Bi-Microporous Metal-Organic Frameworks with Cubane [M4(OH)4] (M=Ni, Co) Clusters and Pore-Space Partition for Electrocatalytic Methanol Oxidation Reaction

Embedding cubane [M-4(OH)(4)] (M=Ni, Co) clusters within the matrix of metal-organic frameworks (MOFs) is a strategy to develop materials with unprecedented synergistic properties. Herein, a new material type based on the pore-space partition of the cubic primitive minimal-surface net (MOF-14-type) has been realized. CTGU-15 made from the [Ni-4(OH)(4)] cluster not only has very high BET surface area (3537 m(2) g(-1)), but also exhibits bi-microporous features with well-defined micropores at 0.86 nm and 1.51 nm. Furthermore, CTGU-15 is stable even under high pH (0.1 m KOH), making it well suited for methanol oxidation in basic medium. The optimal hybrid catalyst KB&CTGU-15 (1:2) made from ketjen black (KB) and CTGU-15 exhibits an outstanding performance with a high mass specific peak current of 527 mA mg(-1) and excellent peak current density (29.8 mA cm(-2)) at low potential (0.6 V). The isostructural cobalt structure (CTGU-16) has also been synthesized, further expanding the application potential of this material type.