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Thesis advisor: Dunwei Wang / Metal organic frameworks (MOFs) are a class of compounds that show promising potential for a variety of applications due to their uniformity, highly porous structure, lack of dead volume, and fine-tunability. One of these significant applications is in selective ion transport, which makes MOF films a uniquely good separatory material for dual-electrolyte setups, such as those being investigated with Mg-Br batteries. This research has important environmental and industrial ramifications, considering the various drawbacks associated with commercially available batteries such as the lithium-ion battery. The MOF investigated was Mg-MOF-74, which showed promising selective Mg2+ transport abilities. Both Mg-MOF-74 powder and films were synthesized via a vapor-assisted conversion process to maximize efficiency. To characterize the MOF, XRD and SEM imaging was used. This allowed us to gain a nuanced understanding of the material and its properties for further applications. / Thesis (BA) — Boston College, 2022. / Submitted to: Boston College. College of Arts and Sciences. / Discipline: Departmental Honors. / Discipline: Chemistry.

Access to clean water is one of the world's foremost challenges that has been addressed on a large scale by membrane-based separation processes for the last six decades. Commercial membrane technology within one operation, reverse osmosis, has remained consistent since the late 1970s, however within the last two decades, access to nanotechnology has created a realm of study involving thin film nanocomposite (TFN) membranes, in which nanoparticles are incorporated into existing membrane designs. Desirable properties of the nanoparticles may positively impact qualities of the membrane like performance, anti-fouling behavior, and physical strength. In the present work, two types of nanoparticles have been evaluated for their potential as TFN additives: cellulose nanocrystals (CNCs) and metal-organic framework (MOF) nanorods. CNCs were chosen due to their high aspect ratios, mechanical strength, and potential for surface functionalization. MOF nanorods are also of interest given their aspect ratios and potential for functionalization, but they also possess defined pores, the sizes of which may be tuned with post-synthetic modification. Both CNCs and MOF nanorods were incorporated into TFN membranes via interfacial polymerization, and the resulting membranes were characterized using a variety of techniques to establish their performances, but also to gain insight into how the presence of each nanoparticle might be affecting the membrane active layer formation. A resulting CNC membrane (0.5 wt% loading) exhibited a 160% increase in water flux and an improvement in salt rejection to 98.98 ± 0.41 % compared to 97.53 ± 0.31 % for a plain polyamide control membrane. Likewise, a MOF nanorod membrane (0.01 wt% loading) with a high ratio of acid chain modification exhibited a 95% flux increase with maintained high salt rejection. For the CNCs, the flux increase is attributed to the formation of nanoscale voids along the length of each particle that form during the interfacial polymerization. These nanochannels introduce new rapid water transport pathways within the active layer of each membrane while maintaining ion rejection. The proposed mechanism for the MOF nanorods also introduces nanochannels into each membrane, but the presence of each nanorod's pore structure may offer another transport pathway for water molecules, one that varies with pore size. In combination, these results have allowed the study of molecular transport of water molecules and various ion species within the active layer of a thin film composite RO membrane. Understanding these phenomena will allow the development of smarter membrane materials to address present-day and future separations challenges. Carbon nanotubes are also demonstrated as surface modifiers for forward osmosis (FO) membranes to address issues unique to the FO process, namely reverse solute flux (RSF). This method shows promise, as a coating density of 0.97 g/m2 reduced RSF for many draw solution species, including a 55% reduction for sodium chloride. / Doctor of Philosophy / Access to clean water is one of the world's foremost challenges that has been addressed on a large scale by membrane-based separation processes for the last six decades. Commercial membrane technology within one operation, reverse osmosis, has remained consistent since the late 1970s, however within the last two decades, access to nanotechnology has created a recent realm of study in which nanoparticles are incorporated into existing membrane designs. It is desired to use nanotechnology, or nanoparticles to improve membrane performance, i.e. create a membrane with better rejection of unwanted ions or contaminants or improve the amount of water that passes through the membrane. In the present work, two types of nanoparticles have been evaluated for their potential as TFN additives: cellulose nanocrystals (CNCs) and metal-organic framework (MOF) nanorods. Both CNCs and MOF nanorods were incorporated into membranes and the resulting membranes were characterized using a variety of techniques to establish how the nanoparticles affected performance. A resulting CNC membrane (0.5 wt% loading) exhibited a 160% increase in water flux (the amount of water passing through an area in a given amount of time) and an improvement in salt rejection. Likewise, a MOF nanorod membrane with a high ratio of acid chain modification exhibited a 95% flux increase with maintained high salt rejection. For both the CNCs and the MOFs, these performance changes are attributed to new pathways within each membrane for water flow that exist due to the presence of the nanoparticles in each system. In combination, these results have allowed the study of transport of water molecules and various ion species in each membrane. Understanding these results will allow the development of smarter membrane materials to address present-day and future separations challenges.

