硅酸盐学报

新型自支撑ZIF玻璃膜的制备及气体分离性能

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叶茂 ¹^,² , 奥德 ¹^,⁵ , 孙玉绣 ¹^,³ , 顾振杰 ¹^,⁴ , 杨紫博 ⁶ , 乔志华 ¹^,³

硅酸盐学报 | MOF玻璃研究新进展专题—研究论文 2024,52(8): 2545-2552

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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) : 2545 -2552

新型自支撑ZIF玻璃膜的制备及气体分离性能

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叶茂¹^,², 奥德¹^,⁵, 孙玉绣¹^,³, 顾振杰¹^,⁴, 杨紫博⁶, 乔志华¹^,³

作者信息

^1．天津工业大学省部共建分离膜与膜过程国家重点实验室，天津 300387

^2．天津工业大学纺织科学与工程学院，天津 300387

^3．天津工业大学化学工程与技术学院，天津 300387

^4．天津工业大学物理科学与技术学院，天津 300387

^5．天津工业大学材料科学与工程学院，天津 300387

^6．邯郸学院，河北省杂环化合物重点实验室，河北邯郸 056006

通讯作者:

杨紫博（1991—），男，博士，讲师；

乔志华（1985—），男，博士，教授。

作者简介:

叶茂（2000—），男，硕士研究生。

Preparation and Performance of a Novel Self-supported ZIF Glass Membrane for Gas Separation

Mao YE¹^,², De AO¹^,⁵, Yuxiu SUN¹^,³, Zhenjie GU¹^,⁴, Zibo YANG⁶, Zhihua QIAO¹^,³

Affiliations

^1.State Key Laboratory of Separation Membranes and Membrane Processes, Tiangong University, Tianjin 300387, China

^2.School of Textile Science and Engineering, Tiangong University, Tianjin 300387, China

^3.School of Chemical Engineering and Technology, Tiangong University, Tianjin 300387, China

^4.School of Physical Science and Technology, Tiangong University, Tianjin 300387, China

^5.School of Materials Science and Engineering, Tiangong University, Tianjin 300387, China

^6.Hebei Key Laboratory of Heterocyclic Compounds, Handan University, Handan 056006, Hebei, China

Corresponding Author:

YANG Zibo (1991-), male, Ph.D., Lecturer. E-mail: yangzibo0125@163.com;

QIAO Zhihua (1985-), male, Ph.D., Professor. qiaozhihua@tiangong.edu.cn

YE Mao (2000-), male, Master candidate. E-mail: 15020367203@163.com

出版时间: 2024-08-20 doi: 10.14062/j.issn.0454-5648.20230864

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摘要

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金属-有机骨架（MOF）材料因其较高的比表面积、丰富的化学官能团、可调的孔隙结构和良好的热化学稳定性而可作为膜材料备受关注。本工作利用液体辅助球磨法合成了沸石型咪唑酯骨架材料（ZIF-62），通过对压制的ZIF-62薄片进行热处理，得到了具有良好气体分离性能的自支撑ZIF-62玻璃膜。结果表明，热处理过程未改变ZIF-62晶体的化学键和配体组成，实现了ZIF-62晶体从晶态到无定形玻璃态的转化。通过改变ZIF-62粉末的添加量，可以得到不同厚度的自支撑ZIF-62玻璃膜，随着厚度的不断降低，制备的ZIF-62玻璃膜的CO₂渗透速率不断增加，CO₂/CH₄分离选择性不断降低。此外，在48 h的连续测试过程中，ZIF-62玻璃膜的气体分离性能依旧保持良好的稳定性。本工作对MOF材料在膜气体分离领域中的应用具有参考意义。

关键词

金属-有机骨架 / 玻璃膜 / 可加工性 / 气体分离

Abstract

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Introduction

MOF gas separation membranes have attracted much attention due to the large BET surface area, flexible functional groups, adjustable structure, and good thermo-chemical stability, which can significantly improve the separation efficiency and purity of the gas separation process. However, MOF gas separation membranes have unavoidable grain boundaries and are prone to non-selective defects, which greatly destroys the intrinsic separation properties of pure MOF materials, posing a serious of challenges during the preparation and application. MOF glass membranes is an emerging type of gas separation membrane with the advantages of easy processing, no grain boundary defects and permanent porosity, and have become a new access for the preparation of high-performance gas separation membranes. However, the typical MOF glass membranes are normally formed on support layers, and the presence of the supporting layers greatly limits the processability and gas permeability enhancement. In this work, a novel preparation method of self-supported MOF glass membranes is proposed, and a serious of self-supported ZIF-62 glass membranes performing excellent CO₂/CH₄ gas separation property are obtained.

