Structural and Dynamic Analysis of Sulphur Dioxide Adsorption in a Series of Zirconium‐Based Metal–Organic Frameworks

We report reversible high capacity adsorption of SO(2) in robust Zr‐based metal–organic framework (MOF) materials. Zr‐bptc (H(4)bptc=biphenyl‐3,3′,5,5′‐tetracarboxylic acid) shows a high SO(2) uptake of 6.2 mmol g(−1) at 0.1 bar and 298 K, reflecting excellent capture capability and removal of SO(2) at low concentration (2500 ppm). Dynamic breakthrough experiments confirm that the introduction of amine, atomically‐dispersed Cu(II) or heteroatomic sulphur sites into the pores enhance the capture of SO(2) at low concentrations. The captured SO(2) can be converted quantitatively to a pharmaceutical intermediate, aryl N‐aminosulfonamide, thus converting waste to chemical values. In situ X‐ray diffraction, infrared micro‐spectroscopy and inelastic neutron scattering enable the visualisation of the binding domains of adsorbed SO(2) molecules and host–guest binding dynamics in these materials at the atomic level. Refinement of the pore environment plays a critical role in designing efficient sorbent materials.