硅酸盐学报

串联扰动型金属有机框架玻璃的热诱导晶化及结构转变

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刘涛 ¹^,² , 殷政 ² , 匡小军 ¹ , 曾明华 ¹^,²

硅酸盐学报 | MOF玻璃研究新进展专题—研究论文 2024,52(8): 2566-2574

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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) : 2566 -2574

串联扰动型金属有机框架玻璃的热诱导晶化及结构转变

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刘涛¹^,², 殷政², 匡小军¹, 曾明华¹^,²

作者信息

^1．广西电磁化学功能物质重点实验室，桂林理工大学化学与生物工程学院，广西桂林 541004

^2．药用资源化学与药物分子工程省部共建国家重点实验室，广西师范大学化学与药学学院，广西桂林 541004

通讯作者:

殷政（1988—），男，博士，教授；

匡小军（1978—），男，博士，研究员；

曾明华（1972—），男，博士，教授。

作者简介:

刘涛（1997—），男，硕士研究生。

Thermal Induced Crystallization and Structure Transformation of Metal-Organic Framework Glass Fabricated by Sequential Perturbation Method

Tao LIU¹^,², Zheng YIN², Xiaojun KUANG¹, Minghua ZENG¹^,²

Affiliations

^1.Guangxi' Key Laboratory of Electrochemical and Magneto-chemical Functional Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541004, Guangxi

^2.State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004, Guangxi

Corresponding Author:

YIN Zheng (1988-), male, Ph.D., Professor. E-mail: yinzheng@sust.edu.cn;

KUANG Xiaojun (1978-), male, Ph.D., Professor. kuangxj@glut.edu.cn;

ZENG Minghua (1972-), male, Ph.D., Professor. zmh@mailbox.gxnu.edu.cn

LIU Tao (1997-), male, Master candidate. E-mail: 2538595568@qq.com

出版时间: 2024-08-20 doi: 10.14062/j.issn.0454-5648.20240145

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摘要

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晶化行为极大影响玻璃材料的加工赋形及力学、光、电等性能，但晶化过程中微观结构演变机制远不明晰；对于全新类别金属有机框架（MOF）玻璃，相关晶化及高温动态配位化学系统研究更为匮乏。动态高孔穴四重穿插钻石网型MOF-［Co（L1）₂］₄_n，在水分子配位及热去除多层级协同扰动下可不经高温熔融直接玻璃化。作为首个串联扰动法获得的传统MOF成功玻璃化实例，热重和差热分析发现去水扰动不定形态MOF在T_g = 560 K处发生玻璃化转变，过冷液体于558 ~ 586 K间稳定，随后在T_c = 597 K处发生明显晶化，并进一步在T_d = 695 K以上发生结构分解；原位变温（PXRD）跟踪并证实了MOF去水无定形→玻璃化→过冷液化→再晶化的相态演变过程；X射线全散射原子对分布函数（PDF）揭示了玻璃态及再晶化态样品的短-中-长程结构特征。基于CCDC数据库结构检索以及铜基同构MOF的合成，结合MOF玻璃晶化相高分辨PXRD谱的Rietveld拟合结构验证，确认了致密六重穿插钻石网MOF-［Co（L1）₂］₆_n的生成。MOF过冷液体不同温度淬冷所制备玻璃保有气体可接触孔性并呈现温度依赖变化，揭示了相均一MOF过冷液体内部液态结构差异性。这一研究构建了MOF“晶态-扰动态-过冷液态-玻璃态-晶化态”多相结构演变有趣例证，揭示了MOF玻璃及其过冷液体独特的高温配位自识别和有序化结构自组装行为。

关键词

金属有机框架玻璃 / 结构与相态演变 / 过冷液体 / 晶化 / 气体吸附

Abstract

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Introduction

Metal-organic frameworks are a class of organic-inorganic hybrid and crystalline materials based on coordinatively bonded porous network. But the structure and function have been seldom investigated. The effective processing of MOF devices have always been hindered by the intrinsic feature of crystalline powders. The utilization of thermal rheology of glass material is expected to realize the effective preparation of grain-boundary-free and isotropic MOF glass membrane, which is one of the key goals of porous chemistry in the future. Different types of MOF glasses have been prepared by covering melt-quenching, mechanical or pressure treatment, bottom-up assembly in solution, ionic liquid-assisted melting and sequential perturbation. Nevertheless, the crystallization behavior of liquid and supercooled liquid greatly affects the processing and mechanical, optical, and electrical properties of glass materials, but the mechanism of microstructure evolution during the crystallization process is far from clear. It's even less clear on systematic study of the crystallization and high-temperature dynamic coordination chemistry for new MOF glass.

