硅酸盐学报

金属有机框架材料玻璃化转变温度的节点金属混合效应

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杜子娟 ¹ , 葛璇 ²^,³ , 乔昂 ¹^,⁴ , 师彩娟 ⁵ , 杜涛 ³ , 岳远征 ³ , 陶海征 ¹

硅酸盐学报 | 研究论文 2024,52(12): 3673-3684

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硅酸盐学报 |研究论文 2024 , 52 (12) : 3673 -3684

金属有机框架材料玻璃化转变温度的节点金属混合效应

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杜子娟¹, 葛璇²^,³, 乔昂¹^,⁴, 师彩娟⁵, 杜涛³, 岳远征³, 陶海征¹

作者信息

^1．武汉理工大学，硅酸盐建筑材料国家重点实验室，武汉 430070，中国

^2．上海交通大学材料科学与工程学院，上海市激光制造与材料改性重点实验室，上海 200240，中国

^3．奥尔堡大学化学与生物科学系，奥尔堡 DK-9220，丹麦

^4．中山市武汉理工大学先进工程技术研究院，广东中山 528400，中国

^5．中国科学院高能物理研究所，北京同步辐射装置，北京 100049，中国

通讯作者:

陶海征（1973—），男，博士，教授。

葛璇（1992—），男，博士。

作者简介:

杜子娟（1995—），女，博士研究生。

Node Metal Mixing Effect on Glass Transition Temperature of Metal-Organic Framework Materials

Zijuan DU¹, Xuan GE²^,³, Ang QIAO¹^,⁴, Caijuan SHI⁵, Tao DU³, Yuanzheng YUE³, Haizheng TAO¹

Affiliations

^1.State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, China

^2.School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai Key Laboratory of Materials Laser Processing and Modification, Shanghai 200240, China

^3.Department of Chemistry and Bioscience, Aalborg University, Aalborg DK-9220, Denmark

^4.Wuhan University of Technology Advanced Engineering Technology Research Institute of Zhongshan City, Zhongshan 528437, Guangdong, China

^5.Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China

Corresponding Author:

TAO Haizheng (1973-), male, Ph.D., Professor. E-mail: thz@whut.edu.cn;

GE Xuan (1992-), male, Ph.D. xuge@bio.aau.dk

DU Zijuan (1995-), female, Doctoral candidate. E-mail: 219808@whut.edu.cn

出版时间: 2024-12-20 doi: 10.14062/j.issn.0454-5648.20240224

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摘要

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作为金属有机框架玻璃的子集，沸石咪唑酯骨架（ZIF）玻璃结构上由配位键所主导，具有高玻璃形成能力等一系列独特的性能。金属离子的替代会显著影响该类材料的功能，使玻璃化转变温度（T_g）等性质随替代金属节点离子浓度的线性改变呈现出非线性的变化规律，即混合金属节点效应。通过对比Zn_1-_xCo_x（C₃H₃N₂）₂（Zn_1-_xCo_x-ZIF-4）高密度非晶相（HDA）和Zn_1-_xCo_x（C₃H₃N₂）_1.75（C₇H₅N₂）_0.25（Zn_1-_xCo_x-ZIF-62）熔融淬冷玻璃（MQG）的T_g，发现拥有混合配体的Zn_1-_xCo_x-ZIF-62 MQG的T_g均高于拥有单一配体的Zn_1-_xCo_x-ZIF-4 HDA的T_g。通过混合金属节点效应强度［（ΔT_g）_max］的对比，发现与单配体Zn_1-_xCo_x-ZIF-4玻璃相比，混合配体Zn_1-_xCo_x-ZIF-62玻璃中（ΔT_g）_max更高。基于拓扑束缚理论和化学键特性，同时结合全散射实验对分布函数和配位四面体结构参数计算，本工作解析了Zn_1-_xCo_x-ZIF-4和Zn_1-_xCo_x-ZIF-62玻璃化转变温度和混合金属节点效应强度出现差异的结构和化学起源。

