Tuning the Formations of Metal–Organic Frameworks by Modification of Ratio of Reactant, Acidity of Reaction System, and Use of a Secondary Ligand
- Beijing University of Technology (China). College of Environmental and Energy Engineering; Texas A & M Univ., College Station, TX (United States). Dept. of Chemistry
- Texas A & M Univ., College Station, TX (United States). Dept. of Chemistry
- Beijing University of Technology (China). College of Environmental and Energy Engineering
Four porous coordination networks (PCNs), {[Zn₃O(H₂O)₃(adc)₃]·2(C₂H₆NH₂)·2(DMF)·3(H₂O)}n (PCN-131), Zn₂(DMA)₂(adc)₂]·2(DMA)}n (PCN-132), {[Zn₃O(DMF)(adc)₃(4,4'-bpy)]·2(C₂H₆NH₂)·S}n (PCN-131'), and {[Zn(adc)(4,4'-bpy)0.5]·S}n (PCN-132'), have been synthesized by the assembly of anthrancene-9,10-dicarboxylic acid (H₂adc) with Zn(II) under different reaction conditions, including modifications of reactant ratio, acidity variations, and the use of a secondary ligand. Single-crystal X-ray diffraction studies reveal that PCN-131, obtained from the dimethylformamide (DMF) solution under acid condition, has a three-dimentional (3D) framework structure with one-dimensional (1D) honeycomb channels. PCN-132 isolated from dimethylacetamide (DMA) solution without adding acid in synthesis is a two-dimensional (2D) layer compound. By employing 4,4'-bipyridyl (4,4'-bpy) as a secondary ligand, PCN-131' and PCN-132' were synchronously synthesized as a mixture outcome with more PCN-131' than PCN-132'. In PCN-131', 4,4'-bpy acting as a secondary ligand is arranged inside the honeycomb channel of the 3D PCN-131, resulting in an effective improvement of thermal stability of the network, while in PCN-132', 4,4'-bpy ligands link 2D layers of PCN-132 to form a pillared-layer 3D framework. Gas adsorption has been performed for selected materials. The results show that the framework of PCN-131 is thermally unstable after removing the solvent molecules coordinated to their metal sites. While PCN-131' is stable for gas uptake, with an evaluated Langmuir surface area of 199.04 m² g–1, it shows a selective adsorption of CO₂ over CH₄.
- Research Organization:
- Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- DOE Contract Number:
- SC0001015
- OSTI ID:
- 1065969
- Journal Information:
- Crystal Growth and Design, Vol. 12, Issue 1; Related Information: CGS partners with University of California, Berkeley; University of California, Davis; Lawrence Berkeley National Laboratory; University of Minnesota; National Energy Technology Laboratory; Texas A&M University; ISSN 1528-7483
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
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