Methods

A highly porous and flexible MOF of [Co(L1)₂]₄_n with 4-fold interpenetrated dia-net frameworks and another reference compound of Cu(L1)₂]₆_n with 6-fold interpenetrated dia-net and dense frameworks, were synthesized by solvothermal reactions. The vapor treatment and subsequent thermal dehydration generated the h-CoL1 and dh-CoL1, respectively. The TG and DSC measurements were used to confirm the phase evolution from amorphous, through glass transition, to supercooled liquid, until either quenched glass or high-temperature re-crystallized phase. The in-suit and temperature dependent PXRD further confirmed the structure transformation process. X-ray total scattering atom pair distribution function spectra uncovered the short-middle-long range structure characters of both the glassy and re-crystallized MOFs. Infrared and Raman spectroscopy were used to analyze the coordination geometry changes among different states of MOF. The porosity of glassy g-CoL1 and recrystallized rec-CoL1 were investigated by using CO₂ adsorption-desorption curves at 195 K.

Results and discussion

The [Co(L1)₂]₄_n can turn into glassy state directly without high-temperature melting, facilitated by the multi-level synergistic perturbations of water coordination and subsequent thermal removal. As the first successful example of glass generated from traditional MOF based on sequential perturbation. TG and DSC revealed a glass transition at T_g = 560 K of the dehydrated and amorphous MOF, the subsequent formation of stable super-cooled liquid in the range of 558-586 K, the crystallization of the super-cooled liquid at T_c = 597 K, and the final decomposition above T_d = 695 K. Crystalline sample c-CoL1, glassy g-CoL1 obtained by quenching super-cooled liquid at different temperatures (563, 573, 583 K), and recrystallized rec-CoL1 at 593 K, at 195 K were tested CO₂ for isothermal adsorption. Based on structure match in the CCDC database and the synthesis of iso-reticular Cu-MOF, coupled with the Rietveld fitting analysis of PXRD spectrum, the structure of the recrystallized phase was verified to be a dense, 6-fold interpenetrated, and dia-net framework of [Co(L1)₂]₆_n. Glass prepared by quenching MOF super-cooled liquids at different temperatures retained gas-accessible porosity and showed temperature-dependent variations, revealing the inherent structure difference in phase-homogeneous MOF super-cooled liquids.

Conclusions

The highly flexible, porous, and 4-fold interpenetrated dia-net frameworks of [Co(L1)₂]₄_n can be perturbated by water molecule coordination and thermal dehydration to achieve structural disorder and direct glass transition without the need of traditional melting. The obtained MOF super-cooled liquid further transforms to a dense and six-fold interpenetrated dia-net MOF, through the coordinative self-assembly during high-temperature crystallization process. Gas accessible porosity of the quenched MOF glass was verified by gas sorption. Based on the relevance between the quenching temperature of super-cooled liquid and the corresponding porosity of the MOF glasses, the internal liquid structure difference of the homogeneous MOF super-cooled liquid is revealed. This study presents a vivid example of the multiphase structure evolution of MOF, covering different steps of crystalline, perturbated, super-cooled liquid, glass, re-crystallized states. This work thus reveals the unique high-temperature coordinative self-recognition and well-ordered self-assembly of MOF super-cooled liquid. Such new era of high-temperature dynamic chemistry also offers great opportunity for material processing and function loading of MOF based on the super-cooled liquid, glass and re-crystallized states of MOF.

Key words

metal-organic framework / glass / structure and phase transformation / super-cooled liquid / crystallization / gas adsorption

引用本文

刘涛, 殷政, 匡小军, 曾明华. 串联扰动型金属有机框架玻璃的热诱导晶化及结构转变. 硅酸盐学报, 2024 , 52 (8) : 2566 -2574 . DOI: 10.14062/j.issn.0454-5648.20240145

Tao LIU, Zheng YIN, Xiaojun KUANG, Minghua ZENG. Thermal Induced Crystallization and Structure Transformation of Metal-Organic Framework Glass Fabricated by Sequential Perturbation Method[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (8) : 2566 -2574 . DOI: 10.14062/j.issn.0454-5648.20240145

基金

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广西八桂英才项目(2019AC26001)
国家自然科学基金(U23A2080; 22371173; 22171075)
霍英东教育基金会高等院校青年教师基金(171110)

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2024年第52卷第8期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240145

接收时间：2024-02-24
首发时间：2026-10-22
出版时间：2024-08-20

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收稿日期：2024-02-24
修回日期：2024-04-01

基金

广西八桂英才项目(2019AC26001)

国家自然科学基金(U23A2080; 22371173; 22171075)

霍英东教育基金会高等院校青年教师基金(171110)

作者信息

^1．广西电磁化学功能物质重点实验室，桂林理工大学化学与生物工程学院，广西桂林 541004

^2．药用资源化学与药物分子工程省部共建国家重点实验室，广西师范大学化学与药学学院，广西桂林 541004

通讯作者:

殷政（1988—），男，博士，教授；

匡小军（1978—），男，博士，研究员；

曾明华（1972—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240145

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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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