Post-synthetic metalation of organic cage for enhanced porosity and catalytic performance  

作　　者：Miao Yang Xun Chen Yifei Xie El-Sayed MEl-Sayed Ning Xu Wenjing Wang Kongzhao Su Daqiang Yuan 

机构地区：[1]State Key Lab of Structure Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China [2]University of the Chinese Academy of Sciences,Beijing 100049,China [3]College of Chemistry,Fuzhou University,Fuzhou 310116,China [4]Chemical Refining Laboratory,Refining Department,Egyptian Petroleum Research Institute,Nasr City 11727,Egypt

出　　处：《Science China Chemistry》2023年第6期1763-1770,共8页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(22071244);the Youth Innovation Promotion Association CAS(2022305);the Natural Science Foundation of Fujian Province of China(2022J01503,2020J05087);the China Postdoctoral Science Foundation(2020M671954)。

摘　　要：Porous organic cages(POCs)have shown great potential in many applications,and post-synthetic modification(PSM)has been confirmed to be an effective strategy to tailor their structures and related functionalities.However,it is extremely challenging to develop a general platform for simple-to-make functional POCs for advanced applications by PSM method.Herein,we reported that octahedral calix[4]resorcinarene-based hydrazone-linked porous organic cage(HPOC-401)provides an excellent platform for post-synthetic metalation by various transition metal(TM)ions under mild conditions due to the abundance of coordination sites in its skeleton.Such metalated products(HPOC-401-TM)exhibit Brunauer-Emmett-Teller(BET)surface area up to1,456 m^(2)g^(-1),much higher than that of the pristine HPOC-401,which has a BET value of 474 m^(2)g^(-1).Moreover,the metalation and porosity increases further influence their gas capture,separation,as well as catalytic performance.For instance,HPOC-401-TM products exhibit higher CO_(2),H_(2),and C2 hydrocarbon gas uptake,as well as higher C_(2)H_(6)/C_(2)H_(4) selectivity than HPOC-401.Moreover,the HPOC-401-TM also shows better catalytic performance in the cycloaddition of CO_(2) with epoxides compared to HPOC-401.These findings uncover a simple yet effective approach for modifying the porosity characteristics of organic cages,which will undoubtedly expand their future implementations.

关 键 词：porous organic cage(POC) resorcinarene post-synthetic metalation(PSM) gas adsorption and separation CO_(2)cycloaddition 

分 类 号：O643.3[理学—物理化学]