<p>Metal-organic frameworks (MOFs) are considered as a type of very useful materials for the gas separation/purification industries. However, control over the growing position and growing shape of the crystals remains a challenge and must be overcome in order to realize the commercial potentials of MOFs.</p> <p>In this thesis, a method based on interfacial coordination is developed to address this issue. Zinc-benzenedicarboxyl (Zn-BDC) is chosen as a model system for the proof of concept. In a typical liquid-liquid interface protocol, the MOF precursors, zinc nitrate [Zn(NO3)2] and terephthalic acid (TPA or H2BDC), and the catalyst, triethylamine (TEA), were dissolved into two immiscible solvents, dimethylformamide (DMF) and hexane, respectively. The reaction site, i.e. the MOF growing position could thereby be confined at the interface of the two solvents. It was found that a free-standing membrane could be formed with the combinations of high Zn-H2BDC and low TEA concentrations. The combinations of low Zn-H2BDC and high TEA concentrations yielded MOF particles precipitated out from DMF. Similar results were obtained by changing the liquid-liquid interface to liquid-gas interface, with the TEA-hexane solution replaced by saturated TEA vapor. The dependence of product shape on precursor and catalyst concentrations can be explained by the competition between MOF formation and TEA diffusion into the precursor phase.</p> <p>The morphology, constitution and surface area of the MOF products were characterized by SEM, XRD and nitrogen adsorption testing, respectively. The particles were found to be exclusively MOF-5. The membranes were characterized as asymmetric. The top layer was particulate while the bottom layer had a sheet-like morphology. This was further revealed by XRD data as MOF-5 and MOF-2 (ZnBDC·DMF), respectively. This asymmetry was caused by a change of TEA diffusion rate during the synthesis process, which might result in a change in pH value for the membrane growth. Decent surface areas of the particles and membranes were measured.</p> <p>Apart from the free-standing membranes, MOF membranes on Anodisc support were also synthesized employing the same interfacial techniques. The MOF formation site, i.e. the interface, was confined to the upper end Anodisc pores and sealing the pores after the reaction. The difference in wetting force between DMF and hexane with Anodisc membrane material resulted in the difference of MOF layer morphology from liquid-liquid protocol and liquid-gas protocol. The later gave a continuous MOF membrane due to the absence of air bubble interference.</p> / Master of Science (MSc)

New synthetic advances in the control of nanoparticle size and shape along with the development of new surface modifications facilitates the growing use of nanomaterials in biomedical applications. Of particular interest are functional and biocompatible nanomaterials for sensing, imaging, and drug delivery. The goal of this research is to tailor the function of nanomaterials for biomedical applications by improving the biocompatibility of the systems. Our work demonstrates both a bottom up and a post synthetic approach for incorporating stability, stealth, and biocompatibility to metal based nanoparticle systems. Two main nanomaterial projects are the focus of this dissertation. We first investigated the development of a green synthetic procedure to produce gold nanoparticles for biological imaging and sensing. The size and morphology of gold nanoparticles directly impact their optical properties, which are important for their function as imaging agents or their use in sensor systems. In this project, a synthetic route based on the natural process of biomineralization was developed, where a designed protein scaffold initiates the nucleation and subsequent growth of gold ions. To gain insight into controlling the size and morphology of the synthesized nanoparticles, interactions between the gold ions and the protein surface were studied along with the effect of ionic strength on interactions and then subsequent crystal growth. We are able to control the size and morphology of the gold nanoparticles by altering the concentration or identity of protein scaffold, salt, or reducing agent. The second project involves the design and optimization of metal organic framework nanoparticles for an external stimulus triggered drug delivery system. This work demonstrates the advantages of using surface coatings for improved stability and functionalization. We show that the addition of a polyethylene glycol surface coating improved the colloidal stability and biocompatibility of the system. The nanoparticle was shown to successfully encapsulate a variety of small molecule cargo. This is the first report of photo-triggered degradation and subsequent release of the loaded cargo as a mechanism of stimuli-controlled drug delivery. Each of the aforementioned projects demonstrates the design, synthesis, and optimization of metal-based systems for use in biomedical applications. / Ph. D.

