多孔聚咔唑用于二氧化碳捕获与催化转化  

Carbazole-based porous organic polymers for carbon dioxide capture and catalytic conversion

作　　者：王天雄 韩宝航[1,2] Tianxiong Wang;Baohang Han(CAS Key Laboratory of Nanosystem and Hierarchical Fabrication,CAS Center for Excellence in Nanoscience,National Center for Nanoscience and Technology,Beijing 100190,China;University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]国家纳米科学中心,中国科学院纳米科学卓越创新中心,中国科学院纳米系统与多级次制造重点实验室,北京100190 [2]中国科学院大学,北京100049

出　　处：《科学通报》2020年第31期3389-3400,共12页Chinese Science Bulletin

基　　金：国家自然科学基金(21574032,21674026);中德科学中心中德合作研究项目(GZ1286);中国科学院国际伙伴计划(121D11KYSB20170031)资助。

摘　　要：二氧化碳作为一种常见的温室气体,其浓度的升高造成了全球性的生态环境问题,有效地捕集和利用二氧化碳,不仅具有环境保护意义,也具有工业和经济意义.有机多孔聚合物(POPs)作为一种新兴的多孔材料,具有高孔隙率、低密度、可设计的结构和组成、易于官能化和高稳定性等特点,在气体存储/分离、生物医药、污染处理、能源、催化等领域具有广阔的应用前景.咔唑类化合物构建的聚咔唑具有微孔结构,富含氮元素,对二氧化碳具有高吸附容量和选择性;功能性基团的引入也有助于进一步提升材料的吸附性能.线型的二氧化碳分子具有高稳定性,其转化需要催化剂的参与以实现高效反应.利用功能性分子直接构建或后修饰策略,均能制备出具有催化活性的聚咔唑,多孔性、吸附性、催化活性的结合使聚合物在二氧化碳化学转化、电催化和光催化还原中表现出优异的性能.与分子催化剂相比,聚咔唑的多孔性不仅能保证催化位点与反应物充分接触,而且可实现底物的富集并对反应有限域作用,提升反应效率和选择性.作为异相催化剂,聚咔唑回收方便,在循环实验中依然能保持高催化活性.本文将重点介绍多孔聚咔唑的制备方法及其在二氧化碳吸附与催化转化等方面的应用,分析材料结构与性能的关系,总结高性能聚合物所需的关键因素.Carbon dioxide is a kind of notorious greenhouse gas,and its rapidly increased concentration has caused global ecological and environmental problems.The efficient capture and conversion of carbon dioxide not only possess significance for environment,but also contribute to the development of industry and economy.Porous organic polymers(POPs)are a new class of porous materials that possess high porosity,high thermal/chemical stability,low density,designable structures and compositions,and facile functionalization strategies.POPs have been widely researched and applied in gas storage/separation,biomedicine,contaminant treatment,energy,catalysis and other fields.Polycarbazoles and polymers containing carbazole units can be constructed through various reactions depending on the structure and property of monomers.The oxidative coupling reaction and other reactions,such as Sonogashira-Hagihara coupling reaction,Suzuki coupling reaction,and Yamamoto reaction,have been employed to the construction of conjugated porous polymers.Monomers with suitable functional groups are utilized to fabricate hypercrosslinked porous polycarbazoles.Triazine-based polymers can be prepared from nitriles by a cyclotrimerization reaction.Covalent organic frameworks are constructed through Schiff-base reaction between amine-modified monomers and aldehyde compounds.Moreover,electropolymerization is a facile method to deposit porous films with a high monomer density on the surface of electrodes.Carbazole-based porous organic polymers possess microporous structures and abundant nitrogen contents,which show high sorption capacity and selectivity for carbon dioxide.For example,CPOP-1 constructed from 1,3,5-tri(9-carbazolyl)-benzene possesses a high adsorbing capacity of 21.2 wt%at 273 K and 1.0 bar.Furthermore,the introduction of functional moieties,such as pyridine and hydrazine,helps to improve the adsorption performance.The transformation of linear carbon dioxide requires a significant energy input because of its thermodynamic stability,the disso

关 键 词：咔唑 有机多孔聚合物 二氧化碳 吸附 转化 

分 类 号：TQ426[化学工程] X701[环境科学与工程—环境工程]