Bi‐Microporous Metal–Organic Frameworks with Cubane [M4(OH)4] (M=Ni, Co) Clusters and Pore‐Space Partition for Electrocatalytic Methanol Oxidation Reaction. Issue 35 (5th August 2019)

• Record Type: Journal Article
• Authors: Wu, Ya‐Pan; Tian, Jun‐Wu; Liu, Shan; Li, Bo; Zhao, Jun; Ma, Lu‐Fang; Li, Dong‐Sheng; Lan, Ya‐Qian; Bu, Xianhui
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 35(2019)
• Page Start: 12185
• Page End: 12189
• Publication Date: 2019-08-05
• Subjects: cluster compounds -- electrocatalysis -- methanol oxidation reaction -- metal–organic frameworks; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201907136
• Languages: English
• ISSNs: 1433-7851

Abstract

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 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. Abstract : 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).