High-performance functional electrode materials are critical for the development of electrochemical energy conversion and storage technologies. Among various advanced materials, three-dimensional (3D) porous structures have attracted extensive interest due to their high surface area and capability for efficient mass transport. Metal-organic frameworks (MOFs) are a novel class of porous coordination polymers constructed with organic linkers connected by inorganic nodes. Their extraordinarily high surface area, permanent pores/channels, good thermal and chemical stabilities have made MOFs one of the most promising materials for various electrochemical applications, including electrocatalysis, supercapacitors, Lithium-ion batteries, chemical sensors, etc. The present dissertation focuses on the investigation of charge transfer mechanism in MOF films so as to establish design rules for future MOF design, and the exploration of MOF-based materials for electrochemical and photoelectrochemical applications. To promote the use of MOF-based materials in electrochemical applications, efficient charge transfer is a necessity. In redox-active MOFs, charge transfer can happen through redox hopping, i.e. site-to-site electron hopping coupled to diffusion of counter ions to balance electroneutrality. While the apparent diffusion coefficient (Dapp) has been employed to describe the overall charge transfer efficiency, independent elucidation of electron and ion diffusion is crucial for providing insights into the mechanism of charge transfer in MOFs. In Chapter 2, we investigated the MOF pore size effect on electron and ion diffusion. Three redox-active ferrocene-doped MOF (Fc-MOF) films with different pore sizes immobilized on conductive substrates were prepared, and electron and ion diffusion coefficients and rate constants were quantified by applying a theoretical model to chronoamperometric responses. Increasing MOF pore size led to an increase in ion diffusion rate constant and a decrease in electron diffusion rate constant. The overall charge transfer rate constant increased when MOF pore size increased, implying the ability of promoting efficient charge transfer through control of MOF pore size. As charge transfer via redox hopping proved to be feasible, Chapter 3 focused on the application of a ruthenium(II)-polypyridyl doped MOF film immobilized on a conductive substrate, UiO-67-Ru@FTO, for solid-state electrochemiluminescence (ECL). In the presence of tripropylamine as a coreactant, UiO-67-Ru@FTO exhibited higher ECL intensity and better reproducibility compared to corresponding solution-based ECL system. Subsequently, UiO-67-Ru@FTO was successfully used for dopamine detection, highlighting the great potential of using MOF-based materials as solid-state ECL detector for practical applications. Covalent-organic frameworks (COFs) are a recently emerging family of crystalline organic polymers constructed with organic building blocks linked by covalent bonds. In addition to advantages including high surface area and high porosity that are similar to MOFs, COFs possess low density due to the constitution of light-weighted elements and excellent stability owing to the robust covalent bonds. Therefore, it is of our interest to investigate the properties and potential applications of COFs. Two-dimensional (2D) COFs are composed of conjugated organic layers stacked via - interactions. Chapter 4 focused on understanding the effects of intraplanar -conjugation and interplanar -stacking on the photophysical properties of a 2D COF, TpBpy. Compared to the two building blocks, TpBpy exhibited a red-shifted emission, due to the - stacking. Density functional theory (DFT) calculations were performed on energies of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). It was found that the extended structure of the framework resulted in a decrease in the HOMO-LUMO gap. The experimental and computational studies reveal the important influence of intraplanar and interplanar interactions on photophysical properties in 2D COFs. In Chapter 5, we modified the COF TpBpy with nickel(II) and investigated its application as an electrocatalyst for 5-hydroxymethylfufural (HMF) oxidation. Unlike TpBpy characterized in Chapter 4, TpBpy thin films were prepared by an interfacial crystallization strategy. The films were transferred to conductive substrates and then post-synthetically modified by nickel acetate. Similar to redox-active MOFs, the resulting TpBpy-Ni COF film exhibited redox conductivity. TpBpy-Ni showed good catalytic activity for HMF oxidation under basic conditions. This study suggests the great potential of functionalized COFs for electrochemical applications. / Doctor of Philosophy / The increasing demand for clean and efficient energy has triggered a great deal of research interest in developing novel energy conversion and storage technologies. In particular, electrochemical (EC) systems including supercapacitors, Lithium-ion batteries, artificial photosynthetic system, fuel cells, etc. have drawn significant attention. The key component in high-performance EC energy conversion and storage devices is the functional electrode materials. Three-dimensional (3D) porous nanostructures have been widely applied as advanced electrode materials due to their high surface area that enables more liquid/solid interfacial interactions, and pores/channels that allows efficient mass diffusion and transport. Metal-organic frameworks (MOFs), made of organic ligands bridged by inorganic nodes, are a novel kind of porous materials with extraordinarily high surface area and permanent porosity. As a result, there is great potential in developing MOF-based electrode materials for EC applications. As the name itself suggests, EC systems rely on electrochemical reactions that involve transfer of charges (i.e. electrons and ions). Therefore, efficient charge transfer is vital for achieving high performance. While MOFs used for gas separation and storage have been reported, their electrochemical applications are still in early stages. The fundamental understanding of charge transfer in MOFs is in its infancy. As a result, there is an urgent demand for understanding the nature of charge transfer in MOFs. In this dissertation, we investigated the mechanism of charge transfer by independent quantification of electron and ion transfer rate constants. With a better understanding in hand, we also explored two electrochemical applications in MOFs, electrocatalysis and electrogenerated chemiluminescence.

