Salimi Saeideh, Akhbari Kamran, Farnia S Morteza F, Tylianakis Emmanuel, Froudakis Georg E, White Jonathan M
School of Chemistry, College of Science, University of Tehran, Tehran, Iran.
Department of Chemistry, University of Crete, 71003, Heraklion, Greece.
Chempluschem. 2024 Jan;89(1):e202300455. doi: 10.1002/cplu.202300455. Epub 2023 Oct 26.
In this report, a microporous metal-organic framework of [Ca(TDC)(DMA)] (1) and a two-dimensional coordination polymer of [Ca(TDC)(DMF) ] (2), (TDC =Thiophene-2,5-dicarboxylate, DMA=N, N'-dimethylacetamide and DMF=N, N'-dimethylformamide) based on Ca(II) were designed by the effect of solvent, and X-ray analysis was performed for the single crystals of 1 and 2. Then, compound 1 was synthesized in three different methods and identified with a set of analyses. Compared to other adsorbents, MOFs are widely used in the field of adsorption and separation of various gases due to a series of distinctive features such as diverse and adjustable structures pores with different dimensions, high porosity and surface area with regular distribution of active sites. Therefore, the ability of 1 to uptake single gases (CH , CO , C H , H and N ) and separation of several binary mixtures of gases (CO /CH , CO /N , CO /H and CO /C H ), were investigated using Grand Canonical Monte Carlo simulations. Volumetric and gravimetric adsorption isotherms in various operating conditions, the isosteric heat of adsorption (q ), the chemical potential for each thermodynamic state, and snapshots during the simulation process were reported in all cases. The results obtained from the adsorption simulation indicate that compound 1 has a high capacity for uptake of H (16 mmol g ) and N (12.5 mmol g ), CO (6.6 mmol g ), C H (5 mmol g ) and CH (1.5 mmol g ) gases at 1 bar. It also performs well in separating CO in binary mixtures, which can be attributed to the presence of open metal sites in nodes of 1 and their electrostatic tendency to interact with CO containing the higher quadrupole dipole moment compared to other components of the mixture.
在本报告中，基于溶剂效应设计了一种[Ca(TDC)(DMA)]（1）的微孔金属有机框架和一种[Ca(TDC)(DMF)]（2）的二维配位聚合物（TDC = 噻吩 - 2,5 - 二羧酸，DMA = N，N'-二甲基乙酰胺，DMF = N，N'-二甲基甲酰胺），并对1和2的单晶进行了X射线分析。然后，用三种不同方法合成了化合物1，并通过一系列分析对其进行了鉴定。与其他吸附剂相比，金属有机框架由于具有一系列独特的特征，如具有不同尺寸的多样且可调节的结构孔隙、高孔隙率和表面积以及活性位点的规则分布，而被广泛应用于各种气体的吸附和分离领域。因此，使用巨正则蒙特卡罗模拟研究了1对单一气体（CH₄、CO₂、C₂H₄、H₂和N₂）的吸附能力以及几种二元气体混合物（CO₂/CH₄、CO₂/N₂、CO₂/H₂和CO₂/C₂H₄）的分离能力。在所有情况下都报告了各种操作条件下的体积和重量吸附等温线、吸附等量热（qst）、每个热力学状态的化学势以及模拟过程中的快照。吸附模拟得到的结果表明，化合物1在1 bar下对H₂（16 mmol g⁻¹）、N₂（12.5 mmol g⁻¹）、CO₂（6.6 mmol g⁻¹）、C₂H₄（5 mmol g⁻¹）和CH₄（1.5 mmol g⁻¹）气体具有高吸附容量。它在二元混合物中分离CO₂方面也表现良好，这可归因于1的节点中存在开放金属位点以及它们与混合物中其他组分相比具有与具有更高四极偶极矩的CO₂相互作用的静电倾向。
