Electrochemistry of Metal-Organic Frameworks

The singular porosity of MOFs allows for a significant redox conductivity that, in contrast with zeolites and other microporous aluminosilicates, can involve all units of the material. This is the case of Cu-- and ZrF -based MOFs with terephtalic acid in these materials, both metal centers and organic units are potentially electroactive in contact with suitable electrolytes. 

The relevant properties of MOFs have prompted their use for catalysis, gas storage, and separation (Janiak, 2003 Chun et al., 2005 Kaye and Long, 2005 Rowsell and Yaghi, 2006), as well as for fuel cells (Mueller et al., 2006), Li-based batteries (Li et al., 2006 Ferey et al., 2007), and electrocatalysis (Wang et al., 2008). Conversely, MOFs can be synthesized electrochemically, as described by Mueller et al. (2006). MOFs are indirectly related with other electrochemical applications acting as a template for the synthesis of porous carbon to be applied as double-layer electrochemical capacitor (Liu et al., 2008). 

In addition, the involvement of certain transition metal ions makes it possible for us to study electrochemical processes resulting in the formation of metal particles or deposits from MOFs. This is of interest with regard to recent developments in oscillatory 

FIGURE 5.1 Schematic representation of the ab plane of the CuibpyX 11/))2(BF4)2(bpy) MOF crystal. (Adapted from Jiang et al., 2008. 7. Catal. 257 390-395, with permission.) 

In this chapter, the electrochemistry of MOFs will be studied with particular attention to their peculiarities with respect to other microporous materials. Two general types of electrochemical processes will be considered those involving an ion insertion-driven electrochemical process that, in principle, does not demand sharp structural changes and those involving formation of metal particles, thus requiring the formation of a new phase. The electrochemistry of solid materials with miscibility gaps has been theoretically treated by Lovric et al. (2000). 

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Domenech, A., Garcia, H., Domenech, M.T., andLlahres-i-Xamena, F. 2007d. Electrochemistry of metal-organic frameworks A description from the voltammetry of microparticles approach. Journal of Physical Chemistry C 111, 13701-13711. 

Dr. Li s ciurent work focuses on electrochemistry and catalysis. Her research interests include anode materials on lithium batteries, flow batteries, and MOFs (metal-organic frameworks) for catalytic applications. She has published more than 20 articles in various peer-reviewed journals. Dr. Li is a member of the Electrochemical Society and American Institute of Chemical Engineers. She is also accredited by Engineers Australia as a chartered professional engineer (CPEng), and Institute of Materials, Mineral and Mining as a chartered scientist (CSci). 

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