TB-COP对I_(2)和硝基苯酚的吸附性能及机理研究  

Research on the adsorption performance and mechanism of TB-COP for I_(2)and nitrophenol

作　　者：黄仁兰 梁晓童 高戈[1] 伍晚花 杨成 HUANG Ren-Lan;LIANG Xiao-Tong;GAO Ge;WU Wan-Hua;YANG Cheng(Key Laboratory of Green Chemistry&Technology of Ministry of Education,College of Chemistry,Sichuan University,Chengdu 610064,China)

机构地区：[1]四川大学化学学院绿色化学与技术教育部重点实验室,成都610064

出　　处：《四川大学学报(自然科学版)》2025年第1期169-181,共13页Journal of Sichuan University(Natural Science Edition)

基　　金：国家自然科学基金(22271201,92056116,21871194,22171194,21971169)。

摘　　要：放射性碘(包括^(129)I和^(131)I)和硝基酚类化合物是两种危害人体健康的工业污染物,对它们的高效捕获和存储存在着诸多挑战.本文通过曼尼希反应构筑了一种由朝格尔碱(Troger’s base,TB)桥联5,10,15,20-四(4-氨基苯基)卟啉(Por)的多孔有机材料TB‑COP.该材料具有较大的比表面积(525.5 m^(2)·g^(−1))和孔隙率(65%),能够分别对I_(2)蒸汽以及水溶液中I_(2)实现4.12和3.80 g·g^(−1)的高吸附量以及可逆释放,并且在6次循环实验后仍能保持不低于原来95%的高捕获能力.此外,TB‑COP还被证实能在水溶液中吸附硝基苯酚.通过红外、拉曼等实验和密度泛函理论(DFT)计算对TB‑COP吸附I_(2)、硝基苯酚的机理进行了研究,结果表明大量的富N结合位点、TB‑COP的共轭结构和TB中叔胺通过电荷转移作用参与的化学吸附过程是实现对这些污染物高量吸附的原因.Radioactive iodine(including ^(129)I and ^(131)I)and nitrophenol compounds are prevalent industrial pollutants known to pose significant risks to human health.The efficient capture and storage of these pollutants present critical challenges in environmental research.Developing effective adsorption materials for the capture and storage of I_(2)presents a promising approach to mitigating this issue.In this paper,a porous organic material(TB‑COP)consisting of 5,10,15,20-tetraki(s 4-aminophenyl)porphyrin(Por)bridged by Troger’s base(TB)has been constructed via the Mannich reaction.TB‑COP exhibited a large surface area(525.5 m^(2)·g^(−1))and porosity(65%),leading to high adsorption capacity of 4.12 and 3.80 g·g^(−1)for I_(2)vapor and I_(2)aqueous solution,respectively.The captured I_(2)could be effectively released.Even after six cycles,TB‑COP maintained a high capture capacity of over 95%of the original.In addition,TB‑COP demonstrated adsorption capacity for nitrophenol in aqueous solutions.The mechanism underlying TB‑COP's adsorption of I_(2)and nitrophenol was elucidated through IR and LR experiments and density functional theory(DFT)calculations.The results indicate that the high adsorption of these pollutants can be attributed to the large number of N-containing binding sites,the conjugated structure of TB‑COP,and the chemical adsorption process of tertiary amines in TB by charge transfer.

关 键 词：朝格尔碱 共价有机聚合物 碘吸附 硝基苯酚 

分 类 号：O632.6[理学—高分子化学]