Investigations of Fundamental Chemistry and Practical Implementations of Stratified Metal-Organic Frameworks

He, Yiwen (2024) Investigations of Fundamental Chemistry and Practical Implementations of Stratified Metal-Organic Frameworks. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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Abstract

This dissertation presents innovative strategies for designing and synthesizing advanced metal-organic frameworks (MOFs) with multi-domain architectures, aimed at enhancing functionality for specific applications. The four key objectives are: 1) controlling ligand exchange to create stratified MOFs (sMOFs) with distinct compositional domains; 2) employing a linker scissoring strategy to synthesize anisotropic multi-domain MOFs, increasing architectural complexity; 3) utilizing modulators during seed synthesis and outer domain growth to generate unique architectures, such as tubular and disc-like domains; 4) designing sMOFs for improved CO2 capture performance under humid conditions.
Chapter 2 investigates ligand exchange processes to achieve complex functional domains in UiO-67 sMOFs, focusing on how sterics and incubation time control secondary strata growth. Steric hindrance was shown to reduce ligand exchange, enabling the creation of blocking layers that maintain the compositional integrity of binary and ternary sMOFs over extended period. Chapter 3 introduces a linker scissoring strategy, whereby a ditopic modulator directs outer domain growth on specific facets, resulting in 12 anisotropic MOF architectures. This approach offers precise control over domain distribution of MOFs, with potential applications in advanced MOF materials. Chapter 4 examines the use of modulators in seed synthesis and outer domain growth, leading to three distinct seed morphologies with unique outer domain behavior. Varying modulator type and amount during secondary growth enabled the formation of complex architectures, including tubular and disc-like domains, significantly enhancing MOF tunability and structural complexity. Chapter 5 presents a core-shell MOF design optimized for CO2 capture in humid environments. Computational screening identified an optimal CO2-selective core and water-blocking shell, which was synthesized and shown to effectively reduce water’s impact on CO2 uptake.
This dissertation advances the design and synthesis of multi-domain MOFs, offering novel methodologies that significantly enhance control over their domain distribution, functionality and architecture. The research presents not only introduces synthetic strategies for controlling ligand exchange and constructing complex domain arrangement in multi-domain MOFs, but also provides the design strategy for specific applications. The insights and techniques developed in this work provide powerful tools for expanding the versatility and performance of MOFs, opening new pathways for their application in gas separation and beyond.

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Details

Item Type:	University of Pittsburgh ETD
Status:	Unpublished
Creators/Authors:	Creators Email Pitt Username ORCID He, Yiwen yih77@pitt.edu yih77
ETD Committee:	Title Member Email Address Pitt Username ORCID Committee Chair Rosi, Nathaniel L. nrosi@pitt.edu nrosi Committee Member Hutchison, Geoffrey R. geoffh@pitt.edu geoffh Committee Member Gui, Xin XIG75@pitt.edu XIG75 Committee Member Wilmer, Christopher E. c.wilmer@pitt.edu c.wilmer
Date:	20 December 2024
Date Type:	Publication
Defense Date:	7 November 2024
Approval Date:	20 December 2024
Submission Date:	11 November 2024
Access Restriction:	2 year -- Restrict access to University of Pittsburgh for a period of 2 years.
Number of Pages:	280
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 framework; core-shell MOF; porous material; stratified MOF; carbon capture
Date Deposited:	20 Dec 2024 14:28
Last Modified:	20 Dec 2024 14:28
URI:	http://d-scholarship.pitt.edu/id/eprint/47128

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