Pore tuning in multivariate Zr/Ce-MOFs utilizing C4 natural linkers through room-temperature synthesis for customized adsorptive separation of gases and vapours

Abstract

Multivariate metal–organic frameworks (MTV-MOFs), inspired by the sequence-controlled organization of natural systems, offer a promising platform for tailoring functional properties through precise structural modularity. However, conventional synthetic approaches for MTV-MOFs—primarily relying on thermal reactions or limited room-temperature (RT) protocols—face challenges in achieving optimal functional diversity and application-specific performance. Here, we report a green, RT synthesis strategy for MTV-MOF-801 derivatives incorporating mixed fumarate/aspartate linkers. Systematic investigations have revealed that pore architecture can be finely tuned by modulating the fumarate/aspartate ratio, enabling dynamic structural adaptability to external stimuli. Furthermore, replacing Zr₆ clusters with Ce₆ clusters in the MOF-801 framework markedly enhances its capacity to integrate flexible aspartate ligands while improving the separation efficiency for CO₂/N₂ mixtures and C₆ isomers. These results underscore the synergistic role of linker composition and metal-node substitution in property optimization. The RT-driven methodology demonstrated here provides a sustainable and versatile pathway for designing advanced MTV-MOFs with enhanced functionality for gas separation and beyond.