Regulating C₂H₂/CO₂ adsorption selectivity by electronic-state manipulation of iron in metal-organic frameworks

The separation of C₂H₂ from C₂H₂/CO₂ mixture is of great importance, yet highly challenging in the petrochemical industry due to their similar physicochemical properties. While open-metal sites (OMSs) in metal-organic frameworks (MOFs) are known to possess high affinity toward C₂H₂, its selective adsorption performance regulated by the electronic state of the same OMSs remains unexplored. Here, we report a metal electronic-state manipulation approach to construct a pair of isostructural Fe-MOFs, namely LIFM-26(Fe[II]/Fe[III]) and LIFM-27(Fe[III]) with different Fe[II] or Fe[III] oxidation states on the Fe centers, which display mixed-valent Fe[II]/Fe[III] centers in the former and sole Fe[III] centers in the latter. Remarkably, LIFM-26(Fe[II]/Fe[III]) shows significantly enhanced C₂H₂ uptake capacity than LIFM-27(Fe[III]), attested by adsorption isotherms and IAST calculations, as well as simulated and experimental breakthrough experiments. Furthermore, in situ infrared (IR) and molecular calculations unveil that the presence of Fe[II] in LIFM-26(Fe[II]/Fe[III]) results in stronger Fe[II]–C₂H₂ interactions than Fe[III]–C₂H₂, which plays a key role in the C₂H₂/CO₂ separation.