Citation: HU Yun-Xia, ZHANG Wen-Wei, WANG Li-Feng, BAI Jun-Feng. Synthesis and Gas Sorption Properties of Cupric Microporous Metal-Organic Framework Based on 1,1’-Ethynebenzene-3,3’,5,5’-tetracarboxylate[J]. Chinese Journal of Inorganic Chemistry, ;2013, 29(7): 1471-1479. doi: 10.3969/j.issn.1001-4861.2013.00.200 shu

Synthesis and Gas Sorption Properties of Cupric Microporous Metal-Organic Framework Based on 1,1’-Ethynebenzene-3,3’,5,5’-tetracarboxylate

1.
1 State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China;

Received Date: 7 August 2012
Available Online: 17 March 2013
Fund Project: 国家自然科学基金(No.20771058) (No.20771058)国家自然科学基金创新研究群体(No.20721002) (No.20721002)教育部博士点基金(No.200802840011) (No.200802840011)新疆凝聚态相变与微结构实验室开放课题基金(No.XJDX0912-2011-01)资助项目。 (No.XJDX0912-2011-01)

The synthesis, crystal structure, and sorption properties of [Cu₂(EBTC)(H₂O)₂]·8H₂O·DMF·DMSO (abbreviated as 1, EBTC=1,1'-ethynebenzene-3,3',5,5'-tetracarboxylate; DMF=N,N-dimethyl formamide; DMSO=dimethyl sulfoxide) are reported. 1 features two kinds of cavities with a diameter of 0.85 nm and 0.85×2.15 nm, which are enclosed respectively by six and twelve tetracarboxylate-bridged [Cu₂(CO₂)₄] paddle-wheels and extended by the EBTC linkers into a three-dimensional (3D) supramolecular structure with 1D channels accommodating the solvent molecules. It adopts the (3,4)-c net of fof (sqc 1575) topology, possesses very large solvent accessible pore volume which reaches 72.8% of the unit cell volume. After removal of the solvent molecules, the desolvated 1a exhibits permanent porosity verified by an N₂ sorption isotherm with a Langmuir surface area of 2844 m²·g^-1 and Brunauer-Emmett-Teller (BET) surface area of 1 852 m²·g^-1. It displays significant uptake of gases (H₂, CO₂, CH₄, C₂H₂) and relatively high adsorption enthalpies. Especially, it is notable that 1a exhibits the highest acetylene storage of 252 cm³·g^-1 at 273 K under 1.0×105 Pa with higher adsorption enthalpy (34.5 kJ·mol^-1 at the coverage of 1 mmol·g^-1) among all porous metal-organic materials reported to date. CCDC: 744108.
- microporous MOFs;solvothermal synthesis;crystal structure;adsorption property
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