Increasing energy demand will not only aggravate global warming, but also cause fossil fuels shortage in the near future. Solar energy is an infinite green energy resource that can potentially satisfy our energy usage. By utilizing solar energy to drive reactions like water splitting, solar fuels system are able to produce valuable energy resource. Catalysts for water oxidation are the essential component of water splitting cells which have been intensively studied. As a solid state porous crystalline material with synthetic tunability, Metal-organic framework (MOF) is a promising platform for water oxidation catalysis due to its outstanding properties. Herein, we aimed to develop molecular catalysts incorporated MOF for water oxidation and study the reaction mechanism. Chapter 1 introduces the background of water oxidation and previous research on ruthenium nuclear water oxidation catalysts (WOCs). The reaction mechanism of binuclear and mononuclear ruthenium WOCs was briefly summarized. Opportunities for the design and the synthesis of MOF based WOCs were then discussed. Lastly, studies about MOF based WOCs were categorized based on the difference of the WOCs active site location in frameworks. Water oxidation catalyst [Ru(dcbpy)(tpy)OH2]2+ (RuTB) was incorporated into UiO-67 MOF (resulting materials denoted as RuTB-UiO-67) for chemical water oxidation in Chapter 2. Differences of catalytic reaction behavior between homogeneous RuTB and RuTB incorporated in MOF were examined. Based on MOF particle size dependent catalysis reaction experiments, in-MOF reactivity was anticipated to be primarily arose from redox hopping between RuTB active sites in the framework. In Chapter 3, RuTB-UiO-67 MOF thin films grown on conducting FTO substrate (RuTB-UiO-67/FTO) were synthesized to test their catalytic activity of electrochemical water oxidation. Electrochemical behavior of RuTB-UiO-67/FTO was found to be consistent with homogeneous RuTB by various electrochemistry study and in-situ X-ray absorption spectroscopy characterization. Scan-rate-dependent voltammetry study demonstrated the homogeneous distribution of electrochemical active sites throughout the MOF thin film. Diffusion controlled redox hopping was attributed to be the main charge transfer pathway during catalysis. In order to pursue photo-induced water splitting system, we further our study by investigating MOF based photoelectrochemical catalysis in Chapter 4. Photoelectrochemical alcohol oxidation was chosen as the preliminary-stage study towards the more challenging goal, photoelectrochemical water oxidation. Electron transfer processes of the photosensitizer ([Ru(bpy)2(dcbpy)]2+) and the catalyst (RuTB) doped UiO-67 MOF were investigated with transient absorption spectroscopy analysis. Finally, the role of redox hopping in electrocatalysis by MOF was reviewed in Chapter 5. Pathways of charge transfer in electroactive MOF were first summarized. Redox hopping in MOF was then compared with previous studies on redox active polymer thin films. Lastly, factors that will affect the rate of redox hopping of MOF electrocatalyst were discussed. / Doctor of Philosophy / Solar energy is the most abundant renewable energy resource that can satisfy our energy demand. Solar fuel devices like water splitting systems can generate hydrogen as an environmental friendly energy source. However, the commercialization of water splitting system was hindered by one particular half reaction, water oxidation. Therefore, the development of efficient and stable water oxidation catalysts is critical. Metal-organic framework (MOF) as a porous crystalline material with large surface area is a great platform for stable and reusable solid state water oxidation catalyst. Herein, we incorporated ruthenium based molecular water oxidation catalysts into a MOF denoted as UiO-67. The catalysts doped MOF was able to oxidize water chemically and electrochemically. Furthermore, light absorber molecules were introduced to the MOF to test their catalytic ability towards photoelectrochemical alcohol oxidation. It provides valuable information for the more challenging study of MOF based photoelectrochemcal water oxidation catalysts.

