Fine-Tuning of the Pore Aperture and Framework Flexibility of Mixed-Metal (Zn/Co) Zeolitic Imidazolate Framework-8: An In Situ Positron Annihilation Lifetime Spectroscopy Study under CO₂ Gas Pressure

The mixed-metal (Zn/Co) strategy has been used to enhance the gas separation selectivity of zeolitic imidazolate framework-8 (ZIF-8)-based membranes. The enhancement in selectivity has been attributed to possible modifications in the grain boundary structure, pore architecture, and flexibility of the frameworks. In the present study, we used in situ positron annihilation lifetime spectroscopy (PALS) under varying CO₂ pressure to investigate the tuning of the pore architecture and framework flexibility of mixed-metal (Zn/Co) ZIF-8 frameworks with varying Co contents. The random distribution of Zn and Co metal nodes within the highly crystalline frameworks having an SOD topology was established using electron microscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy. The inherent aperture as well as cavity size of the frameworks, and the pore interconnectivity to the outer surface, were observed to vary with the Co content in ZIF-8 due to the random distribution of Zn and Co metal nodes in the frameworks. The aperture size is reduced with the incorporation of an additional metal (Zn or Co) in ZIF-67 or ZIF-8, respectively. The aperture size remains the smallest for a lower Co content (∼0.20) in ZIF-8. The framework flexibility determined by in situ PALS measurements under CO₂ pressure continuously reduces with increasing Co content in ZIF-8. A smaller aperture size as well as low flexibility of ZIF-8 with a low Co content is seen to be directly correlated to a higher separation selectivity of membranes prepared with this mixed-metal composition.