面向乙烯一步纯化的多组分金属有机框架: 金属配体导向合成与C2混合气高效分离★

doi:10.6023/A26010033

化学学报 ›› 2026, Vol. 84 ›› Issue (5): 659-666.DOI: 10.6023/A26010033 上一篇下一篇

研究论文

面向乙烯一步纯化的多组分金属有机框架: 金属配体导向合成与C₂混合气高效分离^★

张伟宏, 马亚男, 方翰, 薛东旭^*()

陕西师范大学应用表面与胶体化学教育部重点实验室陕西省新概念传感器与分子材料重点实验室化学化工学院西安 710119

投稿日期:2026-01-30 发布日期:2026-04-03
通讯作者: 薛东旭
作者简介:
★“框架材料化学”专辑
基金资助:
国家自然科学基金(22471148); 国家自然科学基金(21871170); 国家重点研发计划(2022YFA1205502); 陕西省千人计划

Multi-Component Metal-Organic Frameworks for One-Step Ethylene Purification: Metalloligand-Directed Synthesis and High-Efficiency Separation of C₂ Mixed Gas^★

Weihong Zhang, Yanan Ma, Han Fang, Dongxu Xue^*()

Key Laboratory of Applied Surface and Colloid Chemistry of Ministry of Education, Shaanxi Provincial Key Laboratory of New Concept Sensors and Molecular Materials, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi?an 710119, China

Received:2026-01-30 Published:2026-04-03
Contact: Dongxu Xue
About author:
★ For the VSI “Chemistry of Framework Materials”.
Supported by:
National Natural Science Foundation of China(22471148); National Natural Science Foundation of China(21871170); National Key Research and Development Program of China(2022YFA1205502); Thousand Talents Program of Shaanxi Province

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摘要/Abstract

一步法纯化乙烯在工业生产中具有重要意义, 而多组分金属有机框架的可控构筑为C₂烃类气体分离及甲醇制烯烃(MTO)产物提纯提供了富有前景的解决方案. 本工作采用2,2'-联喹啉-4,4'-二甲酸(H₂BQDC)与CuBr原位配位形成金属配体单元Cu(BQDC)₂, 进而将其分别与ZrOCl₂、Fe₃O(OAc)₆(H₂O)₃及Bi(NO₃)₃•9H₂O通过溶剂热反应组装, 成功制备了三例结构明确的多组分金属有机框架材料: Zr-Cu-BQDC、Quat-Fe-Cu-BQDC和Quat-Bi-Cu-BQDC. 系统研究表明, 三种材料因其组成与孔道化学环境的差异, 分别对C₂H₂/C₂H₆/C₂H₄三元混合物和MTO典型组分C₃H₆/C₂H₄展现出优异的吸附选择性. 单组分气体吸附、理想吸附溶液理论(IAST)预测以及动态柱穿透实验共同验证了这些材料在常温常压下实现乙烯一步高效纯化的可行性. 本工作不仅发展了基于金属配体策略的多组分金属有机框架合成方法, 也为面向工业需求的烯烃分离材料设计提供了新思路.

关键词: 多组分金属有机框架, C₂气体分离, 甲醇制烯烃(MTO)产物分离, 一步纯化, 吸附分离

One-step purification of ethylene is an important research topic in the petrochemical field, as it directly influences the energy consumption and economic efficiency of olefin production processes. In recent years, multicomponent metal- organic frameworks (MOFs), owing to their structural tunability and functional diversity, have demonstrated significant potential in C₂ hydrocarbon gas separation and purification of products from methanol-to-olefins (MTO) processes. To address the limitations of conventional single-metal-center MOFs, which often suffer from structural simplicity and restricted functionality, this work proposes a controllable construction strategy for multicomponent MOFs based on the assembly of metal- ligand units. Specifically, 2,2′-biquinoline-4,4′-dicarboxylic acid (H₂BQDC) was employed as the organic ligand and coordinated with CuBr via an in situ reaction to form the metal-ligand unit Cu(BQDC)₂. Subsequently, solvothermal reactions with ZrOCl₂, Fe₃O(OAc)₆(H₂O)₃, and Bi(NO₃)₃•9H₂O successfully yielded three structurally well-defined multicomponent MOF materials: Zr-Cu-BQDC, Quat-Fe-Cu-BQDC, and Quat-Bi-Cu-BQDC. Comprehensive structural characterization and gas adsorption measurements reveal that the introduction of different metal centers leads to significant variations in pore size, coordination environment, and surface chemical properties, which in turn result in distinct adsorption and separation behaviors. Among them, Zr-Cu-BQDC and Quat-Fe-Cu-BQDC exhibit preferential adsorption toward C₂H₂ and C₂H₆, enabling one-step separation of high-purity C₂H₄ from ternary C₂H₂/C₂H₆/C₂H₄ mixtures. In contrast, Quat-Bi-Cu-BQDC shows stronger affinity for C₃H₆ and demonstrates effective separation performance for C₃H₆/C₂H₄ mixtures typically found in MTO products. The feasibility of achieving efficient one-step ethylene purification under ambient conditions was validated through single-component gas adsorption measurements, ideal adsorbed solution theory (IAST) predictions, and dynamic breakthrough experiments. This work not only develops an efficient synthesis strategy for multicomponent MOFs based on metal-ligand units and enriches the preparation pathways of multicomponent MOFs, but also provides new insights and theoreti- cal guidance for the rational design of olefin separation materials tailored for practical industrial applications, highlighting both significant academic value and promising industrial potential.

