eprintid: 20116
rev_number: 15
userid: 2868
dir: disk0/00/02/01/16
datestamp: 2015-01-31 06:00:03
lastmod: 2016-11-15 14:16:01
status_changed: 2015-01-31 06:00:02
type: thesis_degree
metadata_visibility: show
contact_email: li.tao.fudanchem@gmail.com
item_issues_count: 0
eprint_status: archive
creators_name: Li, Tao
creators_email: li.tao.fudanchem@gmail.com
title: DESIGN AND MODULATION OF ADENINE BASED METAL-ORGANIC FRAMEWORKS AND EXPLORATION OF THEIR NEW PROPERTIES
ispublished: unpub
divisions: sch_as_chemistry
full_text_status: public
keywords: metal-organic framework, bio-MOF, ligand exchange, core-shell, CO2 capture
abstract: 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.

date: 2014-01-31
date_type: published
pages: 272
institution: University of Pittsburgh
refereed: TRUE
etdcommittee_type: committee_chair
etdcommittee_type: committee_member
etdcommittee_type: committee_member
etdcommittee_type: committee_member
etdcommittee_name: Rosi, Nathaniel/NR
etdcommittee_name: Star, Alex/AS
etdcommittee_name: Hutchison, Geoffery/GH
etdcommittee_name: Johnson, Karl/KJ
etdcommittee_email: nrosi@pitt.edu
etdcommittee_email: astar@pitt.edu
etdcommittee_email: geoffh@pitt.edu
etdcommittee_email: karlj@pitt.edu
etdcommittee_id: NROSI
etdcommittee_id: ASTAR
etdcommittee_id: GEOFFH
etdcommittee_id: KARLJ
etd_defense_date: 2013-10-15
etd_approval_date: 2014-01-31
etd_submission_date: 2013-11-27
etd_release_date: 2014-01-31
etd_access_restriction: immediate
etd_patent_pending: TRUE
thesis_type: dissertation
degree: PhD
citation:   Li, Tao  (2014) DESIGN AND MODULATION OF ADENINE BASED METAL-ORGANIC FRAMEWORKS AND EXPLORATION OF THEIR NEW PROPERTIES.  Doctoral Dissertation, University of Pittsburgh.    (Unpublished)  
document_url: http://d-scholarship-dev.library.pitt.edu/20116/1/ETD_PhD_Thesis_Tao_Li_for_submission3.pdf