High Efficient Liquid‐Phase Breakthrough of Hexane Isomers Via a Robust Heteroporous TiCo‐MOF

ABSTRACT The separation of hexane isomers remains one of the most demanding challenges in petrochemical refining due to their nearly identical physicochemical properties. Conventional vapor‐phase adsorption or liquid‐phase extraction using metal–organic frameworks (MOFs) is constrained by low throughput and sluggish kinetics. Here we introduce a heteroporous titanium–cobalt MOF, TiCo‐TPT , that harmonizes diffusion kinetics and thermodynamic selectivity through a dual‐cage framework design. The robust Ti─O─Co network endows exceptional chemical and thermal stability, while the coexistence of narrow and wide cages enables both rapid molecular transport and size‐selective adsorption. TiCo‐TPT exhibits record adsorption capacities for n ‐hexane (4.77 mmol/g) and 3‐methylpentane (4.47 mmol/g), outperforming all previously reported rigid MOFs capable of discriminating between mono‐ and dibranched isomers. More importantly, TiCo‐TPT achieves continuous‐flow liquid‐phase separation of hexane isomers under ambient conditions, yielding high‐purity 2,2‐dimethylbutane with >99.9% purity and significantly enhanced octane number. This work establishes a design paradigm for heteroporous MOFs, demonstrating how multiscale pore environments can overcome the kinetic–thermodynamic trade‐off that has long limited molecular separations, thereby opening new avenues for energy‐efficient hydrocarbon upgrading.