Metal-Organic Framework Composites★

doi:10.6023/A25040117

Acta Chimica Sinica ›› 2025, Vol. 83 ›› Issue (8): 962-980.DOI: 10.6023/A25040117 Previous Articles

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金属有机框架复合材料^★

高春^a, 张松涛^b^,^*(), 庞欢^b^,^c^,^*()

^a 江苏商贸职业学院继续教育学院南通 226011
^b 扬州大学化学化工学院测试中心扬州 225009
^c 南京大学配位化学国家重点实验室南京 210023

投稿日期:2025-04-12 发布日期:2025-06-18
通讯作者: 张松涛, 庞欢

作者简介:

高春, 江苏商贸职业学院继续教育学院副院长, 副教授, 长期从事化学教育研究和高校继续教育工作.

张松涛, 扬州大学测试中心助理研究员. 2016年毕业于南京航空航天大学, 获材料物理与化学博士学位. 近年来主要从事开发应用于电化学储能的MOF基功能材料和介孔基纳米复合材料.

庞欢, 男, 扬州大学化学化工学院院长, 二级教授, 博士生导师. 于2011年获得南京大学理学博士学位. 为教育部青年长江学者、新世纪优秀人才、江苏省杰出青年、英国皇家化学学会会士及全球高被引学者, 兼任《国家科学评论》学科编辑组成员及Nano Res.、Rare Met.等期刊编委. 主要从事纳米配合物及其衍生物的合成、功能应用研究, 尤其是纳米金属有机框架(MOF)的电化学研究.

^★ “中国青年化学家”专辑.

基金资助:
国家自然科学基金项目(52371240); 江苏高校优势学科建设工程和配位化学国家重点实验室资助

Metal-Organic Framework Composites^★

Chun Gao^a, Songtao Zhang^b^,^*(), Huan Pang^b^,^c^,^*()

^a Continuous Education College, Jiangsu Commercial Vocational College, Nantong 226011
^b Testing Center, College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225009
^c State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210023

Received:2025-04-12 Published:2025-06-18
Contact: Songtao Zhang, Huan Pang
About author:
^★ For the VSI “Rising Stars in Chemistry”.
Supported by:
National Natural Science Foundation of China(52371240); Priority Academic Program Development of Jiangsu Higher Education Institutions and the State Key Laboratory of Coordination Chemistry

With the intensification of environmental challenges and the ever-growing global energy demand, conventional materials are increasingly unable to satisfy the stringent requirements in energy and environmental fields. Metal-organic frameworks (MOFs), as a class of crystalline porous materials composed of metal nodes and organic ligands, have emerged as promising candidates due to their tunable pore structures, exceptionally high surface areas, and versatile functionalities. These features enable MOFs to play a significant role in applications such as adsorption and electrochemical energy storage. However, the poor intrinsic electrical conductivity and limited structural stability of pristine MOFs restrict their practical implementation. To address these limitations, MOF-based composites have been developed by integrating MOFs with a variety of guest materials including inorganic carbonaceous materials (e.g., graphene, carbon nanotubes), metal oxides, and conductive polymers. These composites not only retain the inherent advantages of MOFs but also enhance conductivity, mechanical robustness, and chemical stability through synergistic interactions. Importantly, the integration strategies often involve the construction of heterostructures, interface engineering, and the introduction of chemically bonded interfaces, thereby promoting efficient charge transfer and long-term cycling stability. Herein, a comprehensive summary of MOF composites and their emerging applications in electrochemical energy storage systems, such as supercapacitors, lithium-ion batteries, lithium-sulfur batteries and aqueous zinc ion batteries, as well as in environmental adsorption processes targeting heavy metals and CO₂ capture, is offered. The discussion also emphasizes dimensional design from zero-dimensional (0D) nanoparticles to three-dimensional (3D) frameworks, each exhibiting unique advantages in terms of electron transport, ion diffusion, and active site accessibility. The relationships of these composites are analyzed, highlighting how different combinations and morphologies (e.g., core-shell architectures, layered hybrids, and flexible films) influence their functional performance. MOF composites represent a promising frontier for the development of next-generation functional materials. Their tunable dimensionality, enhanced chemical properties and multifunctional adaptability open up new avenues for solving urgent global issues in energy sustainability and environmental remediation.