Key words: multicomponent metal-organic frameworks, C₂ gas separation, methanol-to-olefins (MTO) product separation, one-step purification, adsorptive separation

引用此文

张伟宏, 马亚男, 方翰, 薛东旭. 面向乙烯一步纯化的多组分金属有机框架: 金属配体导向合成与C₂混合气高效分离^★[J]. 化学学报, 2026, 84(5): 659-666.

Weihong Zhang, Yanan Ma, Han Fang, Dongxu Xue. Multi-Component Metal-Organic Frameworks for One-Step Ethylene Purification: Metalloligand-Directed Synthesis and High-Efficiency Separation of C₂ Mixed Gas^★[J]. Acta Chimica Sinica, 2026, 84(5): 659-666.

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图/表 6

图1. Zr-Cu-BQDC由BQDC和两种金属节点组装流程及其对应笼尺寸的示意图. 碳: 灰色, 锆: 绿色, 铜: 橙色, 氧: 红色, 氮: 天蓝色. 为清晰起见省略氢原子

Figure 1. Schematic diagram of the assembly process of Zr-Cu-BQDC from BQDC and two metal nodes, along with their corresponding cage sizes. C: gray, Zr: green, Cu: orange, O: red, N: sky blue. Hydrogen atoms are omitted for clarity

图2. Quat-Fe-Cu-BQDC由BQDC和三种金属节点组装流程及其一维通道尺寸示意图. 铁: 绿色, 铜: 橙色, 溴: 黄色. 为清晰起见省略了氢原子

Figure 2. Schematic diagram of the assembly process of Quat-Fe-Cu-BQDC from BQDC and three metal nodes, together with the 1D channel dimensions. Fe: green, Cu: orange, Br: yellow. Hydrogen atoms are omitted for clarity

图3. Quat-Bi-Cu-BQDC由BQDC和三种金属节点组装流程及其3D通道尺寸示意图. 铋: 绿色, 铜: 橙色. 为清晰起见省略了氢原子

Figure 3. Schematic diagram illustrating the assembly process of Quat-Bi-Cu-BQDC from BQDC and three metal nodes, along with its corresponding 3D channel dimensions. Bi: green, Cu: orange. Hydrogen atoms are omitted for clarity

图4. Zr-Cu-BQDC的(a) 77 K下N2吸附等温线; (b)孔径分布图; (c)单组分气体吸附等温线; (d) C2气体的吸附焓; (e) 298 K下, C2H2/C2H4和C2H6/C2H4的吸附选择性; (f) C2混合气体穿透曲线

Figure 4. For Zr-Cu-BQDC: (a) N2 adsorption isotherm at 77 K; (b) pore size distribution; (c) single-component gas adsorption isotherms; (d) Qst of C2 gases; (e) adsorption selectivity for C2H2/C2H4 and C2H6/C2H4 at 298 K; (f) breakthrough curves of C2 mixed gases

图5. Quat-Fe-Cu-BQDC的(a) 77 K下N2吸附等温线; (b)孔径分布图; (c)单组分气体吸附等温线; (d) C2气体的吸附焓; (e) 298 K下, C2H2/C2H4和C2H6/C2H4的吸附选择性; (f) C2混合气体穿透曲线

Figure 5. For Quat-Fe-Cu-BQDC: (a) N2 adsorption isotherm at 77 K; (b) pore size distribution; (c) single-component gas adsorption isotherms; (d) Qst of C2 gases; (e) adsorption selectivity for C2H2/C2H4 and C2H6/C2H4 at 298 K; (f) breakthrough curves of C2 mixed gases

图6. Quat-Bi-Cu-BQDC的(a) 77 K下N2吸附等温线; (b)孔径分布图; (c)单组分气体吸附等温线; (d) C3H6/C2H4气体的吸附焓; (e) 298 K下, C3H6/C2H4的吸附选择性; (f) C3H6/C2H4混合气体穿透曲线

Figure 6. For Quat-Bi-Cu-BQDC: (a) N2 adsorption isotherm at 77 K; (b) pore size distribution; (c) single-component gas adsorption isotherms; (d) Qst of C3H6/C2H4 gases; (e) adsorption selectivity for C3H6/C2H4 at 298 K; (f) breakthrough curves of C3H6/C2H4 mixed gases

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面向乙烯一步纯化的多组分金属有机框架: 金属配体导向合成与C₂混合气高效分离^★

Multi-Component Metal-Organic Frameworks for One-Step Ethylene Purification: Metalloligand-Directed Synthesis and High-Efficiency Separation of C₂ Mixed Gas^★

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