二维金属有机框架材料的制备及其应用

doi:10.16085/j.issn.1000-6613.2020-2288

化工进展 ›› 2021, Vol. 40 ›› Issue (11): 6195-6210.DOI: 10.16085/j.issn.1000-6613.2020-2288

二维金属有机框架材料的制备及其应用

张素珍¹(), 杨蓉²(), 龚乐¹, 樊潮江², 燕映霖¹, 许云华²^,³

^1. 西安理工大学理学院，复合材料及其产品智能制造技术国际联合研究中心，陕西西安 710048
^2. 西安理工大学材料科学与工程学院，陕西西安 710048
^3. 榆林学院化学与化工学院，陕西榆林 719000

收稿日期:2020-11-16 修回日期:2021-02-08 出版日期:2021-11-05 发布日期:2021-11-19
通讯作者: 杨蓉
作者简介:张素珍（1996—），女，硕士研究生，研究方向为电化学。E-mail：1626867242@qq.com。
基金资助:
国家国际科技合作专项(2015DFR50350);国家自然科学基金(51702256);中国博士后面上项目(2019M653706);陕西省科技厅“创新人才推进计划-科技创新团队”项目(2019TD-019);陕西省创新能力支撑计划-国际科技合作基地(2018GHJD-17);西安理工大学校级项目(xsz2002)

Research on preparation and application of 2D MOFs

ZHANG Suzhen¹(), YANG Rong²(), GONG Le¹, FAN Chaojiang², YAN Yinglin¹, XU Yunhua²^,³

^1. International Research Center for Composite and Intelligent Manufacturing Technology, School of Science, Xi’an University of Technology, Xi’an 710048, Shaanxi, China
^2. School of Materials Science and Engineering, Xi’an University of Technology, Xi’an 710048, Shaanxi, China
^3. School of Chemistry & Chemical Engineering, Yulin University, Yulin 719000, Shaanxi, China

Received:2020-11-16 Revised:2021-02-08 Online:2021-11-05 Published:2021-11-19
Contact: YANG Rong

摘要/Abstract

摘要：

二维金属有机框架（MOFs）作为一类新型的二维多孔材料，具有厚度小、比表面积大、孔隙率高、可接触活性位点丰富等优点，在众多领域都具有研究和潜在的应用价值。本文简要综述了近年来二维MOFs的制备方法，包括“自上而下”和“自下而上”两种策略。自上而下法操作简单，有广泛的适用性；自下而上法可以通过控制实验条件在一定程度上实现对材料的可控制备。阐述了二维MOFs在电化学储能、催化、传感、气体分离等领域的应用研究。深层剖析了二维MOFs的特性对储能器件电化学性能以及反应催化活性的影响。此外，二维MOFs的高电导率和电荷转移率还促进了其在电化学传感器方面的发展；基于二维MOFs的分子筛膜也越来越受到研究人员的关注。最后指出了二维MOFs存在易团聚、厚度难以精确控制、制取成本较高、产率偏低等问题，提出了解决方案及其未来的发展方向。

关键词: 二维金属有机框架, 制备, 电化学储能, 催化, 传感, 分离

Abstract:

As a new type of two-dimensional porous materials, two-dimensional metal-organic frameworks (2D-MOFs) have the advantages of small thickness, large specific surface area, high porosity and rich access to active sites. These advantages enable potential value of 2D-MOFs in energy storage, catalysis, sensing, separation and other fields. In this article, the preparation methods of 2D-MOFs in recent years were reviewed briefly, including top-down and bottom-up strategies. The top-down method was easy to operate and has wide applicability, while the bottom-up method can control the preparation of materials to a certain extent by controlling the experimental conditions. The influence of structural characteristics of 2D-MOFs on the electrochemical performance of energy storage devices and the catalytic activity of the reaction was analyzed elaborately. In addition, the high electrical conductivity and charge transfer rate of 2D-MOFs had promoted their development in electrochemical sensors. Molecular sieve membranes based on 2D-MOFs had also received increasing attention from researchers. Finally, the difficulty of controlling the thickness of 2D-MOFs, high cost and low yield were listed as current problems. It proposed that optimizing preparation scheme and doping and compounding it with other materials would be the future development directions to improve the performance of 2D-MOFs.

Key words: two-dimensional metal-organic frameworks (2D-MOFs), preparation, electrochemical energy storage, catalysis, sensor, separation

中图分类号:

O646

张素珍, 杨蓉, 龚乐, 樊潮江, 燕映霖, 许云华. 二维金属有机框架材料的制备及其应用[J]. 化工进展, 2021, 40(11): 6195-6210.

