多孔有机笼用于能源转换及储存的研究进展

doi:10.6023/A25030098

化学学报 ›› 2025, Vol. 83 ›› Issue (6): 624-638.DOI: 10.6023/A25030098 上一篇下一篇

综述

多孔有机笼用于能源转换及储存的研究进展

崔雨琪^†, 李军玉^†, 孙建科^*()

北京理工大学化学与化工学院原子分子簇科学教育部重点实验室北京 102488

投稿日期:2025-03-28 发布日期:2025-05-15

作者简介:

崔雨琪, 2022年北京理工大学在读硕士研究生, 主要研究方向为多孔有机笼复合材料的制备及其催化性能研究.

李军玉, 2024年北京理工大学在读博士研究生, 主要研究方向为多孔有机笼复合材料的制备及其催化性能研究.

孙建科, 博士, 北京理工大学化学与化工学院教授, 博士生导师. 长期从事功能多孔材料与团簇催化化学方面的交叉研究工作, 在高效合成多孔(笼)材料并将其用于绿色催化、复合团簇仿生催化、仿生通道等领域取得了一系列研究成果. 迄今在Nature、Nat. Commun.、J. Am. Chem. Soc.、Angew. Chem. Int. Ed.、Chem. Soc. Rev.、Acc. Chem. Res.、Acc. Mater. Res.、CCS Chem.等国际著名期刊杂志发表SCI论文70余篇, 多篇入选ESI高被引论文.

基金资助:
国家自然科学基金(22471018); 国家自然科学基金(22071008)

Advances in Porous Organic Cages for Energy Conversion and Storage

Yuqi Cui, Junyu Li, Jianke Sun^*()

Key Laboratory of Cluster Science, Ministry of Education of China, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488

Received:2025-03-28 Published:2025-05-15
Contact: *E-mail: jiankesun@bit.edu.cn
About author:
^†These authors contributed equally to this work
Supported by:
National Natural Science Foundation of China(22471018); National Natural Science Foundation of China(22071008)

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摘要/Abstract

在国家能源结构转型和可持续发展战略的推动下, 高效储能及能量转换新材料与技术的开发正面临关键挑战. 其中, 对新型能量储存载体的探索及物质/电荷传输机制的深入研究, 已经成为该领域的热点. 多孔有机笼(Porous Organic Cages, POCs)作为一类新兴多孔材料, 凭借其结构可调性, 既可通过骨架功能化修饰, 又可利用离散型纳米空腔及表面结合位点将功能单元与笼结构整合, 从而成为构建功能复合材料的理想基元, 在光电能量转换与存储领域展现出广阔的应用前景. 本文综述了多孔有机笼的设计与合成策略, 重点总结了POCs功能材料在能量转换与储存方面的研究进展, 并进一步探讨了其在该领域发展中面临的挑战及未来发展方向, 以期为能源导向型POCs材料的合理设计及应用提供参考.

关键词: 多孔有机笼, 合成, 光催化, 电催化, 能量储存与转换

The national transition toward sustainable energy solutions necessitates the development of advanced materials and technologies for efficient energy conversion and storage. Addressing this demand requires innovative approaches to overcome existing limitations in energy systems, including the need for high-capacity storage, rapid charge transfer, and long term stability. In this context, research on innovative energy storage carriers and mass/charge transfer mechanisms has become a pivotal focus at the forefront of materials science and energy technology. Porous organic cages (POCs), a unique class of low crystalline density porous materials, have attracted significant interest due to their well-defined molecular structures, discrete nanopore cavities and high porosity. These properties make them highly effective for applications in gas adsorption/separation and catalysis. Unlike traditional extended framework materials such as metal organic frameworks (MOFs) or covalent organic frameworks (COFs), POCs are discrete and solution-processable molecules that offer superior solubility and structural tunability, which can be easily designed as various functional composites, broadening their applicability in emerging energy technologies. A particularly promising avenue for POCs lies in energy conversion and storage. Recent studies have demonstrated that functionalized POCs can serve as efficient charge transport materials, facilitating electron and ion movement in energy storage applications. Despite their immense potential, several challenges must be addressed before POCs can be widely adopted in commercial energy technologies. Key challenges include improving the scalability of POC synthesis, optimizing their stability under operational conditions, and enhancing their conductivity for broader energy applications. Furthermore, fundamental research is needed to better understand the charge transport mechanisms within POC-based materials, which will be crucial for advancing their practical implementation. This review provides a comprehensive overview of the design and synthesis strategies of POCs, summarizes recent advancements in their energy-related applications, and discusses the challenges and future research directions in the field. By offering theoretical insights into the strategic development of POCs for energy conversion and storage, this work aims to drive further innovation in sustainable energy technologies, contributing to the ongoing efforts to address global energy challenges.

