Entrapment
of radioactive inert gases, Xe and Kr, generated from
the spent nuclear fuel reprocessing or nuclear accidents is one of
the challenging issues in successful implementation of nuclear energy
as an alternative and sustainable energy. Metal–organic frameworks
(MOFs) gained immense research interest for adsorption and separation
of various important gases because of their fine tunable pore chemistry
and topology. Here, we investigated a series of MOFs, MFM-300(M) (M
= Al, In, Ga, Sc, V, Cr, and Fe), for selective entrapment of Xe over
Kr using both density functional theory (DFT) and grand canonical
Monte Carlo (GCMC) simulation techniques. The calculated structural
parameters of all of the considered MOFs are consistent with the reported
experimental results. Different textural properties such as pore-limiting
diameter, largest cavity diameter, surface area, void fraction, etc.,
are measured. From the binding energies calculated through DFT calculations
at different loading capacities, adsorption of Xe is found to be stronger
as compared to adsorption of Kr, and the binding energy is found to
increase with loading. GCMC simulations indicate that the considered
MOFs have significantly higher uptake capacities and are selective
for Xe over Kr. Energy decomposition analysis indicates a strong adsorbate–adsorbate
interaction at higher loading, which is more significant for Xe as
compared to Kr. The strong adsorbate–adsorbate interactions
are driven by the confinement effects of the one-dimensional cylindrical
channels present in MFM-300(M). Among the series of MOFs considered,
MFM-300(In) is shown to have the best selectivity for Xe over Kr.
Our computational studies can provide valuable inputs for exploring
MFM-300(M) MOFs for selective separation and storage of noble gases.