The development of controllable drug delivery systems is crucial for reducing toxicity and minimizing off-target drug effects for patients undergoing chemotherapy. Metal–organic frameworks (MOFs) are a class of hybrid materials that have become of interest in the field of drug delivery. MOFs are composed of metal nodes and organic bridging ligands. MOFs have a wide range of desirable properties including chemical stability, high porosity, and structural tunability which have positioned them as successful drug carriers. Through judicious choice of linker, stimuli-responsive MOFs can be synthesized to achieve precise control over cargo release. Previously, our lab developed a novel light-responsive drug delivery system using a framework known as UiO-AZB (UiO= University of Oslo, AZB=4,4ʹ-azobenzenedicarboxylic acid). This MOF contains a photoswitchable azobenzene linker. Upon irradiation with ultraviolet light, the compound undergoes a structural change known as photoisomerization, resulting in degradation of the MOF structure and simultaneous release of encapsulated cargo. To improve the clinical relevance of our framework, we focus on developing synthetic methods for production of visible light-responsive azobenzene photoswitches. A green light-responsive MOF (UiO-AZB-F) containing a 4,4ʹ-(diazene-1,2- diyl)bis(3,5-difluorobenzoic acid) linker was developed as a drug delivery system for the treatment of colorectal cancer. Our work also focuses on optimizing various aspects of MOF design to maximize and diversify cargo loading and precisely control cargo release rates. A combined computational and experimental investigation of drug adsorption process reveals that the presence of solvent can significantly impact the adsorption of drug molecules within MOF pores. To address these concerns, a variety of drug loading procedures were screened to determine conditions for maximizing the loading of diverse drug cargoes. Conditions for the loading of single agents as well as chemotherapy cocktails were explored to expand the application of our delivery platform to other cancer types including lung, pancreatic, bladder and cervical. To modulate the release of cargo, a series of MOFs containing precise ratios of green light-responsive linker were synthesized to create a platform for sustained release. Remarkably, several MOF derivatives showed enhancement in drug adsorption, highlighting the important role of host–guest interactions in nanocarrier development. Holistically, this work highlights the promise of stimuli-responsive MOFs as drug delivery platforms. / Doctor of Philosophy / Cancer is one of the leading causes of death worldwide. In 2021, nearly 2 million people in the U.S. were diagnosed with cancer. For patients undergoing chemotherapy treatment, the side effects of potent chemotherapeutics are often debilitating. Drug- delivery systems serve as a promising platform for localizing the delivery of chemotherapeutic drugs within a diseased area. When chemotherapeutics are delivered precisely to tumor regions via drug delivery systems, systemic side effects are significantly diminished. In this work, a series of materials known as metal–organic frameworks (MOFs) are developed as carriers for chemotherapeutic cargo. Due to the incorporation of photoactivated compounds within the backbone, these MOFs can be degraded on-demand through green light irradiation. As the framework degrades into small molecule components, drug cargo is simultaneously released. Methods for maximizing MOF drug loadings, diversifying the types of cargo that can be incorporated, and modifying cargo release rates are also investigated. This work establishes stimuli-responsive MOFs as promising materials for on-demand drug delivery.

Les nanoMOFs – nanoparticles poreuses hybrides ont récemment été introduites dans le domaine de la vectorisation des médicaments afin de combiner les avantages de systèmes purement organiques ou inorganiques. Les nanoMOFs biodégradables et biocompatibles à base de trimesate de fer (MIL-100) ont été étudiées. Une méthode de synthèse «verte» a été développée et validée, ouvrant la voie à la production à grande échelle et à l’utilisation de ces matériaux pour des applications biologiques. Par la suite, les MIL-100 nanoMOFs ont été proposées comme potentiels vecteurs pour l’administration de médicaments hydrophiles antirétroviraux et anti-cancéreux, tels que les analogues nucléosidiques azydothimidines mono et triphosphates ou encore le Topotécan. Finalement, une nouvelle stratégie de modification de surface des nanoMOFs par leur recouvrement avec une couronne à base de dérivés de la β cyclodextrine, a été developpée. / Hybrid porous materials, as Metal Organic Frameworks (MOF) have been recently introduced in the drug delivery field in the attempt to combine advantages of the conventional “purely organic” or “purely inorganic” nanocarriers, such as important loading capability and controlled release.In this work the potential of biodegradable and biocompatible MOF nanoparticles made of iron trimesate (MIL-100 nanoMOF) has been investigated. A “green” synthetic procedure has been developed and validated, opening the way to the scale up synthesis of these materials for biological applications. MIL-100 nanoMOFs have been further applied to the delivery of hydrophilic drugs such as antiretroviral nucleoside analogues mono and triphosphate (azydothimidine mono and triphosphate) and the anticancer drug topotecan. Finally a new method of nanoMOFs surface modification, based on the nanoparticles coating with a β cyclodextrin-based extrenall shell, has been developed