RESUMEN
Metal-organic cages (MOCs) are an emerging class of porous materials with promising applications. However, controlling the configuration of the cage packing, which can influence the overall porosity of the materials, remains a difficulty, as many factors can influence the cage assembly and stacking. Herein, we report a solvent strategy to fine-tune the packing configuration of a bilayer MOC, a small triangular prism cage (six Cu ions act as vertices, three nitrate ions act as pillars, and six nitrate ions act as caps) incorporated into a large triangular prism cage (another six Cu ions act as vertices, a couple of oxygen atoms act as pillars and six ligands (L1: 3,5-bis(pyridine-3-yl)-4H-1,2,4-triazole) act as a jointed cap) by the coordination between the triazole nitrogen from L1 and the inner vertex Cu ions. The involved solvents water, acetonitrile (MeCN) and N,N'-dimethylformamide (DMF) form hydrogen bonds with this bilayer MOC, resulting in three different types of packing associated with systemically tuned porosity (NTU-93: 12.2%, NTU-94: 19.3%, and NTU-95: 42.1%). Gas adsorption and breakthrough tests demonstrate that NTU-95 has potential ability for C2H2/C2H4 separation. This work not only shows a case of finely tuned packing of coordination cages, but also provides a powerful tool that may be extended to other cage families.
RESUMEN
Highly efficient ethylene (C2H4) and acetylene (C2H2) separation is a great challenge and an important process in current industries. Herein, we finely tune a new family of 6-c metal-organic frameworks (MOFs) with crab-like carboxylic pincers for the recognition of a C2H2 tetramer and afford NTU-72 with high adsorption C2H2/C2H4 selectivity (56-441, 298 K) as well as unprecedented recovery of both highly pure C2H4 (99.95%) and C2H2 (99.36%). Furthermore, the effective binding of a C2H2 tetramer by NTU-72's carboxylic pincers has been revealed by gas-loaded crystallography and Raman spectral studies. Our work provides a novel approach for the selective binding of a small molecular cluster for designing high-performance MOFs.
RESUMEN
The development of efficient porous absorbents with high uptake and selectivity remains a great challenge, especially for the recovery of acetylene (C2H2) from its carbon dioxide (CO2)-containing mixtures. Here, we propose and report an anion-planting strategy for regulating the scu topological porous coordination polymers (PCPs) into the C2H2 trap. The three electronegative anions SiF62-, TiF62-, and ZrF62-, in addition to the ligand of 3,5-di(1H-imidazol-1-yl)benzoic acid (HL) and Cu2+ ion, were employed to construct highly porous PCPs (NTU-60, NTU-61, and NTU-62) with varied window aperture. Especially, due to a matching distance (dF-F) of 5.7 Å along the c-axis, the limited space that can be assigned as a single C2H2 trap enables NTU-61 to show optimal ability for C2H2 (van der Waals (vdW) parameters of the two H atoms: â¼5.72 Å) recognition, validated by Grand Canonical Monte Carlo (GCMC) calculations and Raman spectra. These characteristics allow the NTU-series to show higher C2H2 uptake, as well as excellent C2H2/CO2 separation performance under dynamic conditions. The molecular insight and strategy here not only permit balanced adsorption and separation in a single domain but also exhibit an opportunity to develop advanced adsorbents in nearly all frameworks with lattice or coordinated ions, which may act as the platforms for various selective guest trappings with on-demand time and/or spatial resolution.
RESUMEN
Metal-organic frameworks (MOFs) have attracted much attention in the areas of biomedicine and medicine owing to their versatile porous structure. However, the oversize and high cellular toxicity of some metal-based MOF particles have hindered their development. Therefore, a series of small Ti-based MOFs are prepared with the introduction of tetraethyl orthosilicate (TEOS) into the reaction system. Compared with the Ti-based MOFs prepared by traditional methods, the size of the Ti-based MOFs prepared with this method is decreased by 42.78%. Meanwhile, the good biocompatibility of the prepared Ti-based MOF particles toward the L929 cell lines is proven using CCK-8 assays. Furthermore, the controlled release property of the Ti-based MOFs is evaluated by using ibuprofen (IBU) as a model drug. The amount of drug loaded in the samples is shown to be approximately 10%, and approximately 95% of the IBU is released from the MOFs after exposure to PBS for 24 h. We conclude that the size-decreased Ti-based MOFs prepared with the introduction of TEOS into the reaction systems are potential drug carriers in terms of their good biocompatibility and effective performance in the controlled release of a drug.