Methods

In the present work, ZIF-62 crystals were prepared according to the previous literature. Zinc hydroxide, zinc acetate dihydrate (purity 99%, manufacturers are Shanghai Aladdin Biochemistry Science and Technology Co., Ltd.), imidazole (purity 99.5%, manufacturers are Anhui Zesheng Science and Technology Co., Ltd.), benzimidazole (purity 96% manufacturers are Shanghai McLean Biochemistry Science and Technology Co., Ltd.), N,N- N,N- dimethylformamide (purity of analytical purity, the manufacturers are Sinopharm Chemical Reagent Co., Ltd.), etc were used. Then, the ZIF-62 crystals were pressed to thin pellets in specific molds, and were heat-treated by a preset heating procedure, so as to prepare the homogeneous and dense self-supported amorphous ZIF-62 glass (a_gZIF-62) membranes. The difference of the properties between ZIF-62 crystals and a_gZIF-62 membranes were characterized. After that, self-supported a_gZIF-62 membranes with different thicknesses were prepared by changing the dosage of ZIF-62 crystals. The influence of thickness on the surface morphology and the CO₂/CH₄ separation performance of self-supported a_gZIF-62 membranes were investigated.

Results and discussion

It is proved by XRD, DSC and TG curves that the ZIF-62 crystals will be fully melted and transformed from crystalline to amorphous glassy state under the heat treatment condition of holding at 440 ℃ for 20 min. Meanwhile, the chemical bonds and ligands of the periodic crystalline structure of the ZIF-62 crystals will not be changed after heat treatment verified by FTIR and ¹H NMR analyses.

According to the SEM images, it can be observed that the surface of self-supported a_gZIF-62 membranes is dense without obvious defects, indicating that the prepared self-supported a_gZIF-62 membrane qualifies the process requirements of gas separation. Combining with XPS and adsorption isotherms of CO₂ and CH₄, it is proved that the self-supported a_gZIF-62 membranes have an excellent CO₂/CH₄ separation performance. With increasing thickness of self-supported a_gZIF-62 membranes, the CO₂ permeance gradually decreases, while the separation selectivity of CO₂/CH₄ is improved. What's more, the self-supported a_gZIF-62 membrane possesses good performance and long-term stability in CO₂/CH₄ separation.

Conclusions

ZIF-62 crystals with uniform particle size were prepared by liquid-assisted ball milling method, and self-supported ZIF-62 glass membranes were prepared by pressing ZIF-62 crystal powders in special designed molds succeeding with heat treatment. The thickness of the a_gZIF-62 membranes can be easily regulated to obtain gas separation membranes with excellent gas separation performance. The prepared a_gZIF-62 membranes also show excellent long-term stability with their performance remaining essentially unchanged during continuous testing for about 48 h, which is potentially advantageous for industrial CO₂ separation. The proposed scheme for the preparation of self-supported ZIF-62 glass membranes is highly adjustable. By changing the shape of the mold, self-supported MOF glass membranes with different shape and size can be obtained, giving advantages of the processability of MOF glass membranes, which is of great significance for the application of MOF glass membranes in different fields.

Key words

metal-organic framework / glass membrane / processability / gas separation

引用本文

叶茂, 奥德, 孙玉绣, 顾振杰, 杨紫博, 乔志华. 新型自支撑ZIF玻璃膜的制备及气体分离性能. 硅酸盐学报, 2024 , 52 (8) : 2545 -2552 . DOI: 10.14062/j.issn.0454-5648.20230864

Mao YE, De AO, Yuxiu SUN, Zhenjie GU, Zibo YANG, Zhihua QIAO. Preparation and Performance of a Novel Self-supported ZIF Glass Membrane for Gas Separation[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (8) : 2545 -2552 . DOI: 10.14062/j.issn.0454-5648.20230864

基金

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河北省科技计划(22373709D)
河北省高等学校科学研究项目(BJK2024029)

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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.0454-5648.20230864

接收时间：2023-11-12
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：2023-11-12
修回日期：2023-12-05

基金

河北省科技计划(22373709D)

河北省高等学校科学研究项目(BJK2024029)

作者信息

^1．天津工业大学省部共建分离膜与膜过程国家重点实验室，天津 300387

^2．天津工业大学纺织科学与工程学院，天津 300387

^3．天津工业大学化学工程与技术学院，天津 300387

^4．天津工业大学物理科学与技术学院，天津 300387

^5．天津工业大学材料科学与工程学院，天津 300387

^6．邯郸学院，河北省杂环化合物重点实验室，河北邯郸 056006

通讯作者:

杨紫博（1991—），男，博士，讲师；

乔志华（1985—），男，博士，教授。

参考文献

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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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