Adsorption of Sulfur Dioxide in Cu(II)-Carboxylate Framework Materials: The Role of Ligand Functionalization and Open...

The development of efficient sorbent materials for sulfur dioxide (SO₂) is of key industrial interest. However, due to the corrosive nature of SO₂, conventional porous materials often exhibit poor reversibility and limited uptake toward SO₂ sorption. Here, we report high adsorption of SO₂ in a series of Cu(II)-carboxylate-based metal-organic framework materials. We describe the impact of ligand functionalization and open metal sites on the uptake and reversibility of SO₂ adsorption. Specifically, MFM-101 and MFM-190(F) show fully reversible SO₂ adsorption with remarkable capacities of 18.7 and 18.3 mmol g^-1, respectively, at 298 K and 1 bar; the former represents the highest reversible uptake of SO₂ under ambient conditions among all porous solids reported to date. In situ neutron powder diffraction and synchrotron infrared microspectroscopy enable the direct visualization of binding domains of adsorbed SO₂ molecules as well as host-guest binding dynamics. We have found that the combination of open Cu(II) sites and ligand functionalization, together with the size and geometry of metal-ligand cages, plays an integral role in the enhancement of SO₂ binding.