Core–Shell Zeolitic Imidazolate Frameworks for Enhanced Hydrogen Storage

Core–shell ZIF-8@ZIF-67- and ZIF-67@ZIF-8-based zeolitic imidazolate frameworks (ZIFs) were synthesized solvothermally using a seed-mediated methodology. Transmission electron microscopy–energy-dispersive X-ray spectrometry, line scan, elemental mapping, X-ray photoelectron spectroscopy, and inductively coupled plasma-atomic emission spectroscopy analyses were performed to confirm the formation of a core–shell structure with the controlled Co/Zn elemental composition of ∼0.50 for both the core–shell ZIFs. The synthesized core–shell ZIF-8@ZIF-67 and ZIF-67@ZIF-8 frameworks conferred enhanced H₂ (2.03 and 1.69 wt %) storage properties at 77 K and 1 bar, which are ca. 41 and 18%, respectively, higher than that of the parent ZIF-8. Notably, the distinctly remarkable H₂ storage properties shown by both the core–shell ZIFs over the bimetallic Co/Zn-ZIF and the physical mixture of ZIF-8 and ZIF-67 clearly evidenced their unique structural properties (confinement of porosity) and elemental heterogeneity due to the core–shell morphology of the outperforming core–shell ZIFs. Moreover, H₂ adsorption isotherm data of these frameworks are best fitted with the Langmuir model (R² ≥ 0.9999). Along with the remarkably enhanced H₂ storage capacities, the core–shell ZIFs also displayed an improved CO₂ capture behavior. Hence, we demonstrated here that the controlled structural features endorsed by the rationally designed porous materials may find high potential in H₂ storage applications.