多酸基多孔离子晶体的前沿与应用  

Frontiers and applications of polyoxometalates-based porous ionic crystals

作　　者：田文玉 郭琳 胡汉斌 楚进锋[1] 何蕾 宋宇飞[1,2] Wenyu Tian;Lin Guo;Hanbin Hu;Jinfeng Chu;Lei He;Yu-Fei Song(State Key Laboratory of Chemical Resource Engineering,Beijing University of Chemical Technology,Beijing 100029,China;Beijing Advanced Innovation Center for Soft Matter Science and Engineering,Beijing University of Chemical Technology,Beijing 100029,China)

机构地区：[1]北京化工大学化工资源有效利用国家重点实验室,北京100029 [2]北京化工大学北京软物质科学与工程高精尖创新中心,北京100029

出　　处：《科学通报》2022年第7期655-669,共15页Chinese Science Bulletin

基　　金：国家重点研发计划(2017YFB0307303);国家杰出青年科学基金(21625101);国家自然科学基金(22178019,U1707603,21521005,22007004);中央高校基金(XK1802-6,XK1803-05,XK1902,12060093063);中央高校基本科研业务费专项资金(buctrc202010)资助。

摘　　要：多酸基多孔离子晶体(polyoxometalates-based porous ionic crystals,PPICs)是由带相反电荷的无机多酸阴离子(polyoxometalates,POMs)和配位化合物阳离子簇通过离子键或氢键相互作用形成的一类独特的多孔材料.其孔道尺寸可调、组成可控、合成方法简便.PPICs兼具阴、阳离子的优点,各组分间协同驱动,表现出比单一组分更优异的性能.通过对PPICs各组分的合理设计,可以有效调控其理化性质.本文系统地总结了PPICs的结构组成,阐述了PPICs可调的孔道结构、独特的氧化还原特征、强酸性及磁性等性质,列举了PPICs在选择性吸附、酸催化、电化学等领域的应用进展,并对其未来发展方向进行了展望.Polyoxometalates(denoted as POMs) are discrete metal-oxide anions of V,Mo,W,etc.,with variable structures and subnanometer sizes.Plenty of POMs and their derivatives have been reported due to their oxygen-enriched surface and abundant substitutional chemistry.However,few studies have focused on the modulation of the counter cations so far.Different from common cations,such as Na^(+),NH_(4)^(+) and other organic ammonium ions(tetramethylammonium,tetrabutylammonium,etc.),cation clusters with larger size can also be used as counter ions of POMs.They are arranged alternately through ionic bonds or hydrogen bonds to form the solid ionic crystal materials with special properties,which are named POM-based porous ionic crystals(PPICs).The use of cation clusters with different compositions greatly enriches the structure and type of PPICs,which further boosts the development of polyoxometalates chemistry.The POMs anions and large metal complex cations in PPICs are regularly arranged into a porous honeycomb or layered structure.Some PPICs also contain monovalent cations such as H+and alkali metal ions to balance their extra negative charges.The use of ion clusters facilitates the formation of pore structures in the PPICs lattice because they can reduce the electrostatic interaction between cations and anions.Thus,the pore structure of PPICs is much larger than that of POMs.Note that the pore size in PPICs can be easily adjusted by changing the shape,size and charges of cation and anions.Apart from the electrostatic interaction,anisotropic π-π stacking and hydrogen bonding network among the components of PPICs also contribute to their assembly.All these interaction modes will affect the arrangement of anions and cations in the PPICs lattice,resulting in the formation of different hole sizes and various channels characteristics in the crystal lattice,such as hydrophilic,hydrophobic and amphiphilic pores.In addition,the long-range Coulomb interaction works isotropically,leading to the easy transformation of the flexible PPIC

关 键 词：多酸 离子晶体 多孔性 氧化还原性 选择性吸附 

分 类 号：TB383.4[一般工业技术—材料科学与工程] O641.4[理学—物理化学]