于对抗化学战剂(CWA)具有很高的需求。然而,一步法快速合成具有开放金属位点的二维金属有机层极具挑战性。在此,一种利用微波辅助合成金属有机层的简便自下而上方法被用于制备Zr/Hf-BTB金属有机层,其由六连接的MO(OH)和三齿羧酸盐配体1,3,5-三(4-羧基苯基)苯(BTB)组成。合成和配体交换步骤可以合并为一步,直接得到具有活性开放位点的金属有机层。所合成的金属有机层对化学战剂模拟物的降解表现出优异的催化性能。理论计算证实,高催化活性是由于与金属节点配位的甲酸根基团被羟基取代。本工作不仅开发了一种一步法快速合成具有活性开放金属位点的二维金属有机层的方法,还为二维金属配位材料在化学战剂防护中的应用提供了首个例证。