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  • Title: Enhanced Gas Adsorption on Cu3(BTC)2 Metal-Organic Framework by Post-Synthetic Cation Exchange and Computational Analysis.
    Author: Veleta JM, Arrieta RA, Wu Y, Baeza MA, Castañeda K, Villagrán D.
    Journal: Langmuir; 2023 Jun 13; 39(23):8091-8099. PubMed ID: 37267477.
    Abstract:
    Increased gas adsorption in a series of post-synthetically modified metal-organic frameworks (MOFs) of the type HKUST-1 was achieved by the partial cation exchange process. Manipulation of post-synthetic conditions demonstrates high tunability in the site substitution and gas adsorption properties during the dynamic equilibrium process. In this work, post-synthetic modification of Cu3(BTC)2 is carried on by exposure to TM2+ solutions (TM = Mn, Fe, Co, Ni) at different time intervals. The crystal structure, composition, and morphology were studied by powder X-ray diffraction, Fourier-transform infrared spectroscopy, inductively coupled plasma optical emission spectroscopy, and scanning electron microscopy. Structural analysis supports the retention of the crystal structure and partial substitution of the Cu metal nodes within the framework. A linear increase in the transmetalation process is observed with Fe and Co with a maximum percentage of 39 and 18%, respectively. Conversely, relatively low cation exchange is observed with Mn having a maximum percentage of 2.40% and Ni with only 2.02%. Gas adsorption measurements and surface area analysis were determined for each species. Interestingly, (Cu/Mn)3(BTC)2 revealed the highest CO2 adsorption capacity of 5.47 mmol/g, compared to 3.08 mmol/g for Cu3(BTC)2. The overall increased gas adsorption can be attributed to the formation of defects in the crystal structure during the cation exchange process. These results demonstrate the outstanding potential of post-synthetic ion exchange as a general approach to fine-tuning the physical properties of existing MOF architectures.
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