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Freshwater as the resource for the survival of humans and all lives on earth is very precious but scarce. The shortage of the original freshwater resources and the interfering activities by human and other natural factors form this issue together. To reduce the water supply pressure and deterioration of freshwater

Freshwater as the resource for the survival of humans and all lives on earth is very precious but scarce. The shortage of the original freshwater resources and the interfering activities by human and other natural factors form this issue together. To reduce the water supply pressure and deterioration of freshwater systems (for example, river, wetland, and groundwater), the quantity-increase and the quality-increase strategies should be implemented at the same time. Therefore, corresponding membrane technologies have been developed to achieve water purification with high efficiency and low cost. For desalinating seawater and other types of saline water, pervaporation has been proved that has the potential to complete desalination with salt rejection rate over 99 % when dealing with high salinity water that reverse osmosis (RO) cannot handle. In this dissertation, except the discussion of commonly used materials to synthesize pervaporation membranes, two types of novel pervaporation desalination membranes (nanophotonic-enhanced membrane and free-standing sulfonated membrane) have been presented and discussed. The novel membranes were tested to see the potential of pervaporation to desalinate seawater and saline water with more complex ionic composition, and the possibility of achieving zero liquid discharge in the desalination field when having pervaporation as the assistance. For mitigating polluted water that is caused by human activities, especially agricultural activities, electrodialysis is an effective method to remove specific ions from water, and it does not require extra chemical cost or regeneration. A type of anion exchange membranes inspired by ion exchange resins was synthesized and tested, and the performance on nitrate removal has been evaluated in this dissertation.
ContributorsLi, Yusi (Author) / Lind, Mary Laura (Thesis advisor) / Perreault, Francois (Thesis advisor) / Forzani, Erica (Committee member) / Seo, S. Eileen (Committee member) / Walker, W. Shane (Committee member) / Arizona State University (Publisher)
Created2023
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Description
The large-scale anthropogenic emission of carbon dioxide into the atmosphere leads to many unintended consequences, from rising sea levels to ocean acidification. While a clean energy infrastructure is growing, mid-term strategies that are compatible with the current infrastructure should be developed. Carbon capture and storage in fossil-fuel power plants is

The large-scale anthropogenic emission of carbon dioxide into the atmosphere leads to many unintended consequences, from rising sea levels to ocean acidification. While a clean energy infrastructure is growing, mid-term strategies that are compatible with the current infrastructure should be developed. Carbon capture and storage in fossil-fuel power plants is one way to avoid our current gigaton-scale emission of carbon dioxide into the atmosphere. However, for this to be possible, separation techniques are necessary to remove the nitrogen from air before combustion or from the flue gas after combustion. Metal-organic frameworks (MOFs) are a relatively new class of porous material that show great promise for adsorptive separation processes. Here, potential mechanisms of O2/N2 separation and CO2/N2 separation are explored.

First, a logical categorization of potential adsorptive separation mechanisms in MOFs is outlined by comparing existing data with previously studied materials. Size-selective adsorptive separation is investigated for both gas systems using molecular simulations. A correlation between size-selective equilibrium adsorptive separation capabilities and pore diameter is established in materials with complex pore distributions. A method of generating mobile extra-framework cations which drastically increase adsorptive selectivity toward nitrogen over oxygen via electrostatic interactions is explored through experiments and simulations. Finally, deposition of redox-active ferrocene molecules into systematically generated defects is shown to be an effective method of increasing selectivity towards oxygen.
ContributorsMcIntyre, Sean (Author) / Mu, Bin (Thesis advisor) / Green, Matthew (Committee member) / Lind, Marylaura (Committee member) / Arizona State University (Publisher)
Created2019
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Description
Reverse osmosis (RO) membranes are considered the most effective treatment to remove salt from water. Specifically, thin film composite (TFC) membranes are considered the gold standard for RO. Despite TFC membranes good performance, there are drawbacks to consider including: permeability-selectivity tradeoff, chlorine damage, and biofouling potential. In order to counter

Reverse osmosis (RO) membranes are considered the most effective treatment to remove salt from water. Specifically, thin film composite (TFC) membranes are considered the gold standard for RO. Despite TFC membranes good performance, there are drawbacks to consider including: permeability-selectivity tradeoff, chlorine damage, and biofouling potential. In order to counter these drawbacks, polyamide matrixes were embedded with various nanomaterials called mixed matrix membranes (MMMs) or thin film nanocomposites (TFNs). This research investigates the use of graphene oxide (GO) and reduced graphene oxide (RGO) into the polyamide matrix of a TFC membrane. GO and RGO have the potential to alter the permeability-selectivity trade off by offering nanochannels for water molecules to sieve through, protect polyamide from trace amounts of chlorine, as well as increase the hydrophilicity of the membrane thereby reducing biofouling potential. This project focuses on the impacts of GO on the permeability selectivity tradeoff. The hypothesis of this work is that the permeability and selectivity of GO can be tuned by controlling the oxidation level of the material. To test this hypothesis, a range of GO materials were produced in the lab using different graphite oxidation methods. The synthesized GOs were characterized by X-ray diffraction and X-ray photoelectron microscopy to show that the spacing is a function of the GO oxygen content. From these materials, two were selected due to their optimal sheet spacing between 3.4 and 7 angstroms and embedded into desalination MMM. This work reveals that the water permeability coefficient of MMM embedded with GO and RGO increased significantly; however, that the salt permeability coefficient of the membrane also increased. Future research directions are proposed to overcome this limitation.
ContributorsInurria, Adam A (Author) / Perreault, Francois (Thesis advisor) / Fox, Peter (Thesis advisor) / Lind, Mary Laura (Committee member) / Arizona State University (Publisher)
Created2017
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Description
This dissertation investigates the mechanisms that lead to fouling, as well as how an understanding of how these mechanisms can be leveraged to mitigate fouling.

