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《Acta Chimica Sinica》 2016-01
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Targeted Syntheses of Charged Porous Aromatic Frameworks for Iodine Enrichment and Release

Yan,Zhuojun;Yuan,Ye;Liu,Jia;Li,Qin;Nguyen,Nam-Trung;Zhang,Daming;Tian,Yuyang;Zhu,Guangshan;State Key Laboratory on Integrated Optoelectronics,College of Electronic Science and Engineering,Jilin University;Key Laboratory of Polyoxometalate Science of the Ministry of Education,Faculty of Chemistry,Northeast Normal University;Queensland Micro-and Nanotechnology Centre,Griffith University;  
In this paper, we synthesized two charged porous aromatic frameworks(PAF-21 and PAF-22) using lithium tetrakis(4-iodophenyl)borate as tetrahedral units and 1,4-benzenediboronic acid or 4,4'-biphenyldiboronic acid as linear linkers via a Suzuki coupling reaction. FTIR spectra prove the completion of the coupling reaction. The absence of the B-OH band(at 3370 cm-1) and the C-I bands(at 480 and 506 cm-1) in the FTIR spectra indicate the formation of polymeric networks. The solid-state 13 C CP/MAS NMR spectra of PAF-21 and PAF-22 showed the carbon resonances with chemical shift in the range of δ 120~145, which are related to aromatic carbon atoms of framework-building phenylene groups. Simultaneously, the only resonance at δ-26 shown in 11 B MAS NMR spectra can be attributed to the central B atom in the framework. Both 13 C CP/MAS NMR and 11 B MAS NMR analyses show the absence of other resonances, testifying that an almost complete coupling reaction has taken place. Powder X-ray diffraction(PXRD) of these PAFs revealed their amorphous texture, no long-range ordered frameworks could be detected due to the distortion and interpenetration of the phenyl rings. Scanning electron microscopy(SEM) images showed that PAF-21 and PAF-22 were composed of large fused polymer masses. Transmission electron microscopy(TEM) images also revealed that they were amorphous materials. Thermogravimetric analysis(TGA) showed that PAF-21 and PAF-22 were thermally stable up to 350 °C under atmosphere. In addition, these materials also exhibit high chemical stability, as verified by no dissolution or decomposition in common organic solvents such as methanol, ethanol, acetone, THF, CH2Cl2, CHCl3, DMF, etc. Carbon dioxide sorption isotherms were measured on the activated samples at 273 K and 1 bar. The CO2 uptake is 19.2 mg/g for PAF-21 and 22.5 mg/g for PAF-22, respectively. Compared with other materials such as zeolites and metal-organic frameworks, these PAFs show very high affinity and capacity for iodine(1520 mg/g for PAF-21 and 1960 mg/g for PAF-22 respectively) due to their special charged aromatic networks. Significantly, PAF-21 and PAF-22 could reversibly release iodine molecules in ethanol solution, might be used in practical and commercial applications for contaminative iodine treatment.
【Fund】: 国家重点基础研究发展计划(973计划;No.2012CB821700);; 重大国际(地区)合作研究(No.21120102034);; 国家自然科学基金(No.20831002)资助~~
【CateGory Index】: O625;O647.33
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