Li Mingyan, Chen Liangjun, Du Jiawei, Gong Chengtao, Li Tingting, Wang Jian, Li Feili, She Yuanbin, Jia Jianhong
College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China.
Innovation Research Center for Advanced Environmental Technology, Eco-industrial Innovation Institute ZJUT, 2 Rong-chang East Road, Quzhou 324400, China.
ACS Appl Mater Interfaces. 2024 Feb 21;16(7):8688-8696. doi: 10.1021/acsami.3c16227. Epub 2024 Feb 7.
As a common water pollutant, Pb has harmful effects on the nervous, hematopoietic, digestive, renal, cardiovascular, and endocrine systems. Due to the drawbacks of traditional adsorbents such as structural disorder, poor stability, and difficulty in introducing adsorption active sites, the adsorption capacity is low, and it is difficult to accurately study the adsorption mechanism. Herein, vinyl-functionalized covalent organic frameworks (COFs) were synthesized at room temperature, and sulfur-containing active groups were introduced by the click reaction. By precisely tuning the chemical structure of the sulfur-containing reactive groups through the click reaction, we found that the adsorption activity of the sulfhydryl group was higher than that of the sulfur atom in the thioether. Moreover, the incorporation of flexible linking groups was observed to enhance the adsorption activity at the active site. The maximum adsorption capacity of the postmodified COF TAVA-S-Et-SH for Pb(II) reached 303.0 mg/g, which is 2.9 times higher than that of the unmodified COF. This work not only demonstrates the remarkable potential of the "thiol-ene" click reaction for the customization of active adsorption sites but also demonstrates the remarkable potential of the "thiol-alkene" click reaction to explore the structure-effect relationship between the active adsorption sites and the metal ion adsorption capacity.
作为一种常见的水污染物,铅对神经、造血、消化、肾脏、心血管和内分泌系统都有有害影响。由于传统吸附剂存在结构无序、稳定性差以及难以引入吸附活性位点等缺点,其吸附能力较低,且难以准确研究吸附机理。在此,在室温下合成了乙烯基官能化的共价有机框架(COF),并通过点击反应引入含硫活性基团。通过点击反应精确调控含硫反应基团的化学结构,我们发现巯基的吸附活性高于硫醚中的硫原子。此外,观察到引入柔性连接基团可增强活性位点的吸附活性。后修饰的COF TAVA-S-Et-SH对Pb(II)的最大吸附容量达到303.0 mg/g,比未修饰的COF高2.9倍。这项工作不仅证明了“硫醇-烯”点击反应在定制活性吸附位点方面的巨大潜力,还证明了“硫醇-烯烃”点击反应在探索活性吸附位点与金属离子吸附容量之间的构效关系方面的巨大潜力。