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The recovery processes of critical metals from multiple sources have turned more and more attention due to the increasing demand and consumption of them in modern industry. Many metals are used as significant components in manufacturing of a variety of products and equipment, playing significant roles in the economic security and national security; those metals involve rare earth elements (REEs), precious metals which include gold, silver, and platinum group metals (PGMs), and other valuable metals such as lithium, uranium, nickel, et al. The traditional approach to obtaining the above metals is by hardrock mining of natural ores via chemical and physical processes. However, this method of mining and refining metals from minerals is usually energy-consuming, costly, and environmental-destructive. Thus, various approaches to extracting or recycling target metals from the seawater or the solution of secondary resources as an alternative to traditional hardrock mining have been developed, and thereinto, using functional porous adsorbents to selectively capture specific metal ions from the aqueous resources has attracted increasing attention due to its outstanding merits such as high efficiency, energy-saving process, low cost, and reduced environmental impacts

The purpose of this study is to evaluate the convenience and effectiveness of using a disc filter to treat washing water from the sand filters at Sundet wastewater treatment plant. The disc filter is used aiming for the reduction of suspended solids and phosphorus. The study was divided in two main experimental stages. During the first stage laboratory jar-tests were performed in order to identify which flocculation aid was more suitable, this was further on used to improve the water treatment. Based on the laboratory trials results, two different polymers (1 and 2) were chosen to be tested at pilot scale. The second stage involved the pilot filter operation itself; this period was as well divided in two sub-stages where filter cloths with two different pore openings were tested. During the first sub-stage the pilot operated with an 18 μm pore opening filters cloth and both polymers. At the end of the first half polymer 1 showed to be more efficient and so it was further used throughout the second sub-stage in combination with a 10μm pore opening filter cloth. As from theoretical knowledge the phosphorus and suspended solid removal were expected to be between 75% and 90%, results which were achieved during both laboratory trials and pilot filter. The best results were observed with the 10μm pore opening filter cloth and polymer 1. Also, additional results from pilot trials performed at Sundet after the study period are presented.

The global transition to renewable energy sources is placing high demands on the development of effective energy storage methods, the most prevalent being batteries. Dual-ion batteries are a new battery technology that takes advantage of the simultaneous intercalation of both cations and anions. Dual-ion batteries can be made from environmentally friendly materials such as organic compounds or conductive polymers that are made up of highly abundant elements. These often have a lower cell voltage than metal-based batteries, allowing water-based electrolytes to be used without decomposing. This master’s thesis presents the synthesis, and electrochemical testing of a nanofibrous polyaniline cathode. It also presents the synthesis and electrochemical testing of two anodes being and graphene-enhanced polyimide, and perylene tetracarboxylic diimide (PTCDI). Aqueous ammonium sulfate of 1 M or 3 M concentration is used as electrolyte. A novel full-cell dual-ion battery is also constructed using polyaniline and PTCDI as electrodes. The addition of graphene to polyimide results in changes in morphology with decreased pore size and increased surface area for supposed improved reaction kinetics with the electrolyte. The electrochemical testing of this anode is however not successful. The polyaniline cathode has an early charge/discharge capacity of 184.5/85.2 mAh/g that decreases to 40.4/45.8 mAh/g after 100 cycles. The PTCDI anode has an early charge/discharge capacity of 80.2/87.3 mAh/g but cannot be evaluated after a few cycles due to electrolyte decomposition. For this reason, the electrolyte dependence on ammonium sulfate concentration is also investigated. An increase in molarity from 1 M to 3 M leads to increased stability of the electrolyte. The polyaniline//PTCDI full-cell has a voltage of 1.2 V and shows an early charge/discharge capacity of 17.6/11.9 mAh/g that decreases to 9.1/7.2 mAh/g after 100 cycles where the efficiency stabilizes at 80%.

