CO 2 Capture in Aluminum‐Based Metal‐organic Frameworks: A Theoretical Study

Based on density functional theory calculations with van der Waals corrected functional, we study the in‐ teractions between CO 2 and two novel Aluminum‐Based metal‐organic frameworks (MOFs) with two kinds of organic linkers: 2, 5‐thiophenedicarboxylic acid (TDC), 2, 5‐furandicarboxylic acid (FDC), named Al‐TDC and Al‐FDC. Our calculations show that CO 2 can interact with Al‐TDC and Al‐FDC MOFs via three kinds of interactions: (1) weak hydrogen bond interactions by an O CO2 with the elec‐ tron‐deficient H atom of the linker (thiophene ring and furan ring) or of the OH ligand; (2) Lewis‐base in‐ teraction by an O CO2 with the linker (thiophene ring and furan ring); (3) lone pair interaction between O CO2 and S atom of thioph ‐ ene ring or O atom of furan ring. We show that a judicious modification of the organic linker increases the binding energy from −30.31∼−33.86 kcal/mol (FDC) to −33.98∼−38.92 kcal/mol (TDC). The results may provide useful information for the design of future CO 2 ‐philes MOFs.