Novel Zeolite-5A@MOF-74 Composite Adsorbents with Core-Shell Structure for H₂ Purification

Hydrogen is considered as one of the most important clean and renewable energy sources for a sustainable energy future. However, its efficient and cost-effective purification still remains challenging. In this work, we report the development of novel zeolite@metal-organic framework (MOF) composites comprised of MOF-74 and zeolite-5A with core-shell structure for efficient purification of H₂. The composites were synthesized hydrothermally through the addition of zeolite particles with and without carboxyl functional groups to the MOF synthesis solution. The zeolite/MOF weight ratio was varied systematically to find the optimum composition based on the adsorption performance. The formation of zeolite@MOF composites was confirmed by various characterization techniques. Single-component adsorption isotherms of CO₂, CO, CH₄, N₂, and H₂ over composites were measured at 25 °C to determine their equilibrium adsorption capacity. It was found that the zeolite-5A@MOF-74 with weight ratio of 5:95 exhibited a similar morphology to that of pristine MOF-74, but with higher surface area and total pore volume. Moreover, this composite showed 20-30% increase in CO₂, CO, CH₄, and N₂ uptake than the bare MOF, which could be attributed to the formation of new mesopores at the MOF-zeolite interface. The estimated selectivity values for CO₂/H₂, CO/H₂, CH₄/H₂, and N₂/H₂ were higher than those of the zeolite and/or MOF. Our results also indicated that surface modification of zeolite prior to composite formation does not enhance the adsorption capacities of the composites. Overall, the findings of this study suggest that the zeolite-5A@MOF-74 composites with core-shell structure are promising candidates for industrial H₂ purification processes.