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

Abstract

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.