Key words: metal-organic framework, composite material, dimension, electrochemical energy storage, adsorption

Cite this article

Chun Gao, Songtao Zhang, Huan Pang. Metal-Organic Framework Composites^★[J]. Acta Chimica Sinica, 2025, 83(8): 962-980.

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Fig. & Tab. 21

MOF复合物类型	结构调控的核心策略	电化学性能提升机制	合成工艺
金属氧化物@MOFs	通过金属价态调控与异质界面设计优化电子结构	法拉第赝电容与协同电子传导	溶剂热、电化学沉积
无机碳材料@MOFs	以MOF为前驱体, 通过热解与孔结构设计实现碳基功能化	双电层电容与表面赝电容	高温热解、模板法中空化
聚合物@MOFs	引入多种官能团, 实现氧化还原活性、离子传导和界面稳定化的协同	增强柔性、离子通透性与稳定性	原位聚合、一锅法

Table 1. Comparison of different types of composite strategies in structural regulation, electrochemical performance, and scalability of synthesis processes

Figure 1. Schematic diagram depicting the synthesis of NiCo-MOF@NiCoO2@Ni[21]

Figure 2. FESEM images of (a, b) NH2-MIL-88B(Fe) and (c, d) g-C3N4/NH2-MIL-88B(Fe)[22], and (e) schematic diagram showing OFL photodegradation on the g-C3N4/NH2-MIL-88B(Fe) composite under visible light irradiation[22]

Figure 3. Schematic diagram of the synthesis of agfZIF-62[24]

Figure 4. Schematic representation for the production of core-shell-type hybrid MOFs (Fe-MIL-88B@Fe-MIL-88C and Fe-MIL-88B@Ga- MIL-88B@Fe-MIL-88C) via the tip-to-middle anisotropic MOF-On-MOF Growth with Mismatched Cell Lattices[30]

Figure 5. (a) SEM and (b) AFM images of NiFe-UMNs[33], and (c) SEM images of PtCu@Cu-TCPP UNSs[34]

Figure 6. (a~d) SEM images of in-situ ZIF-8 nanoparticles in mesoporous channels[35]

Figure 7. Intrinsic conductivity of different materials

Figure 8. (a) Schematic illustration of the synthetic approach for the NiCo2O4@Ni-MOF core/shell hybrid arrays on carbon cloth[47], (b) specific capacity of NiCo2O4@Ni-MOF at various discharge current densities[47], (c) wireframe view of the Mn-MOF[48], and (d) cycling performance of K0.5Mn2O4@Mn-MOF-8 at constant current density of 2 A•g－1[48]

Figure 9. Comparison diagram of traditional porous supercapacitors and porous polyelectrolyte grafted supercapacitors[49]

MOF复合物	客体材料	应用	比容量	容量保持率	文献
PPHK	聚吡咯	锂离子电池阳极	147.2 mAh•g^－1 at 1 C	86.7% after 800 cycles	[59]
Si/CNTs@ZIF-800N	硅, 碳纳米管	锂离子电池阳极	1223 mAh•g^－1 at 0.1 A•g^－1	98.4% after 100 cycles	[60]
Porous ZnCo₂O₄/C	碳纤维	锂离子电池阳极	1707 mAh•g^－1 at 0.1 A•g^－1	67.1% after 100 cycles	[61]
Co-TCPP MOF/rGO	还原氧化石墨烯	锂离子电池阳极	2317 mAh•g^－1 at 0.1 A•g^－1	≈45.3% after 100 cycles	[62]
PPy@Cu-MOFs	聚吡咯	锂离子电池隔膜	150.2 mAh•g^－1 at 0.5 C	≈100% after 200 cycles	[32]
PP@MIL-101-COOH	聚偏二氟乙烯	锂离子电池隔膜	—	95.9% after 150 cycles	[55]
PH-SSE	聚偏二氟乙烯	锂离子电池电解质	—	85.1% after 300 cycles	[54]
BMOF@HF/H-ZIF-8	聚丙烯腈中空纤维	锂离子电池电解质	—	90.45% after 200 cycles	[58]

