Adsorption of CO2 in metal organic frameworks of different metal centres: Grand Canonical Monte Carlo simulations compared to experiments
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A Grand Canonical Monte Carlo study has been performed in order to compare the different CO2 adsorption mechanisms between two members of the MIL-n family of hybrid metal-organic framework materials. The MIL-53 (Al) and MIL-47 (V) systems were considered. The results obtained confirm that there is a structural interchange between a large pore and narrow pore forms of MIL-53 (Al), not seen with the MIL-47 (V) material, which is a consequence of the presence of μ2-OH groups. The interactions between the CO2 molecules and these μ2 OH groups mainly govern the adsorption mechanism in this MIL-53 (Al) material. The subsequent breaking of these adsorption geometries after the adsorbate loading increases past the point where no more preferred adsorption sites are available, are proposed as key features of the breathing phenomenon. After this, any new adsorbates introduced into the MIL-53 (Al) large pore structure experience a homogeneous adsorption environment with no preferential adsorption sites in a similar way to what occurs in MIL-47 (V).
KeywordsCO2, adsorption Metal-organic frameworks Grand Canonical Monte Carlo Microcalorimetry Isotherm Differential adsorption enthalpy, adsorption mechanism, breathing effect
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