A Robust Sulfonate-Based Metal–Organic Framework with Permanent Porosity for Efficient CO2 Capture and Conversion

We report a rare example of a sulfonate-based metal–organic framework (MOF) possessing a prototypical primitive-cubic topology, constructed with Jahn–Teller distorted Cu­(II) centers and a mixed-linker (organosulfonate and N-donor) system. The inherent highly polar, permanent porosity contributes to the highest reported CO2 sorption properties to date among organosulfonate-based MOFs, outperforming the benchmark carboxylate MOF counterpart. Importantly, density functional theory calculations confirm that the CO2–sulfonate interaction plays an important role in CO2 capture. Indeed, the hydrothermal product demonstrates high robustness over a wide pH range as well as aqueous boiling conditions, overcoming the moisture sensitivity of conventional Cu2 paddlewheel-based MOFs. In addition, bulk synthesis of this material has been successfully achieved on a gram scale (>1 g) in a single batch with a high yield. Combining the high CO2 affinity and a robust nature, this sulfonate porous material is also an efficient, recyclable heterogeneous catalyst for CO2 fixation to form cyclic carbonates under ambient conditions.