MOFs can be synthesized using a variety of methods that involve solvothermal, hydrothermal, mechanochemical, and sonochemical strategies. Drawbacks exist for each of these methods, however, including the need for high temperatures and forcing conditions, low yields, phase impurity, need for expensive starting materials, and long synthesis times. The synthesis of MOFs based on high-valent metal cations is particularly challenging and typically require the use of harsh acids and long reaction times to afford crystalline solids. By contrast, MOF synthetic strategies that leverage electrochemistry provide many advantages for the facile synthesis of MOF materials and can enable the use of inexpensive, air-stable starting materials and can produce higher quality crystalline materials. For example, titanium MOFs, which have only been realized recently, represent a class of materials that are compatible with electrochemical methods given the redox-active nature of this metal cation. In this work, we show that a variety of titanium-based MOFs can be synthesized via electrochemical reduction of TiCl4 to Ti3+ in solution. In particular, the electrochemically mediated synthesis of TiIII-MIL-101 from TiCl4 and dicarboxylic acids produces materials that are of superior quality to analogous samples prepared via conventional routes from starting exogenous TiCl3. The electrochemically mediated synthetic strategy has also been adapted for the first reported route to TiIII-MIL-100 and to high-quality samples of Ti3+ based MOFs with expended pore structures and surface areas that approach 6000 m2/g.

Electrochemically mediated synthesis of titanium(III)-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.