ZHANG Suzhen, YANG Rong, GONG Le, FAN Chaojiang, YAN Yinglin, XU Yunhua. Research on preparation and application of 2D MOFs[J]. Chemical Industry and Engineering Progress, 2021, 40(11): 6195-6210.

图/表 17

参考文献 78

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制备方法	优点	缺点	参考文献
自上而下
物理剥离法	广泛的适用性、产物高度结晶、有较大的平面尺寸	剥离过程缺少精度，可控性或可重复性差	［29］
化学剥离法	产率得到了提升，在一定程度上提高了可重复性	难以控制材料的厚度和尺寸	［33］
自下而上
溶剂热法	可获得具有良好分散性的高纵横比纳米片	反应时间相对较长	［44］
界面合成法	条件较温和，可以在常温常压下进行	界面区域面积有限，二维MOFs纳米片产量较低	［37-41］
辅助合成法	快速高效，可调节	辅助剂一般较难去除	［42，48-49］
二维氧化物牺牲法	制备的纳米片厚度较小	需选择合适的牺牲模板	［43］

制备方法	优点	缺点	参考文献
自上而下
物理剥离法	广泛的适用性、产物高度结晶、有较大的平面尺寸	剥离过程缺少精度，可控性或可重复性差	［29］
化学剥离法	产率得到了提升，在一定程度上提高了可重复性	难以控制材料的厚度和尺寸	［33］
自下而上
溶剂热法	可获得具有良好分散性的高纵横比纳米片	反应时间相对较长	［44］
界面合成法	条件较温和，可以在常温常压下进行	界面区域面积有限，二维MOFs纳米片产量较低	［37-41］
辅助合成法	快速高效，可调节	辅助剂一般较难去除	［42，48-49］
二维氧化物牺牲法	制备的纳米片厚度较小	需选择合适的牺牲模板	［43］

2D-MOFs材料	衍生材料	应用器件	性能	参考文献
Cu-MOFs	APC	超级电容器	0.5A·g^-1下比电容为260.5F·g^-1	［51］
Cu^I-MOFs	—	超级电容器	1.0A·g^-1下比电容为828F·g^-1	［52］
Al-MOFs	AMn	锂离子电池钠离子电池	0.1C下100次循环后比容量为825mA·h·g^-1 0.1C下100次循环后比容量为193mA·h·g^-1	［53］
Al-BDC	CPC	超级电容器	1mV·s^-1下的比电容为323F·g^-1	［54］
NH₂-MIL-53(Al)	SNO-HCN	钠离子电池	50mA·g^-1下比容量为522mA·h·g^-1	［55］
Zn(bim)(OAc)	UT-CNS	超级电容器锂离子电池	10A·g^-1下比电容为278F·g^-110A·g^-1下比容量为553mA·h·g^-1	［56］
［Ni(Hppza)₂］ _n	—	超级电容器	0.5mV·s^-1下比电容为184F·g^-1	［57］

2D-MOFs材料	衍生材料	应用器件	性能	参考文献
Cu-MOFs	APC	超级电容器	0.5A·g^-1下比电容为260.5F·g^-1	［51］
Cu^I-MOFs	—	超级电容器	1.0A·g^-1下比电容为828F·g^-1	［52］
Al-MOFs	AMn	锂离子电池钠离子电池	0.1C下100次循环后比容量为825mA·h·g^-1 0.1C下100次循环后比容量为193mA·h·g^-1	［53］
Al-BDC	CPC	超级电容器	1mV·s^-1下的比电容为323F·g^-1	［54］
NH₂-MIL-53(Al)	SNO-HCN	钠离子电池	50mA·g^-1下比容量为522mA·h·g^-1	［55］
Zn(bim)(OAc)	UT-CNS	超级电容器锂离子电池	10A·g^-1下比电容为278F·g^-110A·g^-1下比容量为553mA·h·g^-1	［56］
［Ni(Hppza)₂］ _n	—	超级电容器	0.5mV·s^-1下比电容为184F·g^-1	［57］

2D-MOFs材料	衍生材料	催化反应类型	过电势/mV	Tafel斜率/mV·dec^-1	电流密度/mA·cm^-2	参考文献
Cu-BDC	CuS@C	HER	128	44	10	［58］
Co-MOFs	Gr@Co-MOFs	HER	125	91	10	［60］
Co-MOFs	MoS₂/Co-MOFs	HER	262	51	—	［62］
Co-MOFs	Co₃O₄	OER	205	65.3	51	［59］
NiCo-MOFs	—	OER	310	—	10	［61］
NiFe-UMNs	—	OER	260	30	10	［63］

二维金属有机框架材料的制备及其应用

Research on preparation and application of 2D MOFs

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