We report three novel pore-space-partitioned metal-organic frameworks (MOFs) functionalized with fluorine and hydroxyl groups using 2,3,5,6-tetrafluorobenzene-1,4-dicarboxylic acid (F-BDC) and a new ligand 3,6-difluoro-2,5-dihydroxybenzene-1,4-dicarboxylic acid (F(OH)-BDC) as organic building blocks, with 1,3,5-tris(4-pyridyl)-2,4,6-triazine (TPT) as pore partition agent. With the polar fluorine and hydroxyl groups and the open metal sites being blocked by TPT, moderate molecule-framework interactions can be engineered. These three isoreticular microporous frameworks Mn-TPT-BDC-F (NCKU-21), Mn-TPT-BDC-F(OH) (NCKU-22), and Mg-TPT-BDC-F(OH) (NCKU-23) (NCKU=National Cheng Kung University) exhibit distinct single-component gas adsorption behaviors. Although NCKU-22 uptakes a much lower amount of CH compared to NCKU-21 and -23, dynamic breakthrough experiments show that these three materials are all capable of efficient CH/CH separations. These MOFs possess moderate isosteric heat of adsorption for CH (25.7-32.1 kJ mol), allowing easy regeneration and energy-efficient CH/CH separations.
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http://dx.doi.org/10.1002/asia.202401329 | DOI Listing |
Chem Asian J
January 2025
Institute of Clinical Pharmacy and Pharmaceutical Sciences, School of Pharmacy, College of Medicine, National Cheng Kung University, Tainan City, 70101, Taiwan.
We report three novel pore-space-partitioned metal-organic frameworks (MOFs) functionalized with fluorine and hydroxyl groups using 2,3,5,6-tetrafluorobenzene-1,4-dicarboxylic acid (F-BDC) and a new ligand 3,6-difluoro-2,5-dihydroxybenzene-1,4-dicarboxylic acid (F(OH)-BDC) as organic building blocks, with 1,3,5-tris(4-pyridyl)-2,4,6-triazine (TPT) as pore partition agent. With the polar fluorine and hydroxyl groups and the open metal sites being blocked by TPT, moderate molecule-framework interactions can be engineered. These three isoreticular microporous frameworks Mn-TPT-BDC-F (NCKU-21), Mn-TPT-BDC-F(OH) (NCKU-22), and Mg-TPT-BDC-F(OH) (NCKU-23) (NCKU=National Cheng Kung University) exhibit distinct single-component gas adsorption behaviors.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi'an, 710127, P.R. China.
Efficient separation of acetylene (CH) from carbon dioxide (CO) and ethylene (CH) is a significant challenge in the petrochemical industry due to their similar physicochemical properties. Pore space partition (PSP) has shown promise in enhancing gas adsorption capacity and selectivity by reducing pore size and increasing the density of guest binding sites. Herein, we firstly employ the 2D→3D polycatenation strategy to construct a PSP metal-organic framework (MOF) Ni-dcpp-bpy, incorporating functional N/O sites to enhance CH purification.
View Article and Find Full Text PDFSmall
December 2024
Department of Chemistry and Biochemistry, California State University Long Beach, Long Beach, CA, 90840, USA.
Isoreticular chemistry is among the most powerful strategies for designing novel materials with optimizable pore geometry and properties. Of great significance to the further advance of isoreticular chemistry is the development of broadly applicable new concepts capable of guiding and systematizing the ligand-family expansion as well as establishing correlations between dissimilar and seemingly uncorrelated ligands for better predictive synthetic design and more insightful structure and property analysis. Here ligand circuit concept is proposed and its use has been demonstrated for the synthesis of a family of highly stable, high-performance pore-space-partitioned materials based on an acyclic ligand, trans, trans-muconic acid.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
College of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang, 443002, P. R. China.
The controllable and precise structural regulation of metal-organic frameworks (MOFs) based on isoreticular chemistry is an effective strategy for creating functional material platforms, such as efficient porous adsorbents. Herein, for the first time, mediated by an unprecedented self-adaptive coordination evolution (SACE) on pseudo-D-symmetric [M(μ-O)(COO)] (M=Mn/Fe) clusters, two pore space partitioned MOFs (CTGU-47-Mn/Fe, CTGU=China Three Gorges University) have been successfully constructed. Owing to the more confined adsorption space and dense binding sites produced by pore space partitioning (PSP), the CTGU-47-Mn/Fe exhibit significantly enhanced performance in the capture or recovery SF (greenhouse/electronic specialty gas) from SF/N mixture compared to their non-partitioned homologous structures (CTGU-46-Mn/Fe) with adsorption selectivity increased from 37/72 to 634/157 (v/v, 10/90, 100 kPa).
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Department of Chemistry, University of California, Riverside, 900 University Ave, Riverside, CA-92521, United States.
Compared to exploratory development of new structure types, pushing the limits of isoreticular synthesis on a high-performance MOF platform may have higher probability of achieving targeted properties. Multi-modular MOF platforms could offer even more opportunities by expanding the scope of isoreticular chemistry. However, navigating isoreticular chemistry towards best properties on a multi-modular platform is challenging due to multiple interconnected pathways.
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