Calcium-Based Metal–Organic Framework for Simultaneous Capture of Trace Propyne and Propadiene from Propylene

The simultaneous capture of trace propyne and propadiene from propylene is one of the important but energy demanding industrial processes because of their similar physicochemical properties as well as the ultralow concentration in the mixtures. Herein, a highly stable Ca-based MOF, constructed from an inexpensive precursor (CaCO3) and rigid squaric acid, is capable of preferentially capturing trace propyne and propadiene with record-high uptake capacities of 2.44 and 2.64 mmol/g at pressures as low as 5 mbar, respectively. Direct multicomponent breakthrough experiments confirm that Ca-based MOF exhibits an excellent performance for simultaneous removal of trace propyne and propadiene from propylene. DFT simulation and in situ single-crystal X-ray diffraction of propadiene- and propyne-adsorbed Ca-based MOFs reveal that the strong affinity of the framework toward two species is ascribed to the multiple types of cooperative binding including π–π stacking and C–H···O interactions. The calcium squarate framework sets a new benchmark for adsorptive purification of propylene, showing great potential in the practical application.