| This dissertation describes the development of adenine-based biomolecular metal-organic frameworks (Bio-MOFs). Four specific topics are presented: 1) design of new bio-MOFs for CO2 capture; 2) preparation of core-shell bio-MOFs with enhanced properties; 3) development of new synthetic strategies for increasing bio-MOF porosity; and 4) exploration of new applications of mesoporous bio-MOFs.;Specifically, Chapter 2 reports the preparation of an isoreticular series of cobalt-adeninate bio-MOFs (bio-MOFs-11-14). The pores of bio-MOFs-11-14 are decorated with linear aliphatic pendant groups (acetate, propionate, butyrate, and valerate). The new materials exhibit higher CO2/N2 selectivity and greatly improved water stability. Based on the findings in Chapter 2, Chapter 3 describes the design of a core-shell material comprising a porous bio-MOF-11/14 mixed core and a less porous bio-MOF-14 shell. The resulting core-shell material successfully combined the merits of bio-MOF-11 and 14 and exhibits higher CO2 capacity, the ability to exclude N2, and improved water stability. Chapter 4 demonstrates the use of in situ ligand exchange as a synthetic strategy for the preparation of an isoreticular series of zinc-adeninate bio-MOFs (bio-MOFs-100-103) exhibiting exclusive mesoporosity. Following the work in Chapter 4, Chapter 5 presents the use of these exclusively mesoporous bio-MOFs for the separation of thiolated gold nanoclusters. This is the first demonstration of large species separation using MOFs. |
