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Electrochemical Synthesis of Some Archetypical Zn²⁺, Cu²⁺, and Al³⁺ Metal Organic Frameworks
Summary:
The authors from Delft University of Technology developed multiple archetypical MOFs (HKUST-1, ZIF-8, MIL series) via electrochemical synthesis, achieving efficient preparation with mild conditions and tunable properties in adsorption/catalysis fields.
Background:
1. To address the issues of high temperature, extreme pH, and long time in conventional MOF synthesis, previous researchers proposed sonochemical and mechanochemical methods, but they lacked universality and continuity.
2. The authors proposed an electrochemical synthesis strategy using anodic dissolution to supply metal ions, realizing rapid preparation of diverse MOFs with high Faraday efficiency and controlled morphology.
Research Content:
1.Synthesis: The authors synthesized MOFs via electrochemical anodic dissolution, using corresponding metal plates as electrodes, organic linkers (BTC, MeIM, BDC, etc.), and electrolytes (MTBS, KCl), with adjustable solvent ratio, temperature, and current.
2.Characterizations:
1) BET: HKUST-1 up to 1553 m²/g, ZIF-8 up to 1695 m²/g, MIL-53(Al) up to 1243 m²/g; pore volume 0.163–1.242 cm³/g.
2) SEM/AFM: HKUST-1 (hundreds of nm–several μm), ZIF-8 (<1 μm), NH₂-MIL-53(Al) (<100 nm).
3) Electrochemical tests: Conductivity 0.092–12.9 mS/cm, Faraday efficiency up to 81%.
3.Application: The materials show potential in adsorption, catalysis, and chromatography; chiral MOFs enable effective enantioseparation.
4.Mechanism: Anodic dissolution generates reactive metal ions, and the balance of thermodynamics and diffusion controls MOF formation; rapid kinetics induce grain boundaries, suppressing MIL-53’s breathing effect.
Outlook:
This research establishes a universal, green electrochemical MOF synthesis method, breaking traditional process limitations and laying a foundation for industrial application and performance regulation of MOFs.
Electrochemical Synthesis of Some Archetypical Zn²⁺, Cu²⁺, and Al³⁺ Metal Organic Frameworks
Authors: Alberto Martinez Joaristi, Jana Juan-Alcaniz, Pablo Serra-Crespo, Freek Kapteijn, Jorge Gascon
DOI: 10.1021/cg300552w
Link: https://pubs.acs.org/doi/10.1021/cg300552w
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