金属-多孔有机分子笼纳米复合物的研究进展

doi:10.6023/cjoc202207020

摘要/Abstract

多孔有机分子笼(POC)是一类具有固定腔隙的离散分子, 因其稳定的孔隙结构、较高的比表面积和良好的可溶性, 正成为一类可用于容纳特定大小的分子或离子的新兴功能性材料. 除此之外, 该类材料中稳定存在的开放孔隙结构, 使其在气体分离与储存、传感器件、药物运输等领域具有广泛的应用, 已逐渐成为国内外研究的热点. 目前, 多孔有机分子笼存在能与金属结合的位点, 并具有空间限域效应, 能有效防止金属纳米颗粒的团聚, 故常被用于特定尺寸金属纳米颗粒的制备, 从而形成金属-多孔有机分子笼纳米复合材料. 多孔有机分子笼不仅可调控金属纳米粒子的大小, 还可通过多孔笼体结构的保护, 在不影响其原子表面可及率的条件下, 稳定其微纳结构. 相比于传统金属纳米催化剂, 金属-多孔有机分子笼纳米复合物不仅具有更优越的稳定性, 还可提供更多的催化活性位点. 总结了近年来金属-多孔有机分子笼复合领域的研究成果, 以及其应用领域的重要进展, 为金属-多孔有机分子笼纳米复合物在催化、传感、医学等方面的后续研究提供启示.

关键词: 多孔有机分子笼, 金属纳米颗粒, 纳米复合结构, 原子可及率

Porous organic molecular cage (POC) is a kind of discrete molecule with specific sized cavities. Due to stable pore structure, high specific surface area, and good solubility, POC is emerging as a promising multi-functional material by accepting specific-sized molecules or ions within the cavity. In addition, derived from the stable and open pores, POCs can be utilized to a variety of applications, such as gas separation and storage, sensors, drug delivery, and so on, which is becoming a research hotspot at home and abroad. At present, given to the strong binding sites with metal nanoparticles (MNPs) and spatial confinement effect within the cage, POCs provide a new and stable way to protect metal nanoparticles from aggregation. Therefore, POCs are often used to prepare the metal nanoparticles of specific size, forming the metal-porous organic cage nanocomposites. The advantage of POCs in the metal-POCs nanocomposite is not only to regulate the size of metal nanoparticles but also to stabilize the micro/nanostructures without affecting the surface accessibility of active atoms within cages. Compared with traditional method to stabilize catalytic nanoparticles, MNPs-POCs composite has better stability and more active catalytic centers. The recent research achievements in MNPs-POCs nanocomposites and their important applications are summarized in this review, which is expected to inspire the further application in catalysis, sensors, medicine, etc.

Key words: porous organic cage, metal nanoparticles, nanocomposites, surface atom accessibility

引用此文

陈嘉麟, 马郅蘅, 李禹沣, 曹思炜, 庄强. 金属-多孔有机分子笼纳米复合物的研究进展[J]. 有机化学, 2023, 43(1): 120-129.

Jialin Chen, Zhiheng Ma, Yufeng Li, Siwei Cao, Qiang Zhuang. Research Progress in Metal-Porous Organic Cage Nanocomposites[J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 120-129.

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图/表 7

图1. (a) Cage 1, Cage 2和Cage 3的分子结构[16]、(b) Cage 3a的合成[17]以及(c)李昊等合成的阳离子笼[18]

Figure 1. (a) Molecular structures of Cage 1, Cage 2 and Cage 3,[16] (b) synthesis of Cage 3a,[17] and (c) cationic cage synthesized by Lei[18]

图2. (a) Iwasawa等提出的基于硼酯合成的动态自组装合成方式[20]、(b) Mastalerz及其课题组构筑的大型多孔有机分子[21]以及(c) Ivanova及其课题组构筑的笼形化合物1, 2[22]

Figure 2. (a) Dynamic self-assembly synthesis method based on boron ester generation proposed by Iwasawa[20], (b) large porous organic molecules constructed by Zhang[21], and (c) cages 1, 2 constructed by Ivanova[22]

图3. (a) COP-5的炔烃复分解路线[23]、(b) 4D2h的一步炔烃复分解反应合成[24]、(c) [8???+12]硼酯笼经烯烃复分解反应形成的外腔体结构[25]

Figure 3. (a) Alkyne redecomposition route of COP-5[23], (b) one-step alkyne redecomposition reaction of 4D2h[24], and (c) the outer cavity structure of [8???+12] borate cage formed by olefin redecomposition reaction[25]

图4. (a)引入DABCO构筑的cage-1与cage-2[29]、(b) cage-3与cage-4[30]

Figure 4. (a) cage-1 and cage-2 constructed by DABCO[29], and (b) cage-3 and cage-4[30]

图5. (a)张伟等合成的Au NPs[32]、(b)Masayuki等合成的Fh@MOC结构[35]

Figure 5. (a) Au NPs synthesized by Zhang[32], and (b) Fh@- MOC synthesized by Masayuki[35]

图6. (a) Au-NPs于八面体晶面上自组装形成单层薄膜[37]、(b) Fe3O4-NPs形成致密单层铁氧体纳米超晶格[38]

Figure 6. (a) Au-NPs self-assemble on octahedral crystal plane to form monolayer film[37], and (b) Fe3O4-NPs formation of dense monolayer ferrite nanosuperlattice[38]

图7. Gao等制备的一种半异相金属钯-酶一体化催化剂[43]

Figure 7. Semi-heterogeneous palladium-enzyme integration catalyst prepared by Gao[43]

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