Electrochemical methods for the synthesis of metal-organic frameworks (MOFs) have been widely investigated but have involved indirect routes, where either an anode is dissolved to form a material or a redox event triggers ligand deprotonation needed to drive MOF formation. These methods are limited in scope as the former relies on the presence of an anode of the target metal ion, and the latter on the compatibility of the metal/ligand solution with the pro-base that is subsequently oxidized or reduced. Further, most electrochemical MOF syntheses display limited utility for the controlled modification of an electrode surface. In response to these limitations, we have developed facile electrochemical syntheses of Fe-MIL-101 and Fe-MIL-101-NH<sub>2</sub> via controlled potential electrolysis methods using ITO electrodes. Samples of Fe-MIL-101 materials can be easily generated in this manner in as little as 30 minutes at room temperature, and display appreciable surface areas with particle size and crystallinity that are as good or better when compared to those prepared using the forcing and less convenient conditions (110 °C for 20 hours) solvothermal method that have historically be utilized for MOF syntheses. Characterization of the electrosynthesized MOFs via gas adsorption/desorption, powder X-ray diffraction and a variety of spectroscopic and imaging techniques will also be presented. Lastly, electrochemical growth of Fe-MIL-101 materials directly on the surface of properly functionalized ITO electrodes offers many additional advantages over traditional MOF syntheses and is highly amenable to patterning techniques. Accordingly, our ability to surface functionalize and pattern electrode supports with electrochemically grown MOFs will also be discussed.

Room-temperature electrosynthesis and controlled surface growth of Fe-MIL-101 based metal-organic frameworks

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.