To limit fouling on feed spacers, various coatings were applied. The results showed silver-coated biocidal spacers outperformed other spacers by all measures. The control polypropylene

This dissertation investigates the mechanisms that lead to fouling, as well as how an understanding of how these mechanisms can be leveraged to mitigate fouling.

To limit fouling on feed spacers, various coatings were applied. The results showed silver-coated biocidal spacers outperformed other spacers by all measures. The control polypropylene spacers performed in-line with, or better than, the other coatings. Polypropylene’s relative anti-adhesiveness is due to its surface free energy (SFE; 30.0 +/- 2.8 mN/m), which, according to previously generated models, is near the ideal SFE for resisting adhesion of bacteria and organics (~25 mN/m).

Previous research has indicated that electrochemical surfaces can be used to remove biofilms. To better elucidate the conditions and kinetics of biofilm removal, optical coherence tomography microscopy was used to visualize the biofouling and subsequent cleaning of the surface. The 50.0 mA cm-2 and 87.5 mA cm-2 current densities proved most effective in removing the biofilm. The 50.0 mA cm-2 condition offers the best balance between performance and energy use for anodic operation.

To test the potential to incorporate electrochemical coatings into infrastructure, membranes were coated with carbon nanotubes (CNTs), rendering the membranes electrochemically active. These membranes were biofouled and subsequently cleaned via electrochemical reactions. P. aeruginosa was given 72h to develop a biofilm on the CNT-coated membranes in a synthetic medium simulating desalination brines. Cathodic reactions, which generate H2 gas, produce vigorous bubbling at a current density of 12.5 mA cm-2 and higher, leading to a rapid and complete displacement of the biofilm from the CNT-functionalized membrane surface. In comparison, anodic reactions were unable to disperse the biofilms from the surface at similar current densities.

The scaling behavior of a nanophotonics-enabled solar membrane distillation (NESMD) system was investigated. The results showed the NESMD system to be resistant to scaling. The system operated without any decline in flux up to concentrations 6x higher than the initial salt concentration (8,439 mg/L), whereas in traditional membrane distillation (MD), flux essentially stopped at a salt concentration factor of 2x. Microscope and analytical analyses showed more fouling on the membranes from the MD system.
ContributorsRice, Douglas, Ph.D (Author) / Perreault, Francois (Thesis advisor) / Abbaszadegan, Morteza (Committee member) / Fox, Peter (Committee member) / Lind-Thomas, Mary Laura (Committee member) / Arizona State University (Publisher)
Created2019
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Description
Zwitterionic polymers, due to their supurior capability of electrostatically induced hydration, have been considered as effective functionalities to alleviate bio-fouling of reverse osmosis (RO) membranes. Bulk modification of polysulfone-based matrices to improve hydrophilicity, on the other hand, is favored due to the high membrane performance, processibility, and intrinsic chlorine resistance.

Zwitterionic polymers, due to their supurior capability of electrostatically induced hydration, have been considered as effective functionalities to alleviate bio-fouling of reverse osmosis (RO) membranes. Bulk modification of polysulfone-based matrices to improve hydrophilicity, on the other hand, is favored due to the high membrane performance, processibility, and intrinsic chlorine resistance. Here a novel synthetic method was demonstrated to prepare zwitterionic poly(arylene ether sulfone) (PAES) copolymers, which was blended with native polysulfone (PSf) to fabricate free-standing asymmetric membranes via non-solvent induced phase separation process. Both the porosity of the support layer and surface hydrophilicity increased drastically due to the incorporation of zwitterion functionalities in the rigid polysulfone matrix. The water permeance and antifouling ability of the blend membranes were both remarkably improved to 2.5 Lm−2 h−1 bar−1 and 94% of flux recovery ratio, respectively, while salt rejection remained at a high level (98%) even under the high exposure to chlorine (8,000 ppm•h). Besides the preliminary blended membrane design, for the future membrane property enhancement, this dissertation also focused on polymer structure optimizations via elucidating the fundamentals from two perspectives: 1). Synthetic reaction kinetics and mechanisms on polycondensation of PAES. Interestingly, in combination of experiments and the computational calculations by density functional theory (DFT) methods in this work, only the aryl chlorides (ArCl) monomer follows the classical second-order reaction kinetics of aromatic nucleophilic substitution (SNAr) mechanism, while the kinetics of the aryl fluorides (ArF) reaction fit a third-order rate law. The third order reaction behavior of the ArF monomer is attributed to the activation of the carbon-fluorine bond by two potassium cations (at least one bounded to phenolate), which associate as a strong three-body complex. This complex acts as the predominant reactant during the attack by the nucleophile. 2). Optimized copolymer structures were developed for controlled high molecular weight (Mw ~ 65 kDa) and zwitterionic charge content (0~100 mol%), via off-set stoichiometry during polycondensations, following with thiol-ene click reaction and ring-opening of sultone to introduce the sulfobetaine functional groups. The structure-property-morphology relationships were elucidated for better understanding atomic-level features in the charged polymers for future high-performance desalination applications.
ContributorsYang, Yi, Ph.D (Author) / Green, Matthew D (Thesis advisor) / Lin, Jerry Y.S. (Committee member) / Lind, Marylaura (Committee member) / Perreault, Francois (Committee member) / Deng, Shuguang (Committee member) / Arizona State University (Publisher)
Created2019