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Organic conjugated polymers (CPs) are emerging materials for advanced electronic applications such as organic photovoltaics (OPVs), field-effect transistors (OFETs), light-emitting diodes (OLEDs), flexible and wearable electronics, and biomedicals. High-spin donor-acceptor CPs have been investigated for their potential applications in magnetic and spintronic devices. Inter-chain charge transfer among these high-spin polymers mainly depends on the nature of the local structure of the thin film and pi-stacking between the polymer chains. However, the microscopic structural details of high-spin polymeric materials are rarely studied, especially in the liquid phase, and remain largely unexplored. This study examined the effects of oligomer chain length, side chain, and processing temperature on the organization of the high-spin cyclopentadithiophene-benzobisthiadiazole donor-acceptor conjugated polymer in chloroform solvent. We have found that the oligomers exhibit ordered aggregation based on chain length, with an average pi-stacking distance of 3.38±0.03 (angstrom), aligning well with the experiment. During the solution processing of CPs, smart polymers are widely used for controlling the device performance. Polymethyl-methacrylate (PMMA) is a smart polymer exhibiting solvation behavior in aqueous alcohol mixtures that is different from individual solvents. However, a thorough understanding of the microscopic details underlying PMMA cosolvency remains elusive, which is essential for tailoring smart polymers for advanced applications. Using molecular dynamics simulation, this study elucidates the PMMA's cosolvency behavior in a binary mixture of aqueous tert-butanol and successfully captures the re-collapsing behavior observed experimentally. We have observed that the excess hydrogen bonding between PMMA and water mimics the re-collapsing pattern, suggesting a key role in PMMA's cosolvency. Efforts to discover new organic molecules are hindered by the vast chemical space. Machine learning (ML) approaches offer a promising solution to accelerate the development of new materials. However, predicting properties accurately with ML models typically involves high computational costs and complexity. This study employs a first-generation ML model, ridge regression, to predict the electronic properties — electronic gap, HOMO, LUMO, and singlet-triplet gap of pi-conjugated organic molecules. This research provides molecular-level insights to control device performance by managing aggregation in thin films and reduces the effort required to screen for desirable organic CPs. These findings will facilitate the development of new organic molecules tailored for advanced electronic devices.

La N-méthylphénothiazine (MPT) est une cible de choix pour développer des matériaux organiques redox performants pour électrodes positives de batterie lithium-ion. Ces matériaux dits organiques sont aujourd’hui une alternative crédible aux matériaux inorganiques, actuellement utilisés dans les accumulateurs, de par leurs coûts et toxicité moindres.C’est dans cette optique que des polymères redox contenant l’unité N-méthylphénothiazine ont été synthétisés et caractérisés. Leurs propriétés électrochimiques ont été étudiées en solution via l’utilisation de molécules modèles puis en cellule électrochimique à négative de lithium.Mais pourquoi la N-méthylphénothiazine ? Cette cible redox présente deux systèmes réversibles mais en l’état, seul le premier est exploitable. L’objectif de cette thèse a donc été de modifier chimiquement la molécule afin de moduler les valeurs de potentiels de ses deux systèmes et ainsi les rendre électrochimiquement actifs dans la fenêtre de stabilité des électrolytes de la technologie lithium, permettant de presque doubler la capacité théorique.Ces dérivés ont ensuite pu être polymérisés et testés électrochimiquement, des performances intéressantes ont été obtenues pour certains d’entre eux. Mais malgré l’utilisation de matériaux insolubles à l’état neutre, les cyclages galvanostatiques ont mis en évidence une dissolution des matériaux à l’état oxydé, du moins pour les polymères de plus faibles masses, induisant une diminution de la capacité. / The N-methylphenothiazine (MPT) is a prime target with the aim of developing innovative redox organic materials useful as positive electrode of lithium-ion battery. These organic materials are today a credible alternative to inorganic materials by their lower cost and toxicity.It is in this context that MPT-based redox polymers have been synthesized and characterized. Their electrochemical properties have been investigated in lithium cells to estimate their potential.But why the N-methylphenothiazine ? This redox target has two reversible systems but only the first is exploited. The project was therefore the chemical modification of the MPT molecule to modulate potential values of two systems. These chemical developments thus allow improving notably the MPT derivative theoretical capacities accessible in the electrochemical stability range of lithium-ion technology electrolyte.These derivatives were synthesized and tested in lithium cell. Some of them present interesting performances. But despite the use of insoluble materials at the neutral state, cell tests showed material dissolution in the oxidized state, which decreases significantly the obtained capacities.

