Highly Efficient and Reversible Iodine Capture in Hexaphenylbenzene-Based Conjugated Microporous Polymers

被引:348
作者
Liao, Yaozu [1 ,2 ,3 ]
Weber, Jens [4 ]
Mills, Benjamin M. [3 ]
Ren, Zihao [3 ]
Faul, Charl F. J. [3 ]
机构
[1] Donghua Univ, State Key Lab Modificat Chem Fibers & Polymer Mat, Shanghai 201620, Peoples R China
[2] Donghua Univ, Coll Mat Sci & Engn, Shanghai 201620, Peoples R China
[3] Univ Bristol, Sch Chem, Bristol BS8 1TS, Avon, England
[4] Univ Appl Sci, Dept Chem, Hsch Zittau Gorlitz, Theodor Korner Allee 16, D-02763 Zittau, Germany
基金
英国工程与自然科学研究理事会; 中国国家自然科学基金;
关键词
METAL-ORGANIC FRAMEWORK; SURFACE-AREA; CAMPHORSULFONIC ACID; VOLATILE IODINE; CHARGE-TRANSFER; SINGLE-CRYSTAL; GAS SORPTION; ADSORPTION; CONDUCTIVITY; NETWORKS;
D O I
10.1021/acs.macromol.6b00901
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
The effective and safe capture and storage of radioactive iodine (1291 or 1311) is of significant importance during nuclear waste storage and nuclear energy generation. Here we present detailed evidence of highly efficient and reversible iodine capture in hexaphenylbenzene-based conjugated microporous polymers (HCMPs), synthesized via Buchwald-Hartwig (BH) cross-coupling of a hexakis(4-bromophenyl)benzene (HBB) core and aryl diamine linkers. The HCMPs present moderate surface areas up to 430 m(2) g(-1), with narrow pore size distribution and uniform ultramicropore sizes of less than 1 nm. Porous properties are controlled by the strut lengths and rigidities of linkers, while porosity and uptake properties can be tuned by changing the oxidation state of the HCMPs. The presence of a high number of amine functional groups combined with microporosity provides the HCMPs with extremely high iodine affinity with uptake capacities up to 336 wt %, which is to the best of our knowledge the highest reported to date. Two ways to release the adsorbed iodine were explored: either slow release into ethanol or quick release upon heating (with a high degree of control). Spectral studies indicate that the combination of microporosity, amine functionality, and abundant pi-electrons ensured well-defined host-guest interactions and controlled uptake of iodine. In addition, the HCMPs could be recycled while maintaining 90% iodine uptake capacity (up to 295%). We envisage wider application of these materials in the facile uptake and removal of unwanted oxidants from the environment.
引用
收藏
页码:6322 / 6333
页数:12
相关论文
共 75 条
[1]   Rapid removal of organic micropollutants from water by a porous β-cyclodextrin polymer [J].
Alsbaiee, Alaaeddin ;
Smith, Brian J. ;
Xiao, Leilei ;
Ling, Yuhan ;
Helbling, Damian E. ;
Dichtel, William R. .
NATURE, 2016, 529 (7585) :190-U146
[2]  
[Anonymous], LANDOLTBORNSTEIN
[3]  
[Anonymous], CHEM COMMUN
[4]   Electronic and structural evidences for charge transfer and localization in iodine-doped pentacene [J].
Brinkmann, M ;
Videva, VS ;
Bieber, A ;
André, JJ ;
Turek, P ;
Zuppiroli, L ;
Bugnon, P ;
Schaer, M ;
Nuesch, F ;
Humphry-Baker, R .
JOURNAL OF PHYSICAL CHEMISTRY A, 2004, 108 (40) :8170-8179
[5]   Gas Permeability of Hexaphenylbenzene Based Polymers of Intrinsic Microporosity [J].
Carta, Mariolino ;
Bernardo, Paola ;
Clarizia, Gabriele ;
Jansen, Johannes C. ;
McKeown, Neil B. .
MACROMOLECULES, 2014, 47 (23) :8320-8327
[6]   Hybrid Porous Materials with High Surface Area Derived from Bromophenylethenyl-Functionalized Cubic Siloxane-Based Building Units [J].
Chaikittisilp, Watcharop ;
Sugawara, Ayae ;
Shimojima, Atsushi ;
Okubo, Tatsuya .
CHEMISTRY-A EUROPEAN JOURNAL, 2010, 16 (20) :6006-6014
[7]   Trapping Guests within a Nanoporous Metal-Organic Framework through Pressure-Induced Amorphization [J].
Chapman, Karena W. ;
Sava, Dorina F. ;
Halder, Gregory J. ;
Chupas, Peter J. ;
Nenoff, Tina M. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (46) :18583-18585
[8]   Radioactive Iodine Capture in Silver-Containing Mordenites through Nanoscale Silver Iodide Formation [J].
Chapman, Karena W. ;
Chupas, Peter J. ;
Nenoff, Tina M. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (26) :8897-+
[9]   Porous Organic Polymers Based on Propeller-Like Hexaphenylbenzene Building Units [J].
Chen, Qi ;
Luo, Min ;
Wang, Tao ;
Wang, Jin-Xiang ;
Zhou, Ding ;
Han, Ying ;
Zhang, Chang-Shan ;
Yan, Chao-Guo ;
Han, Bao-Hang .
MACROMOLECULES, 2011, 44 (14) :5573-5577
[10]   Synthesis of conjugated microporous polymer nanotubes with large surface areas as absorbents for iodine and CO2 uptake [J].
Chen, Yingfan ;
Sun, Hanxue ;
Yang, Ruixia ;
Wang, Tingting ;
Pei, Chunjuan ;
Xiang, Zhentao ;
Zhu, Zhaoqi ;
Liang, Weidong ;
Li, An ;
Deng, Weiqiao .
JOURNAL OF MATERIALS CHEMISTRY A, 2015, 3 (01) :87-91