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 M₄(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 Ni₄(OH)₄] cluster not only has very high BET surface area (3537 m² 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.