Theoretical investigation of CO(2) capture in the MIL-88 series: effects of organic linker modification

CO(2) capture is a crucial strategy to mitigate global warming and protect a sustainable environment. Metal–organic frameworks with large surface area, high flexibility, and reversible adsorption and desorption of gases are good candidates for CO(2) capture. Among the synthesized metal–organic frameworks, the MIL-88 series has attracted our attention due to their excellent stability. However, a systematic investigation of CO(2) capture in the MIL-88 series with different organic linkers is not available. Therefore, we clarified the topic via two sections: (1) elucidate physical insights into the CO(2)@MIL-88 interaction by van der Waals-dispersion correction density functional theory calculations, and (2) quantitatively study the CO(2) capture capacity by grand canonical Monte Carlo simulations. We found that the 1π(g), 2σ(u)/1π(u), and 2σ(g) peaks of the CO(2) molecule and the C and O p orbitals of the MIL-88 series are the predominant contributors to the CO(2)@MIL-88 interaction. The MIL-88 series, i.e., MIL-88A, B, C, and D, has the same metal oxide node but different organic linkers: fumarate (MIL-88A), 1,4-benzene-dicarboxylate (MIL-88B), 2,6-naphthalene-dicarboxylate (MIL-88C), and 4,4′-biphenyl-dicarboxylate (MIL-88D). The results exhibited that fumarate should be the best replacement for both the gravimetric and volumetric CO(2) uptakes. We also pointed out a proportional relationship between the capture capacities with electronic properties and other parameters.