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由共价有机框架(COFs)构建分级多孔整体材料及其在双酚 A 去除中的应用。

Construction of hierarchically porous monoliths from covalent organic frameworks (COFs) and their application for bisphenol A removal.

机构信息

Key Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China; University of Chinese Academy of Sciences, Beijing 100049, China.

Key Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.

出版信息

J Hazard Mater. 2018 Aug 5;355:145-153. doi: 10.1016/j.jhazmat.2018.05.022. Epub 2018 May 11.

Abstract

Subject to synthetic conditions, covalent organic frameworks (COFs) are usually in powder form. Herein, taking an azine-linked COF as an example, detailed characterizations indicated that accessible aldehyde groups and hydrazine groups (CNNH, 88 μmol g) concurrently existed on its surface. Intrigued by such feature, we have developed an approach based on ring-opening polymerization to shape COF powder into monoliths. The crystallinity and micropore of COF in monoliths were well remained, meanwhile, the ring-opening polymerization remarkably generated macropores ranging from 0.43 to 3.51 μm, indicating a hierarchically porous structure. The BET surface area of resultant monoliths with different COF mass fractions of 16%, 28% and 43% ranged from 105 to 281 m g. Due to the π-π interaction and hydrogen bond interaction, COF-based monoliths exhibited strong retention and rapid adsorption for bisphenol A (BPA) in aqueous medium. When 29 mL BPA solution (22.8 mg L) passed through COF-based monolith (28%), the adsorption capacity was up to 61.3 mg g. Furthermore, the COF-based monolith demonstrated excellent cycle use for catalyzing Suzuki-Miyaura coupling reaction after being coordinated with palladium acetate.

摘要

在合成条件下,共价有机骨架(COFs)通常呈粉末状。在此,以一种偶氮键合的 COF 为例,详细的表征表明其表面同时存在可及的醛基和腙基(CNNH,88μmol/g)。受这一特征的启发,我们开发了一种基于开环聚合的方法,将 COF 粉末成型为整体式材料。整体式材料中的 COF 结晶度和微孔得以很好地保留,同时,开环聚合显著地产生了孔径范围从 0.43 到 3.51μm 的大孔,表明其具有分级多孔结构。不同 COF 质量分数(16%、28%和 43%)的所得整体式材料的 BET 比表面积范围为 105 到 281m²/g。由于π-π 相互作用和氢键相互作用,基于 COF 的整体式材料在水介质中对双酚 A(BPA)表现出强保留和快速吸附。当 29mL BPA 溶液(22.8mg/L)通过 COF 基整体式材料(28%)时,吸附容量高达 61.3mg/g。此外,COF 基整体式材料在与醋酸钯配位后,用于催化 Suzuki-Miyaura 偶联反应时表现出优异的循环使用性能。

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