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

• Published in: Angewandte Chemie International Edition Vol. 58; no. 35; pp. 12185 - 12189
• Main Authors: Wu, Ya‐Pan, Tian, Jun‐Wu, Liu, Shan, Li, Bo, Zhao, Jun, Ma, Lu‐Fang, Li, Dong‐Sheng, Lan, Ya‐Qian, Bu, Xianhui
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 26.08.2019
• Edition: International ed. in English
• Subjects: Catalysts; cluster compounds; Clusters; Cobalt; Cubane; electrocatalysis; Embedding; Metal-organic frameworks; Methanol; methanol oxidation reaction; Nickel; Oxidation; Partitions; cluster compounds; electrocatalysis; metal-organic frameworks; methanol oxidation reaction
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201907136

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. Split pores: A new 3D microporous metal–organic framework containing cubane [Ni4(OH)4] clusters can serve as an electrocatalyst for the methanol oxidation reaction (MOR). The optimal hybrid material shows impressive electrocatalytic performance including a high mass specific peak current of 527 mA mg−1 and excellent peak current density (29.8 mA cm−2) at a very low potential (0.6 V).