Key words: porous organic cage, synthesis, photocatalysis, electrocatalysis, energy storage and conversion

引用此文

崔雨琪, 李军玉, 孙建科. 多孔有机笼用于能源转换及储存的研究进展[J]. 化学学报, 2025, 83(6): 624-638.

Yuqi Cui, Junyu Li, Jianke Sun. Advances in Porous Organic Cages for Energy Conversion and Storage[J]. Acta Chimica Sinica, 2025, 83(6): 624-638.

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图/表 10

图1. (a) D3h型有机笼Cage-2的化学结构[24]. (b)四棱柱型TPE基有机笼Cage-3的化学结构[25]. (c)四棱柱卟啉笼TPPCage8＋的合成策略[27]

Figure 1. (a) The chemical structure of D3h-organic cage Cage-2[24]. Copyright 2007 The American Chemical Society. (b) The chemical structure of quadrangular prismatic TPE-based cage Cage-3[25]. (c) The synthesis of tetragonal prismatic porphyrin cage TPPCage8＋[27]. Copyright 2018 The American Chemical Society

图2. (a)立方八面体[12＋8]型笼Cage-6a/b的合成[38]. (b)大型硼酸酯笼Cage-7的合成[39]. (c)直角棱柱型有机笼COP-5的合成[42]

Figure 2. (a) The synthesis of cuboctahedral [12＋8] cages Cage-6a/b[38]. Copyright 2014 Wiley-VCH. (b) The synthesis of giant boronic ester cage Cage-7[39]. Copyright 2021 Wiley-VCH. (c) The synthesis of rectangular prismatic cage COP-5[42]. Copyright 2011 The American Chemical Society

图3. (a)八面体笼Cd6La12的合成[48]. (b) [12＋8]型有机笼Cage-9的合成[49]. (c) [4＋4]型有机笼Cage-12的合成[52]. (d)由X射线晶体学确定的CC1、CC2及CC3的结构图[45]. (e)有机笼Cage-11a/b的合成[51]

Figure 3. (a) The synthesis of octahedral cage Cd6La12[48]. Copyright 2011 The Royal Society of Chemistry. (b) The synthesis of [12＋8] organic cage Cage-9[49]. Copyright 2013 The Royal Society of Chemistry. (c) The synthesis of [4＋4] organic cage Cage-12[52]. Copyright 2018 Wiley-VCH. (d) Structure diagram of CC1, CC2 and CC3 determined by X-ray crystallography[45]. (e) The synthesis of organic cages Cage-11a/b[51]

图4. (a)用于光催化析氢的PdNPs@C4R/g-C3N4复合材料的构建示意图. (b)不同Pd纳米颗粒负载量时g-C3N4光催化活性对比. (c)不同催化剂的光催化产氢速率对比[56]

Figure 4. (a) Schematic illustration of the construction of PdNPs@C4R/g-C3N4 composite for photocatalytic hydrogen evolution. (b) The comparison of H2 production for g-C3N4 with different Pd NP loading amounts. (c) The comparison of photocatalytic hydrogen evolution rate for different catalysts[56]. Copyright 2020 The American Chemical Society

图5. (a)光致变色笼TAE-DTE的光异构体[64]. (b) TAE-DTE-O在可见光(左)和全范围(右)光照下的光催化CO2还原表现[64]. (c) FePB-2(P)催化剂的设计策略[66]. (d) FePB-2(P)在CO2饱和CH3CN溶液中的光催化活性[66]. (e)不同催化剂在CO2饱和的DMF溶液中的催化TON值对比(以Fe位点为准)[66]

Figure 5. (a) Photo-isomers of the photochromic organic cage TAE-DTE[64]. (b) The photocatalytic CO2 reduction performance of TAE-DTE-O under visible light (left) and full range light (right)[64]. Copyright 2021 The Royal Society of Chemistry. (c) The design strategy of catalyst FePB-2(P)[66]. (d) The catalytic activity of FePB-2(P) in CO2-saturated CH3CN[66]. (e) TON per[Fe] comparison of photocatalytic CO2RR for different catalysts in CO2-saturated DMF[66]. Copyright 2022 Wiley-VCH

