Augmenting the adsorption mechanisms in metal-organic frameworks via in Silico methods
Metal-organic frameworks (MOFs), intricate structures composed of organic linkers and metal nodes, exhibit remarkable versatility with applications ranging from gas adsorption and separation to drug and energy storage, water absorption, and catalysis. Despite their broad utility, a comprehensive...
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| Format: | Thesis |
| Language: | English |
| Published: |
2023
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| Subjects: | |
| Online Access: | http://psasir.upm.edu.my/id/eprint/119046/ http://psasir.upm.edu.my/id/eprint/119046/1/119046.pdf |
| Summary: | Metal-organic frameworks (MOFs), intricate structures composed of organic linkers and
metal nodes, exhibit remarkable versatility with applications ranging from gas adsorption
and separation to drug and energy storage, water absorption, and catalysis. Despite their
broad utility, a comprehensive understanding of the factors influencing adsorption within
MOFs is essential for optimizing their potential as adsorbents. This study systematically
categorizes and investigates various factors through computer simulations, shedding
light on their nuanced effects.
The first focus centers on the functionalization of IRMOF-74-III with amine groups, a
critical aspect of enhancing drug adsorption. The exploration delves into the impact of
different numbers and positions of amine functional groups on the MOF's behavior,
utilizing density functional theory (DFT) and molecular docking. As the number of
amine group increases, the MOF's pore polar surface area expands, but a reduction in the
energy gap between the HOMO and LUMO orbitals is observed. Electrostatic potential
contours reveal distinct pockets on the amine-functionalized IRMOF-74-III's pore wall,
which fenbufen@MOF showing the most stable drug@MOF complex. The study
emphasizes the crucial role of unsaturated magnesium sites in frameworks and specific
functional groups on drugs for interactions and charge transfer. The second exploration
addresses MOFs' ability to selectively adsorb isomers, as exemplified by MIL-53(Al)
MOF's adsorption of xylene isomers. The introduction of non-polar functional groups on
the organic linker was proposed for enhanced adsorption. Computational analysis of
different configurations of dimethyl-functionalized phenyl rings reveals meta-dimethyl-
MIL-53(Al) (MDM) as an optimal structure for xylene adsorption, demonstrating
superior adsorptive separation of ortho- over meta- and para-xylene. The third study
introduces an innovative alternative to MOF functionalization by directly replacing the
organic linker with a structurally similar compound, preserving the framework topology.
Using computer simulations, the impact of replacing the organic linker in HKUST-1
MOF with borazine is analyzed. Borazine-based HKUST-1(Cu) (hB-HKUST-1(Cu))
exhibits a significant improvement in CO2 adsorption compared to the conventional |
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