Improved CO₂ Capture from Flue Gas by Basic Sites, Charge Gradients, and Missing Linker Defects on Nickel Face Cubic Centered MOFs

The adsorptive properties of the isoreticular series [Ni₈(OH)₄(H₂O)₂(BDP_X)₆] (H₂BDP_X = 1,4‐bis(pyrazol‐4‐yl)benzene‐4‐X with X = H (1), OH (2), NH₂ (3)) can be enhanced by postsynthetic treatment with an excess of KOH in ethanol. In the case of X = H, NH₂, this treatment leads to partial removal of the organic linkers, deprotonation of coordinated water molecules and introduction of extraframework cations, giving rise to materials of K[Ni₈(OH)₅(EtO)‐(H₂O)₂(BDP_X)_5.5] (1@KOH, 3@KOH) formulation, in which the original framework topology is maintained. By contrast, the same treatment with KOH in the [Ni₈(OH)₄(H₂O)₂(BDP_OH)₆] (2) system, enclosing the more acidic phenol residues, leads to a new material containing a larger fraction of missing linker defects and extra‐framework cations as well as phenolate residues, giving rise to the material K₃[Ni₈(OH)₃(EtO)(H₂O)₆(BDP_O)₅] (2@KOH), which also conserves the original face cubic centered (fcu) topology. It is noteworthy that the introduction of missing linker defects leads to a higher accessible pore volume with a concomitant increased adsorption capacity. Moreover, the creation of coordinatively unsaturated metal centers, charge gradients, and phenolate nucleophilic sites in 2@KOH gives rise to a boosting of CO₂ capture features with increased adsorption heat and adsorption capacity, as proven by the measurement of pulse gas chromatography and breakthrough curve measurements of simulated flue gas.