Pillar-Layered Metal–Organic Frameworks Based on a Hexaprismane [Co6(μ3-OH)6] Cluster: Structural Modulation and Catalytic Performance in Aerobic Oxidation Reaction

Embedding a functional metal-oxo cluster within the matrix of metal–organic frameworks (MOFs) is a feasible approach for the development of advanced porous materials. Herein, three isoreticular pillar-layered MOFs (Co6-MOF-1–3) based on a unique [Co6(μ3–OH)6] cluster were designed, synthesized, and structurally characterized. For these Co6-MOFs, tuning of the framework backbone was facilitated due to the existence of second ligands, which results in adjustable apertures (8.8 to 13.4 Å) and high Brunauer–Emmett–Teller surfaces (1896–2401 m2 g–1). As the [Co6(μ3–OH)6] cluster has variable valences, these MOFs were then utilized as heterogeneous catalysts for the selective oxidation of styrene and benzyl alcohol, showing high conversion (>90%) and good selectivity. The selectivity of styrene to styrene oxide surpassed 80% and that of benzyl alcohol to benzaldehyde was up to 98%. The calculated TOF values show that the increase of reaction rate is positively correlated with the enlargement of pore sizes in these MOFs. Further, a stability test and cycling experiment proved that these Co6-MOFs have well-observed stability and recyclability.