硅酸盐学报

金属有机框架有机配体官能团吸/给电子效应及熔点调控

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李续 ¹^,² , 高成伟 ¹^,²^,³ , 周添跃 ¹^,² , 谭林玲 ¹^,² , 康世亮 ¹^,² , 焦清 ¹^,² , 林常规 ¹^,²

硅酸盐学报 | MOF玻璃研究新进展专题—研究论文 2024,52(8): 2559-2565

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硅酸盐学报 |MOF玻璃研究新进展专题—研究论文 2024 , 52 (8) : 2559 -2565

金属有机框架有机配体官能团吸/给电子效应及熔点调控

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李续¹^,², 高成伟¹^,²^,³, 周添跃¹^,², 谭林玲¹^,², 康世亮¹^,², 焦清¹^,², 林常规¹^,²

作者信息

^1．宁波大学高等技术研究院，红外材料及器件实验室，浙江宁波 315211

^2．浙江省光电探测材料及器件重点实验室，浙江宁波 315211

^3．硅酸盐建筑材料国家重点实验室，武汉理工大学，武汉 430070

通讯作者:

高成伟（1991—），男，博士，助理研究员。

作者简介:

李续（1996—），男，硕士研究生。

Electron-Absorbing Functional Groups Modulate Melting Point of Metal-Organic Frameworks

Xu LI¹^,², Chengwei GAO¹^,²^,³, Tianyue ZHOU¹^,², Linling TAN¹^,², Shiliang KANG¹^,², Qing JIAO¹^,², Changgui LIN¹^,²

Affiliations

^1.Laboratory of Infrared Materials and Devices, Institute of Advanced Technology, Ningbo University, Ningbo 315211, Zhejiang, China

^2.Zhejiang Key Laboratory of Optoelectronic Detection Materials and Devices, Ningbo 315211, Zhejiang, China

^3.State Key Laboratory of Silicate Building Materials, Wuhan University of Science and Technology, Wuhan 430070, China

Corresponding Author:

GAO Chengwei (1991-), male, Ph.D., Research Assistant. E-mail: gaochengwei@nbu.edu.cn

LI Xu (1996-), male, Master candidate. E-mail: 2211100323@nbu.edu.cn

出版时间: 2024-08-20 doi: 10.14062/j.issn.0454-5648.20230928

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摘要

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金属有机框架（MOF）玻璃，作为第4种熔融淬冷玻璃，在能源、气体分离等领域都具有潜在的应用价值。但目前只有部分MOF可制备成为玻璃，且其熔点与分解温度相近，导致玻璃成品中分解杂质多，制备能耗高。基于有机配体上官能团的吸/给电子效应，通过调控咪唑基配体的种类和含量，调节配体与金属中心的配位键强弱，可将TIF-4的熔点从375 ℃降至295 ℃。证明了有机配体上官能团吸/给电子效应对MOF熔点调控的有效性和通用性，为指导开发更多MOF玻璃提供了理论基础，有利于促进MOF玻璃的实际应用。

关键词

金属有机框架 / 玻璃 / 熔点调控 / 玻璃化 / 熔融淬冷 / 分解温度

Abstract

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Introduction

MOF-based electrolytes exhibit excellent chemical and thermal stability, which can improve the service life and safety of the whole battery. The research of MOF electrolytes is expected to promote the progress and development of solid-state battery technology with high energy density and high safety.

The MOF electrolytes has more grain boundaries, which tend to cause interfacial problems such as dendrite growth. In order to eliminate the grain boundaries of MOF, vitrification is a more effective strategy. However, the strong coordination bonds between the metal and organic ligands in MOF lead to high melting points and higher energy consumption required for the MOF glass preparation. In addition, the melting point and decomposition temperature of MOF are very close, and only several MOF can melt when heated, and most of MOF will decompose before melting, accompanied by carbonization of organic ligands, and oxidation of metal ions.

Therefore, for most MOF crystals, it is challenging to transform them into glass state by the conventional melt-quenching method. To expand the variety of MOF glasses, researchers have increased the entropy of melting by introducing functional groups with electron-absorbing ability and modified MOFs by strategies such as ion exchange and surface engineering, thereby lowering the melting temperature of MOFs. However, there is no clear mechanistic guidance for the melting point regulation of MOF crystals, and the relationship between its coordination bonds and its melting process is still unclear.