Table 2. Application of MOF composites in lithium-ion batteries

Figure 10. (a) Schematic illustration of the core-shell structural changes in Co-PBA/MXene during the insertion and extraction of Li＋ in the cycling process[61], (b, c) diagram of the lithium storage mechanism of Co-PBA/MXene[61]

Figure 11. (a) schematic diagrams showing the Li＋ plating/stripping behaviors on bare-Cu[62], and (b) schematic diagrams showing the Li＋ plating/stripping behaviors on PPHK@Cu[62]

MOF复合物	客体材料	应用	比容量	容量保持率	文献
Cu-BTC/CNTs	碳纳米管	锂硫电池阴极	805.28 mAh•g⁻¹ at 1 C	60.34% after 200 cycles	[72]
ZIF@T-PVDF	聚偏二氟乙烯	锂硫电池隔膜	1324.2 mAh•g⁻¹ at 2 C	—	[73]
CSUST-1/CNT	CNT	锂硫电池隔膜	1468 mAh•g⁻¹ at 0.1 C	—	[74]
UiO-66/ACNT	酸处理碳纳米管	锂硫电池隔膜	4.01 mAh•cm^－2 at 0.2C	—	[75]

Table 3. Application of MOF composites in lithium sulfur batteries

Figure 12. Schematic diagram of MOF composite as the Li-S battery separator to limit the shuttle effect of polysulfides[74]

MOF复合物	客体材料	应用	比容量	容量保持率	文献.
MIL-88B(V)@rGO	氧化石墨烯	锌离子电池阴极	480 mAh•g^－1 at 0.05 A•g^－1	80.3% after 400 cycles	[84]
Mn-MOF/CNT	碳纳米管	锌离子电池阴极	260 mAh•g^－1 at 0.05 A•g^－1	≈100% after 900 cycles	[85]
V-MOF@graphene	石墨烯	锌离子电池阴极	342 mAh•g^－1 at 0.1A•g^－1	≈89% after 100 cycles	[86]
MXene/Cu-THBQ	MXene	锌离子电池阳极	235.4 mAh•g^－1 at 0.2 A•g^－1	98.7% after 400 cycles	[87]

Table 4. Application of MOF composites in aqueous zinc ion battery

Figure 13. (a1~c1) Schematic diagram of the dissolution behavior of the V-PBA cathode in 3 mol/L Zn(OTf)2, saline, and eutectic electrolytes[89], (a2~c2) schematic diagram of the formation process of zinc dendrites in 3 mol/L Zn(OTf)2, saline, and eutectic electrolytes[[89], and (d) schematic diagram of the mechanism of Zn2＋ storage in V-PBA[89]

Figure 14. (a~c) Ex situ SEM images of the Zn-P anode[87], and (d~f) Ex situ SEM images of the M3DP-MXene/Cu-THBQ/Zn-P anode[87]

Figure 15. (a) Schematic synthetic route of AOPAN/ZIF[96], (b) effect of contact time on the uptake of U(VI) by UN-PA-AO-PANF-2[97], and (c) pathway to fabricate the ZIF-67/SAP composite hydrogel[98]

Figure 16. (a) Adsorption binding mechanisms between BDB-MIL-125(Ti)@Fe3O4 and Pb(II)[99], and (b) binding energy of BDB-MIL-125(Ti)@Fe3O4 and Pb(Ⅱ)[99]

Figure 17. (a) Cross-linking, condensation, and nucleophilic reaction mechanism of PI-UiO/GOs and adsorption interaction sites[101] and (b) conceptual diagram of functional hybrid materials by incorporating CB6 into chromium based MIL-101[104]

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金属有机框架复合材料★

Metal-Organic Framework Composites★

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金属有机框架复合材料^★

Metal-Organic Framework Composites^★