关键词

沸石咪唑酯骨架玻璃 / 配位四面体 / 混合金属节点效应 / 玻璃化转变温度 / 配体

Abstract

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Introduction

Zeolitic imidazolate framework (ZIF) material is a subset of metal-organic framework (MOF) materials with a structure similar to zeolite. Its basic structural unit is the [MN₄] tetrahedron formed by the coordination bond between transition metal center ions M (Co, Zn, etc.) and imidazole anions (Im, C₃H₃N₂^-) and their derivatives. Among them, ZIF-62 [Zn(C₃H₃N₂)₂-_n(C₇H₅N₂)_n] and ZIF-4 [Zn(C₃H₃N₂)₂] crystals can melt and form glasses before decomposition, which are widely used as basic research objects for MOF vitrification. For ZIF-62 and ZIF-4 glasses, changes in metal nodes can cause changes in the local coordination structure, including bond length and tetrahedral symmetry. This could further result in non-linear variations in properties such as glass transition temperature (T_g), which is known as a mixed-metal node effect. The impact of the coexistence of mixed ligands and metal nodes in ZIF structure on thermal properties and their structural origins is not elucidated. Therefore, a further exploration of the node metal mixing effect in ZIF glasses and its dependence on the ligand composition and structure can provide some insights into the relationship between the structure and performances of multi-component ZIF glasses. It is also of great significance to clarify the mixed former effect in inorganic glass and develop novel functional MOF glasses. In this study, the effect of ligand changes on the central metal node content and T_g of ZIF-4 and ZIF-62 glasses were discussed. In addition, the structural origin about the difference in mixed-metal node effect strength [(ΔT_g)_max] between ZIF-4 glass and ZIF-62 glass was also analyzed.

Methods

ZIF-4/62 crystals and ZIF-4/62 melt-quenched glass (MQG) were prepared by solvothermal and melt-quenching methods, respectively. The Zn_1-_xCo_x-ZIF-4 high-density amorphous phase (HDA) was prepared by differential scanning calorimetry instruments. The cobalt contents of bimetallic ZIF-4 samples were characterized by inductively coupled plasma-optical emission spectroscopy. The cobalt contents in bimetallic ZIF-62 samples were determined by ultraviolet-visible spectroscopy. The atomic structures of Zn-ZIF-4 MQG and Zn-ZIF-62 MQG were characterized by high energy synchrotron X-ray diffraction measurements. The total scattering structure factor S(Q) and pair distribution function g(r) were calculated based on the diffraction data. The in-house written code developed was used to calculate the structural parameters of MQG, i.e., the partial pair distribution functions of atom pairs, simulated total structure factor, [ZnN₄] tetrahedral order parameter (TOP), and Zn-N bond length distortion degree.

Results and discussion

According to the results of elemental analysis, the measured cobalt molar ratio (R) in the ZIF-4 and ZIF-62 crystals is lower than the initial one (x). Compared with the single-ligand ZIF-4 crystals, R in the mixed-ligand ZIF-62 crystals is closer to x. This is due to the different coordination reaction rates between different metal ions and ligands. Also, the T_g of the mixed-ligand ZIF-62 MQG is higher than that of the single-ligand ZIF-4 HDA. For instance, the T_g of Zn-ZIF-62 MQG is 31 ℃ higher than that of Zn-ZIF-4 HDA, and the T_g of Co-ZIF-62 MQG is 42 ℃ higher than that of Co-ZIF-4 HDA. These phenomena can be due to the presence of the bIm (C₇H₅N₂^-) ligand in ZIF-62 MQG. Based on the nonlinear variation of T_g with R, the mixed-metal node effect strength [(ΔT_g)_max] of ZIF-62 MQG is greater than that of ZIF-4 HDA. Specifically, the (ΔT_g)_max of ZIF-62 MQG is 7 ℃, which is greater than the (ΔT_g)_max of about 1 ℃ for ZIF-4 HDA.

