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Rational Control of Structure, Composition, and Function in Metal-Organic Frameworks

Muldoon, Patrick (2020) Rational Control of Structure, Composition, and Function in Metal-Organic Frameworks. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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This dissertation aims to address several challenges in the chemistry of metal-organic frameworks (MOFs) related to the ability to precisely incorporate and control the distribution of functional components throughout these unique materials. Herein I present four research projects which span from controlling the composition and structural topology of new types of heterometallic MOFs to developing new methods for the systematic modification and optimization of existing materials for the specific applications of biological imaging and carbon capture.
In Chapter 2 I introduce a bottom-up strategy for the design and synthesis of new MOFs with multiple different heterometallic clusters, achieving systematic and differential control over the coordination of multiple metals during the assembly of these frameworks. Chapter 3 describes a unique post synthetic strategy for optimizing the excitation wavelengths of near infrared (NIR) emitting rare earth based MOFs for biological imaging. This approach circumvents the need for large, highly delocalized organic chromophores and instead relies on the tight packing of π-systems formed from smaller monomer units that are introduced throughout MOF pores. The tight packing of π-systems results in long wavelength excitation/absorption bands that are a synergistic property of the composite material not observed in the individual organic components after disassociation of the MOFs. Chapter 4 describes the combination of MOF-based mixed-matrix membrane (MMM) and polymer blending approaches to form exceptional membranes for CO2/N2 separation. Nano-sized amino-functionalized UiO-66 is added to a two-component polymer blend to create a series of MMMs and the compatibility of the component parts leads to property enhancement, in particular improved gas permeability, mechanical flexibility, and mitigated physical aging. In Chapter 5, a facile method for independently controlling both particle size and surface chemistry of UiO-66 through ligand exchange is demonstrated. This strategy allows for a wide variety of functional groups to be installed at the external surface of nano-sized MOF particles with systematically variable densities which can be used to optimize MOF particles for various applications.


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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Muldoon, Patrickpfm6@pitt.edupfm6
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairRosi,
Committee MemberLiu,
Committee MemberMeyer,
Committee MemberWilmer,
Date: 8 June 2020
Date Type: Publication
Defense Date: 2 April 2020
Approval Date: 8 June 2020
Submission Date: 2 March 2020
Access Restriction: 1 year -- Restrict access to University of Pittsburgh for a period of 1 year.
Number of Pages: 281
Institution: University of Pittsburgh
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Degree: PhD - Doctor of Philosophy
Thesis Type: Doctoral Dissertation
Refereed: Yes
Uncontrolled Keywords: Metal-Organic Frameworks, MOF, MOFs, Inorganic chemistry
Date Deposited: 08 Jun 2020 16:47
Last Modified: 08 Jun 2021 05:15

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