共轭多孔有机聚合物的制备及其对核废料中碘的捕获  

Preparation of conjugated porous organic polymers and its capture of iodine from nuclear waste.

作　　者：苏品杰 王净 褚阔 罗亦夫 孙琪琪 董欣 张红翠 崔博 闫卓君 布乃顺[1] SU Pin-jie;WANG Jing;CHU Kuo;LUO Yi-fu;SUN Qi-qi;DONG Xin;ZHANG Hong-cui;CUI Bo;YAN Zhuo-jun;BU Nai-shun(School of Environmental Science,Liaoning University,Shenyang 110036,China;College of Chemistry,Liaoning University,Shenyang 110036,China)

机构地区：[1]辽宁大学环境学院,辽宁沈阳110036 [2]辽宁大学化学院,辽宁沈阳110036

出　　处：《中国环境科学》2023年第2期568-575,共8页China Environmental Science

基　　金：国家重点研发计划项目(2018YFC1801200);“兴辽英才计划”青年拔尖人才项目(XLYC2007032);辽宁省自然科学基金资助项目(2021-MS-149);辽宁省教育厅科学研究经费项目(LQN202003);辽宁省科技重大专项(2019JH1/10300001);辽宁大学大学生创新创业训练计划项目(X202210140023)。

摘　　要：将1,3,5-三乙炔基苯与2,7-二溴-9,9-二苯基芴进行Sonogashira-Hagihara偶联反应,成功合成了一种共轭多孔有机聚合物(命名为LNU-15).该聚合物的骨架分解温度在350℃以上,且不溶于有机溶剂,具有良好的化学稳定性和热稳定性.LNU-15主要以1.379nm的均一孔径存在.由于单开放通道、大量的强亲和力结合位点以及π共轭结构,LNU-15对碘具有优异的捕获能力,获得2,400mg/g的捕获量.根据拟二级动力学方程可知,LNU-15对碘的吸附速率常数为0.003g/(g⋅min),理论平衡捕获量为2,490mg/g.实际捕获量为理论量的96.4%.此外,LNU-15可在空气中加热或乙醇溶液中可逆释放碘,且具有一定的循环稳定性.LNU-15破解了由孔隙堵塞造成的“死空间”以及客体分子不易进入骨架的问题,可用于环境碘污染控制,并为核工业发展提供重要支撑.A conjugated porous organic polymer(named LNU-15) was successfully synthesized by Sonogashira-Hagihara coupling reaction of 1,3,5-triacetylene benzene and 2,7-dibromo-9, 9-diphenyl fluorene. The skeleton decomposition temperature of LNU-15 was above 350℃, and it was insoluble in organic solvents, showing good chemical and thermal stability. The pore size distribution of LNU-15 presented uniform microporous size of 1.379nm. Because of its single open channel, a large number of strong affinity binding sites, as well as π-conjugated network structure, LNU-15 showed an excellent ability to capture iodine,with a high uptake value of 2,400mg/g. According to the pseudo-second-order kinetic equation, the adsorption rate constant of LNU-15 for iodine was 0.003g/(g·min), and the theoretical equilibrium catch was 2,490mg/g. The actual catch was 96.4% of the theoretical amount. In addition, LNU-15 could reversibly release iodine when heated in air or in ethanol solution, showing a certain cyclic stability. LNU-15 has solved the "dead space" caused by pore blockage and the difficulty for guest molecules to enter the skeleton, which can be used for environmental iodine pollution control and provide important support for the development of nuclear industry.

关 键 词：碘捕获 可逆释放 Sonogashira-Hagihara偶联反应 多孔有机聚合物 共轭结构 

分 类 号：X591[环境科学与工程—环境工程]