Methods

By introducing different functional groups with different electron-withdrawing/donating effects on organic ligands, the strength of coordination bonds between metal ions and organic ligands can be adjusted, through which the mechanism and influence law of MOF melting point regulation is investigated. The ligand and metal ions were dissolved in 15 mL of DMF, and then the above solutions were heated and held at 130 ℃ for 48 h. After cooling, the products were collected by centrifugation, washed out with DMF (dimethylformamide) for three times, and finally dried under vacuum at 120 ℃ for 12 h. The obtained TIF-4 crystals were placed into a tube furnace and further held at 380 ℃ for 5 min under argon gas atmosphere, then cooled to room temperature to obtain TIF-4 glass (a_gTIF-4). A series of TIF-4 crystals using different halogen groups with same structure were prepared via solvothermal method at 130 ℃ in DMF. The strength of the coordination bonds was investigated via FTIR and DSC, from which the influence of the coordination bonds on the melting behavior of MOF were investigated systematically.

Results and discussion

With the enhancement of the electronegativity of functional groups or the increase of the content of strong electronegative functional groups, i.e. the enhancement of the electron-withdrawing effect of functional groups, it can weaken the coordination bond between the ligand and the metal centre and lower the melting point of the MOF; on the contrary, through the introduction of electron-donating groups (methyl groups), it can enhance the coordination bond through the electron-donating effect and increase the melting point of the MOF. A series of TIF-4 crystals using different halogen groups and same structure were prepared, and the Tm of TIF-4 (from 375 ℃ to 295 ℃) gradually decreased with the enhancement of the electron-withdrawing ability of the halogen functional groups. The strength of the coordination bond was regulated by the electron-withdrawing/donating and the low-temperature preparation of MOF glass was realized. Meanwhile, it provides more theoretical guidance for the preparation of MOF glass, effectively avoids the decomposition of MOF in the melting process, improves the quality of MOF glass, reduces the preparation cost of MOF glass, and provides the theoretical basis and technical support for the application of MOF glass in the field of electrolytes and other fields, and also has a certain role in promoting the development and application of MOF.

Conclusions

The relationship between the electron-withdrawing/donating of functional groups on organic ligands and the strength of coordination bonds is clarified, and its influence on the melting point of MOF is revealed, which facilitate the preparation of MOF glass with low melting temperature and high thermal stability. This work shows that the electron-withdrawing/donating effect could be utilized to regulate the melting point of MOF, which provides an effective strategy for the preparation of more different types of MOF glasses. This work could promote the large-scale preparation of low-cost and high-quality MOF glasses and promote the practical application of MOF glasses in different fields.

Key words

metal-organic frameworks glass / melting point regulation / vitrification / melt quenching / decomposition temperature

引用本文

李续, 高成伟, 周添跃, 谭林玲, 康世亮, 焦清, 林常规. 金属有机框架有机配体官能团吸/给电子效应及熔点调控. 硅酸盐学报, 2024 , 52 (8) : 2559 -2565 . DOI: 10.14062/j.issn.0454-5648.20230928

Xu LI, Chengwei GAO, Tianyue ZHOU, Linling TAN, Shiliang KANG, Qing JIAO, Changgui LIN. Electron-Absorbing Functional Groups Modulate Melting Point of Metal-Organic Frameworks[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (8) : 2559 -2565 . DOI: 10.14062/j.issn.0454-5648.20230928

基金

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国家自然科学基金青年基金(52202005)
浙江省自然科学基金(LQ23E020005)
硅酸盐材料工程教育部重点实验室（武汉理工大学）开放课题基金(SYSJJ2023-11)

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排序方式：

2024年第52卷第8期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230928

接收时间：2023-11-30
首发时间：2026-10-22
出版时间：2024-08-20

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出版历史

收稿日期：2023-11-30
修回日期：2023-12-29

基金

国家自然科学基金青年基金(52202005)

浙江省自然科学基金(LQ23E020005)

硅酸盐材料工程教育部重点实验室（武汉理工大学）开放课题基金(SYSJJ2023-11)

作者信息

^1．宁波大学高等技术研究院，红外材料及器件实验室，浙江宁波 315211

^2．浙江省光电探测材料及器件重点实验室，浙江宁波 315211

^3．硅酸盐建筑材料国家重点实验室，武汉理工大学，武汉 430070

通讯作者:

高成伟（1991—），男，博士，助理研究员。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230928

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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