Polar Group and Defect Engineering in a Metal–Organic Framework: Synergistic Promotion of Carbon Dioxide Sorption and Conversion

Abstract A sulfone‐functionalized metal–organic framework (MOF), USTC‐253, has been synthesized that exhibits a much higher CO 2 uptake capacity (168–182 %) than the corresponding unfurnished MOFs. The introduction of trifluoroacetic acid (TFA) during the synthesis of USTC‐253 affords defect‐containing USTC‐253‐TFA with exposed metal centers, which has an increased CO 2 uptake (167 %) compared to pristine USTC‐253. USTC‐253‐TFA exhibits a very high ideal adsorption solution theory selectivity ( S =75) to CO 2 over N 2 at 298 K. In addition, USTC‐253‐TFA demonstrates good catalytic activity and recyclability in the cycloaddition of CO 2 and epoxide at room temperature under 1 bar CO 2 pressure as a result of the presence of Lewis and Brønsted acid sites, which were evaluated by diffuse reflectance infrared Fourier transform spectroscopy with a CO probe molecule. We propose that the CO 2 adsorption capability has a positive correlation with the catalytic performance toward CO 2 conversion.