RESUMEN
Porous metal-organic frameworks (MOFs) are interesting materials owing to their interesting structural features and their many useful properties and applications. In particular, the structural features are greatly important to optimize the MOFs' porosities and so properties. Indeed, the MOFs' well-developed micropore and high surface area are the most important structural features, and as such, many practical applications of MOFs originate from these structural features. We herein demonstrate a strategy for improving the crystallinity of MOFs, and so increasing the porosity and surface area of poorly crystalline MOFs by making them in core-shell-type hybrids through the induced growth on the well-crystalline template. Although poorly crystalline versions of MOFs generate naturally in the absence of the well-crystalline template, well-crystalline versions of MOFs produce inductively in the presence of the well-crystalline template. In addition, the crystallinity enhancement of MOFs brings together the improvement in their porosities and surface areas. The surface areas and pore volumes of the well-crystalline versions of MOFs produced through the induced growth on the template are calculated based on this study, indicating that MOF surface areas increase by up to 7 times compared to the poorly crystalline versions.
RESUMEN
The growth of one metal-organic framework (MOF) on another MOF for constructing a heterocompositional hybrid MOF is an interesting research topic because of the curiosity regarding the occurrence of this phenomenon and the value of hybrid MOFs as multifunctional materials or routes for fine-tuning MOF properties. In particular, the anisotropic growth of MOF on MOF is fascinating for the development of MOFs possessing atypical shapes and heterostructures or abnormal properties. Herein, we clarify the understanding of growth behavior of a secondary MOF on an initial MOF template, such as isotropic or anisotropic ways associated with their cell parameters. The isotropic growth of MIL-68-Br on the MIL-68 template results in the formation of core-shell-type MIL-68@MIL-68-Br. However, the unique anisotropic growth of a secondary MOF (MOF-NDC) on the MIL-68 template results in semitubular particles, and structural features of this unknown secondary MOF are successfully speculated for the first time on the basis of its unique growth behavior and morphological characteristics. Finally, the validation of this structural speculation is verified by the powder X-ray diffraction and the selected area electron diffraction studies. The results suggests that the growth behavior and morphological features of MOFs should be considered to be important factors for understanding the MOFs' structures.
RESUMEN
The controlled formation of metal-organic frameworks (MOFs) or coordination polymers (CPs) with suitable components and structural features is one of the most important themes in MOF research. In particular, the reliable preparation of hybrid MOFs containing more than two different kinds of metal ions or organic linkers and a comprehensive understanding of the structural flexibility of MOFs are the central issues for the production of MOFs with the desired properties. We report the synthesis of micro-sized hybrid MOF particles [also known as coordination polymer particles (CPPs)] containing two or three kinds of metal ions in each particle: {FexMyM'1-x-y}-MIL-88B (MIL stands for Materials of Institut Lavoisier, M and M' = Ga, Co, or Mn). Scanning electron microscopy images revealed the formation of well-defined uniform micro-sized hexagonal rods, and energy-dispersive X-ray spectroscopy and elemental mapping images verified the simultaneous incorporation of two or three kinds of metal ions within the CPPs. Interestingly, the structural features of CPPs made from MIL-88B were controlled by altering the anions involved in the structure. Incorporating large acetylacetonate anions within the structure resulted in the closed MIL-88B structure with a small cell volume. However, the open MIL-88B structure with a large cell volume was obtained when small chloride anions were incorporated. The intermediate semi-open MIL-88B structure was also prepared using nitrate anions. Three different structural forms of MIL-88B were verified by powder X-ray diffraction, whole pattern fitting, and thermogravimetric analysis.