图6. (a)流动电池的工作示意图. (b) Cu-nr/CC3和Cu-nr在不同电位下的电流密度对比. (c) Cu-nr/CC3和Cu-nr在不同电位下C2＋产物的法拉第效率对比. (d) Cu-nr/CC3和Cu-nr在不同电位下H2产物的法拉第效率对比. (e)不同催化剂在－0.9 V电位下的产物法拉第效率对比[69]

Figure 6. (a) Schematic diagram of the flow-cell. (b) The comparison of current density between Cu-nr/CC3 and Cu-nr at different potentials. (c) The FE of C2＋ products and (d) H2 at different potentials over Cu-nr/CC3 and Cu-nr. (e) Comparison of FE of products over different catalysts at －0.9 V potential[69]. Copyright 2022 Wiley-VCH

图7. (a) 通过向卟啉有机笼中引入Au团簇调节活性氧物种的示意图. (b) Au⊂TPPCage•Cl和TPPCage•Cl催化CEES氧化的产率对比. (c) Au⊂TPPCage•POM双催化功能示意图. (d) Au⊂TPPCage•POM和K8[Nb6O19]用于DECP水解的产率对比[74].

Figure 7. (a) The schematic diagram of Au clusters introducing porphyrin cages to regulate ROS. (b) The yield of CEES oxidation comparison of Au⊂TPPCage•Cl and TPPCage•Cl. (c) Schematic illustration of the dual catalytic functionality of Au⊂TPPCage•POM. (d) The yield of DECP hydrolysis comparison of Au⊂TPPCage•POM and K8[Nb6O19][74]. Copyright 2024 Science China Press

图8. (a)由RCC1-Cl到多孔有机笼电解质Li-RCC1-ClO4的合成步骤[14]. (b)不同LiClO4含量的Li-RCC1-ClO4 SSE离子电导率对比[14]. (c) PEO-LiClO4和PEO/Li-RCC1-ClO4的LSV曲线对比[14]. (d) C60@POC的主客体结构示意图[82]. (e)在光照/非光照条件下C60@POC的充放电曲线[82]. (f)在光照/非光照下POC和C60@POC的Nyquist图对比[82]

Figure 8. (a) The synthetic procedure of the porous cage electrolyte Li-RCC1-ClO4 from RCC1-Cl[14]. (b) Ion conductivity of the Li-RCC1-ClO4 SSE with different LiClO4 contents[14]. (c) The LSV results comparison of PEO-LiClO4 and PEO/Li-RCC1-ClO4[14]. Copyright 2022 Springer Nature. (d) The guest-host structure of C60@POC[82]. (e) Charge/discharge curves of C60@POC with/without irradiation[82]. (f) The Nyquist plots comparison of POC and C60@POC with/without irradiation[82]. Copyright 2022 The Royal Society of Chemistry

图9. (a) ⅡC-1@Na2S5的封装步骤示意图[87]. (b) ⅡC-1@Na2S5 LSB的倍率性能[87]. (c) ⅡC-1@Na2S5 LSB的循环性能及库伦效率[87]. (d)装载CC3/PP和CC3隔膜的电池在1 C下循环500次的Li＋和多硫化物离子筛分选择性和循环性能对比[86]. (e) CC3/PP和PP隔膜在不同库伦速率下的倍率性能[86]

Figure 9. (a) The encapsulation procedure of ⅡC-1@Na2S5[87]. (b) The rate performance and (c) cycling performance and coulombic efficiency for ⅡC-1@Na2S5 LSB[87]. Copyright 2022 Elsevier. (d) The comparison of the Li＋ and polysulfide ion sieving selectivity and cycling performance of batteries equipped with CC3/PP and bare PP separators at 1 C over 500 cycles[86]. (e) Rate performance at various C-rates for CC3/PP and PP[86]. Copyright 2022 The American Chemical Society

图10. (a) 基于质子化分子笼盐质子导体的结构图[94]. (b) Nafion- Cage 3复合膜的制备示意图[96]

Figure 10. (a) Structure diagram based on protonated molecular cage salt proton conductor[94]. (b) The schematic illustration of preparation of the Nafion-Cage 3 composite membrane[96]. Copyright 2018 The American Chemical Society

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多孔有机笼用于能源转换及储存的研究进展

Advances in Porous Organic Cages for Energy Conversion and Storage

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