Synthesis of Two-Dimensional Metal-Organic Frameworks and their Alloys

Metal-organic frameworks have made a feature in the cutting-edge technology with a wide variety of applications because they are the new material candidate as adsorbent or membrane with high surface area, various pore sizes, and highly tunable framework functionality properties. The emergence of two-dimensional (2D) metal-organic frameworks has surged an outburst of intense research to understand the feasible synthesis and exciting material properties of these class of materials. Despite their potential, studies to date show that it is extremely challenging to synthesize and manufacture 2D MOF at large scales with ultimate control over crystallinity and thickness.

The field of research to date has produced various synthesis routes which can further be used to design 2D materials with a range of organic ligands and metal linkers. This thesis seeks to extend these design rules to demonstrate the competitive growth of two- dimensional (2D) metal-organic frameworks(MOF) and their alloys to predict which ligands and metals can be combined, study the intercalation of Bromine in these frameworks and their alloys which leads to the discovery of reduced band gap in the layered MOF alloy.

In this study it has been shown that the key factor in achieving layered 2D MOFs and it relies on the use of carefully engineered ligands to terminate the out-of-plane sites on metal clusters thereby eliminating strong interlayer hydrogen bond formation.

The major contribution of pyridine is to replace interlayer hydrogen bonding or other weak chemical bonds. Overall results establish an entirely new synthesis method for producing highly crystalline and scalable 2D MOFs and their alloys. Bromine intercalation merits future studies on band gap engineering in these layered materials.