Reversible Redox Activity in Multicomponent Metal-Organic Frameworks Constructed from Trinuclear Copper Pyrazolate
Binbin Tu1, Qingqing Pang1, Huoshu Xu1
1Department of Chemistry, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University , Shanghai 200433, P. R. China.
Journal of the American Chemical Society
|May 26, 2017
Summary
Researchers developed new metal-organic frameworks (MOFs) using a metalloligand strategy. These functionalized MOFs exhibit controlled inorganic component integration and enhanced catalytic activity for key chemical reactions.
Area of Science:
- Materials Science
- Inorganic Chemistry
- Catalysis
Background:
- Inorganic functionalization of metal-organic frameworks (MOFs) enhances their catalytic properties.
- Incorporating multiple distinct metals and modulating metal charges are key strategies for MOF functionalization.
Purpose of the Study:
- To construct novel multicomponent MOFs with controlled inorganic building blocks.
- To explore the role of 4-pyrazolecarboxylic acid (H2PyC) as a metalloligand precursor.
- To investigate the catalytic applications of the synthesized MOFs.
Main Methods:
- One-pot synthesis of four new MOFs using a trinuclear copper pyrazolate metalloligand.
- Utilized 4-pyrazolecarboxylic acid (H2PyC) to direct the separation of Cu and Zn based on binding affinities.
- Incorporated secondary organic linkers (1,4-benzenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid) for complex MOF construction.
Main Results:
- Successfully synthesized four new multicomponent MOFs with distinct topologies (tub and tap).
- Demonstrated reversible redox transformations between Cu(I) and Cu(II) states without structural changes.
- Achieved significant catalytic activity in CO oxidation, aromatic alcohol oxidation, and H2O2 decomposition.
Conclusions:
- The metalloligand strategy enables precise programming of multiple inorganic components into MOFs.
- Modulating the electronic structures of inorganic units within MOFs offers a high degree of control.
- These functionalized MOFs show promise for advanced catalytic applications.
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