%0 Generic
%9 Doctoral Dissertation
%A Li, Tao
%D 2014
%F pittir:20116
%K metal-organic framework, bio-MOF, ligand exchange, core-shell, CO2 capture
%T DESIGN AND MODULATION OF ADENINE BASED METAL-ORGANIC FRAMEWORKS AND EXPLORATION OF THEIR NEW PROPERTIES
%U http://d-scholarship-dev.library.pitt.edu/20116/
%X 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.