A polyhedron-based metal-organic framework with electronegative donor sites for efficient C2H6/C2H4 separation

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure Pub Date : 2024-09-30 DOI:10.1016/j.molstruc.2024.140166

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Abstract

Ethylene is an important chemical raw material which is widely used in the production of chemical fibers, plastics, rubber, coatings, as well as medicines, and its separation from the gas mixtures of C₂H₆/C₂H₄ is of great importance but a challenging task due to their similar physical properties and molecular dimensions. Herein, we report the C₂H₆ and C₂H₄ sorption studies on a robust anionic metal-organic framework (MOF) {(NH₂Me₂)[Co₃(μ₃OH)(TPT)(TZB)₃](H₂O)₆(DMA)₆}_n (Co-MOF) formed by connection of Co₃(OH) clusters by two N-rich organic ligands 2,4,6-tri(4-pyridyl)-1,3,5-triazine (TPT) and 4-(1H-Tetrazol-5-yl)benzoic acid (H₂TZB). The prepared Co-MOF features a polyhedron stacking network structure composed of trigonal bipyramidal cages and octahedral cage which both contribute to a high C₂H₆ uptake capacity of 6.48 mmol/g and a decent C₂H₆/C₂H₄ selectivity of 1.54 at 298 K and 1 bar. Grand Canonical Monte Carlo (GCMC) simulation results agree well with the experimental tendency, both in the adsorption isotherms and sorption heats, which demonstrated that the suitable pore surfaces with electronegative donor sites generated multiple CH ⋅⋅⋅O/N and CH ⋅⋅⋅π interactions between the framework and C₂H₆, resulting in a stronger interaction between the MOF skeleton and C₂H₆ molecule than C₂H₄ as reflected by the dispersion-corrected density functional theory (DFT) calculation.

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具有电负性供体位点的多面体金属有机框架，可实现 C2H6/C2H4 的高效分离

乙烯是一种重要的化工原料，被广泛应用于化纤、塑料、橡胶、涂料和药品的生产中，从 C2H6/C2H4 混合气体中分离乙烯非常重要，但由于它们具有相似的物理性质和分子尺寸，分离工作极具挑战性。在此，我们报告了由两个富含 N 的有机配体 2 连接 Co3（OH）团簇而形成的强大阴离子金属有机框架（MOF）{(NH2Me2)[Co3(μ3OH)(TPT)(TZB)3](H2O)6(DMA)6}n（Co-MOF）对 C2H6 和 C2H4 的吸附研究、4,6-三（4-吡啶基）-1,3,5-三嗪（TPT）和 4-（1H-四唑-5-基）苯甲酸（H2TZB）连接而成。制备的 Co-MOF 具有由三叉双锥笼和八面体笼组成的多面体堆叠网络结构，这两种结构都有助于在 298 K 和 1 bar 条件下实现 6.48 mmol/g 的高 C2H6 吸收能力和 1.54 的 C2H6/C2H4 选择性。大卡农蒙特卡罗（GCMC）模拟结果与实验趋势非常吻合，无论是吸附等温线还是吸附热，都表明具有电负性供体位点的合适孔隙表面在框架与 C2H6 之间产生了多种 CH⋅⋅O/N 和 CH⋅⋅π 相互作用，从而导致 MOF 骨架与 C2H6 分子之间的相互作用强于 C2H4，这一点在色散校正密度泛函理论（DFT）计算中得到了反映。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Journal of Molecular Structure 化学-物理化学

CiteScore

7.10

自引率

15.80%

发文量

2384

审稿时长

45 days

期刊介绍： The Journal of Molecular Structure is dedicated to the publication of full-length articles and review papers, providing important new structural information on all types of chemical species including: • Stable and unstable molecules in all types of environments (vapour, molecular beam, liquid, solution, liquid crystal, solid state, matrix-isolated, surface-absorbed etc.) • Chemical intermediates • Molecules in excited states • Biological molecules • Polymers. The methods used may include any combination of spectroscopic and non-spectroscopic techniques, for example: • Infrared spectroscopy (mid, far, near) • Raman spectroscopy and non-linear Raman methods (CARS, etc.) • Electronic absorption spectroscopy • Optical rotatory dispersion and circular dichroism • Fluorescence and phosphorescence techniques • Electron spectroscopies (PES, XPS), EXAFS, etc. • Microwave spectroscopy • Electron diffraction • NMR and ESR spectroscopies • Mössbauer spectroscopy • X-ray crystallography • Charge Density Analyses • Computational Studies (supplementing experimental methods) We encourage publications combining theoretical and experimental approaches. The structural insights gained by the studies should be correlated with the properties, activity and/ or reactivity of the molecule under investigation and the relevance of this molecule and its implications should be discussed.