Metal-organic frameworks (MOFs) are a class of porous, crystalline materials constructed by extending the linkages between inorganic and organic molecular building blocks through strong bonds. Because of their high porosities, accessible interconnected pore structures, and designable backbones, MOFs have been used in applications ranging from as catalystsupports, membrane substrates, sensing layers, and casting templatesfor metalsThere are many methods that leverage the tunability of MOFs to introduce extraneous metals, or templating, including (i) metal addition on MOFs’ backbones; (ii) metal-ion exchange in MOFs; (iii) cation metathesis in MOFs; and (iv) growth or encapsulation of metal nanoparticles in MOFs’ pores.
Despite the significant efforts devoted to the reticular metalation in MOFs, there are still numerous challenges that need to be addressed. To name a few, in terms of anchoring individual metal atoms onto MOF’s building units, little is known about the local structures inside metaled MOF’s pores, especially for factors such as metal binding modes, oxidation states, and existing coordination formsWith regards to casting/encapsulating metal nanostructures in MOFs, the accurate control and fundamental understanding of the process have yet to be establishedAs for constructing interfaces between the metallated-MOF and substrate, well-designed synthetic routes need further investigations. The work presented in this thesis aims to answer these questions associated with the reticular metalation in MOFs, from the viewpoints of material synthesis, characterizations, as well as application aspects.
August 30, 2019
Gao, X. (2019). Reticular Metalation in Metal-Organic Frameworks for Nanocasting and Interface Construction. United States: University of California, Berkeley.