A chlorine-rich Zn-based metal-organic framework for efficient separation of C3H6/C2H4 and C2H6/C2H4

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials Pub Date : 2025-03-13 DOI:10.1016/j.micromeso.2025.113600

Jilong Peng , Xunqian Zhang , Rongqing Qin , Fang Lai , Na Shi , Qinggang Ren , Kungang Chai

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Abstract

In the petrochemical industry, efficiently achieving one-step purification of ethylene (C₂H₄) from propylene (C₃H₆) or ethane (C₂H₆) is a highly sought-after yet challenging task. Herein, we present a chlorine-rich Zn-based metal-organic framework (DMOF-1-Cl₂) that retains the essential topology of the parent DMOF-1 through the incorporation of 2,5-dichloroterephthalate linkers. The chlorine atoms within the square pores of DMOF-1-Cl₂, due to their high electronegativity, serve as potential adsorption sites. Gas adsorptive experiments revealed its preferential adsorption of C₃H₆ and C₂H₆ over C₂H₄ at different temperatures. Ideal adsorption solution theory calculation revealed that the selectivity of DMOF-1-Cl₂ for C₃H₆/C₂H₄ and C₂H₆/C₂H₄ reaches 20.8 and 2.2 at 313 K, respectively, outperforming its counterpart (DMOF-1-Br₂) and most previously reported adsorbents. Theoretical calculations indicated that the gas molecules are primarily distributed around the chlorine atoms with multiple interactions. Furthermore, dynamic breakthrough experiments fully demonstrated the actual potential for achieving one-step purification of polymer-grade C₂H₄, in which DMOF-1-Cl₂ displayed high productivity of 206.1 and 31.6 L kg⁻¹ from C₃H₆/C₂H₄ (2/5, v/v) and C₂H₆/C₂H₄ (1/9, v/v), respectively. Despite the fact that the yield of C₂H₄ separation from C₂H₆/C₂H₄ mixtures is not extremely high, it still remains at a satisfactory level, demonstrating the practical value and potential of DMOF-1-Cl₂ for industrial applications.

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一种高效分离C3H6/C2H4和C2H6/C2H4的富氯锌基金属有机骨架

在石油化工行业，高效地实现从丙烯（C3H6）或乙烷（C2H6）中一步提纯乙烯（C2H4）是一项备受追捧但具有挑战性的任务。在此，我们提出了一种富氯的锌基金属有机骨架（DMOF-1- cl2），通过加入2,5-二氯对苯二甲酸酯连接剂，它保留了母体DMOF-1的基本拓扑结构。DMOF-1-Cl2的方形孔中的氯原子由于其高电负性，成为潜在的吸附位点。气体吸附实验表明，在不同温度下，其对C3H6和C2H6的吸附优于C2H4。理想吸附溶液理论计算表明，在313 K时，DMOF-1-Cl2对C3H6/C2H4和C2H6/C2H4的选择性分别达到20.8和2.2，优于其对应物（DMOF-1-Br2）和大多数先前报道的吸附剂。理论计算表明，气体分子主要分布在氯原子周围，存在多重相互作用。此外，动态突破实验充分证明了实现聚合物级C2H4一步提纯的实际潜力，其中DMOF-1-Cl2从C3H6/C2H4 （2/5, v/v）和C2H6/C2H4 （1/9, v/v）中分别表现出206.1和31.6 L kg−1的高生产率。尽管从C2H6/C2H4混合物中分离C2H4的产率不是很高，但仍保持在令人满意的水平，这表明了DMOF-1-Cl2在工业应用中的实用价值和潜力。

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来源期刊

Microporous and Mesoporous Materials 化学-材料科学：综合

CiteScore

10.70

自引率

5.80%

发文量

649

审稿时长

26 days

期刊介绍： Microporous and Mesoporous Materials covers novel and significant aspects of porous solids classified as either microporous (pore size up to 2 nm) or mesoporous (pore size 2 to 50 nm). The porosity should have a specific impact on the material properties or application. Typical examples are zeolites and zeolite-like materials, pillared materials, clathrasils and clathrates, carbon molecular sieves, ordered mesoporous materials, organic/inorganic porous hybrid materials, or porous metal oxides. Both natural and synthetic porous materials are within the scope of the journal. Topics which are particularly of interest include: All aspects of natural microporous and mesoporous solids The synthesis of crystalline or amorphous porous materials The physico-chemical characterization of microporous and mesoporous solids, especially spectroscopic and microscopic The modification of microporous and mesoporous solids, for example by ion exchange or solid-state reactions All topics related to diffusion of mobile species in the pores of microporous and mesoporous materials Adsorption (and other separation techniques) using microporous or mesoporous adsorbents Catalysis by microporous and mesoporous materials Host/guest interactions Theoretical chemistry and modelling of host/guest interactions All topics related to the application of microporous and mesoporous materials in industrial catalysis, separation technology, environmental protection, electrochemistry, membranes, sensors, optical devices, etc.