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Metal-organic frameworks post-synthetically modified with ferrocenyl groups: framework effects on redox processes and
Jonathan E Halls1, Alberto Hernán-Gómez, Andrew D Burrows
1Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK.
Dalton Transactions (Cambridge, England : 2003)
|July 27, 2011
Summary
Ferrocene-functionalized metal-organic frameworks (MOFs) show stable redox behavior in mild organic solvents but degrade in aqueous solutions due to pH-dependent framework dissolution. This impacts their potential for electrochemical applications.
Area of Science:
- Materials Science
- Electrochemistry
- Nanotechnology
Background:
- Metal-organic frameworks (MOFs) offer tunable structures for various applications.
- Incorporating redox-active groups like ferrocene can enable electrochemical functionalities in MOFs.
- Understanding MOF stability and redox behavior in different media is crucial for practical use.
Purpose of the Study:
- To synthesize and electrochemically investigate MOF materials functionalized with ferrocene.
- To determine the optimal conditions for stable ferrocene redox activity within MOFs.
- To elucidate the redox mechanisms and stability of these MOFs in aqueous and non-aqueous environments.
Main Methods:
- Synthesis of zinc(II) and aluminium(III) dicarboxylate MOFs via post-synthetic modification.
- Functionalization with ferrocene redox groups.
- Electrochemical investigation using cyclic voltammetry in aqueous and dichloroethane media.
Main Results:
- Ferrocene oxidation was observed in all synthesized MOFs.
- Chemically reversible and stable ferrocene oxidation occurred in a mild dichloroethane solvent, indicating surface-confined electron transfer.
- In aqueous media, MOFs exhibited pH-dependent, irreversible redox processes leading to framework disintegration, attributed to hydroxide-driven dissolution.
Conclusions:
- Ferrocene-functionalized MOFs demonstrate stable electrochemical activity in specific non-aqueous environments.
- Aqueous environments promote framework instability and irreversible redox behavior, limiting their use.
- The study highlights the critical role of solvent and pH in the electrochemical performance and stability of functionalized MOFs.