The comparison in total scattering structure factors S(Q) shows that the intensity of the first sharp diffraction peak in Zn-ZIF-4 MQG is slightly greater than that of Zn-ZIF-62 MQG. Moreover, from the comparison in pair distribution functions g(r), the full width at half maximum of the peaks for Zn-N₁ and Zn-C atomic connections in the coordination tetrahedron of ZIF-62 MQG are broader, compared to ZIF-4 MQG. The simulations reveal that the TOP (tetrahedral order parameter) value of ZIF-62 MQG is slightly lower than that of ZIF-4 MQG. Also, the Zn—N bond length distortion degree for ZIF-62 MQG is higher than that for ZIF-4 MQG. Based on the results, the coordination tetrahedron units of Zn-ZIF-62 MQG may exhibit a higher disordered degree, compared to Zn-ZIF-4 MQG, implying greater structural flexibility and sensitivity of ZIF-62 glass when the central Zn ion is substituted by other metal ions in the structure. This indicates that the higher (ΔT_g)_max on the T_g of ZIF-62 glass is due to the presence of mixed ligand (Im and bIm).

Conclusions

Based on the solvothermal reaction mechanism of ZIF crystals, a faster reaction rate of Zn²⁺ with ligands to form complexes and a higher stability of the Zn²⁺-ligand coordination tetrahedra result in Zn²⁺ participating more rapidly in the formation of the ZIF network, thus leading to a lower R. Additionally, the stronger electron-donating property of the bIm ligand increases the coordination reaction rate of Co²⁺, leading to a higher R value in mixed-ligand ZIF-62, compared to that of single-ligand ZIF-4 crystals. According to the temperature-dependent topological constraint theory, the bIm increases both the number and strength of topological constraints in the ZIF-62 glass structure. As a result, the T_g of ZIF-62 glass is higher than that of ZIF-4 glass. The atomic arrangement in the [ZnN₄] tetrahedra of Zn-ZIF-62 MQG has a higher disordered degree, compared to that of Zn-ZIF-4 MQG. This can be attributed to the steric hindrance and stronger electron-donating ability of the bIm ligand in the Zn-ZIF-62 MQG. The higher disordered degree of tetrahedra indicates that the local coordination structure around the Zn metal nodes in Zn-ZIF-62 MQG is more susceptible to the influence of substituted Co nodes, thus enhancing the mixed-metal node effect on the T_g of Zn-ZIF-62 MQG.

Key words

zeolitic imidazolate framework glasses / coordination tetrahedra / mixed-metal node effect / glass transition temperature / ligand

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杜子娟, 葛璇, 乔昂, 师彩娟, 杜涛, 岳远征, 陶海征. 金属有机框架材料玻璃化转变温度的节点金属混合效应. 硅酸盐学报, 2024 , 52 (12) : 3673 -3684 . DOI: 10.14062/j.issn.0454-5648.20240224

Zijuan DU, Xuan GE, Ang QIAO, Caijuan SHI, Tao DU, Yuanzheng YUE, Haizheng TAO. Node Metal Mixing Effect on Glass Transition Temperature of Metal-Organic Framework Materials[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (12) : 3673 -3684 . DOI: 10.14062/j.issn.0454-5648.20240224

基金

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国家自然科学基金(22175135)
广东省基础与应用基础研究基金自然科学基金项目(2022A1515010312)

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2024年第52卷第12期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240224

接收时间：2024-03-19
首发时间：2026-10-22
出版时间：2024-12-20

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收稿日期：2024-03-19
修回日期：2024-05-08

基金

国家自然科学基金(22175135)

广东省基础与应用基础研究基金自然科学基金项目(2022A1515010312)

作者信息

^1．武汉理工大学，硅酸盐建筑材料国家重点实验室，武汉 430070，中国

^2．上海交通大学材料科学与工程学院，上海市激光制造与材料改性重点实验室，上海 200240，中国

^3．奥尔堡大学化学与生物科学系，奥尔堡 DK-9220，丹麦

^4．中山市武汉理工大学先进工程技术研究院，广东中山 528400，中国

^5．中国科学院高能物理研究所，北京同步辐射装置，北京 100049，中国

通讯作者:

陶海征（1973—），男，博士，教授。

葛璇（1992—），男，博士。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240224

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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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