The administration of enantiopure drugs brings advantages such as improved efficacy, more predictable pharmacokinetics and reduced toxicity from the point of view of the pharmaceutical area.[1] For this reason, a tremendous amount of supply and demand for enantiomeric pure compounds has been shown not only in market, but industry and academia.[2-4] According to the industry publication Genetic Engineering and Biotechnology News (GEN) in 2014, 22 billion dollars were accounted for enantiopure form of drugs such as Sovaldi® (Sofosbuvir), Crestor® (Rosuvastatin), and Advair® (fluticasone/salmeterol). The fact that one enantiomer can be pharmacologically effective whereas the other enantiomer can be inactive or display non-desirable activity, chiral resolution and asymmetric synthesis research has broken out in recent years to obtain one desired stereoisomer. Enormous amounts of well-organized and rationalized research results for higher enantiomeric selectivity and efficiency has been reported with diverse chiral ligands and transition metals in academia.[5-10] However novelty-driven results from academic area does not meet the requirement in industry field for the practical issue, especially tedious separation process that require high cost and effort. In addition, methodologies developed with privileged chiral ligands and transition metal complexes leave a concern like undesired residue of trace amount of toxic metals in the products. In this dissertation, two types of heterogeneous asymmetric catalyst were investigated to find the alternative that accommodates industrial requirement to obtain enantiomeric pure compounds and novelty-driven academic demands. Firstly, constructions of rationally designed metal organic frameworks (MOFs) using chiral BINOL-derived phosphoric acid ligands were achieved. Overall, catalytic reactions with ocMOFs showed lower enatioselectivity than their homogeneous counterparts, but one of the MOFs, ocMOF-1, was found to exhibit improved enantioselectivity than its homogeneous counterpart in the context of transfer hydrogenation reaction of benzoxazine. Lower enatioselectivity with ocMOFs was rationalized by the chiral environment change by the formation of frameworks in a computational study. In addition, self-supported heterogenization of chiral BINOL-phosphoric acid was achieved by the Yamamoto coupling reaction, and by using catalytically active ocPOP-1 having nanoscopic channels, enantioselectivity was obtained up to 48% in transfer hydrogenation of N-PMP ketimine. Although extension of substituent groups at 3, 3' positions was expected to bring enhanced steric hindrance and to influence to enantioselectivity positively, lack of spatially well-defined interactions induced by this chiral environment change might have lowered the enantiomeric selectivity of the catalytic reaction using ocPOP-1 than its counterpart.

Design and synthesis of porous organic polymers have attracted considerable attentions during the past decade due to their wide range of applications in gas storage, gas separation, energy conversion, and catalysis. Porous organic polymers can be pre-synthetically and post-synthetically functionalized with a wide variety of functionalities for desirable applications. Along these pursuits, we introduced new synthetic strategies for preparation of porous organic polymers for selective CO2 capture. Porous azo-linked polymers (ALPs) were synthesized by an oxidative reaction of amine-based monomers using copper(I) as a catalyst which leads to azo-linkage formation. ALPs exhibit high surface areas of up to 1200 m2 g-1 and have high chemical and thermal stabilities. The nitrogen atoms of the azo group can act as Lewis bases and the carbon atom of CO2 can act as a Lewis acid. Therefore, ALPs show high CO2 uptake capacities due to this Lewis acid-based interaction. The potential applications of ALPs for selective CO2 capture from flue gas, natural gas, and landfill gas under pressure-swing and vacuum swing separation settings were studied. Due to their high CO2 uptake capacity, selectivity, regenerability, and working capacity, ALPs are among the best porous organic frameworks for selective CO2 capture. In our second project, a new bis(imino)pyridine-linked porous polymer (BIPLP-1) was synthesized and post-synthetically functionalized with Cu(BF4)2 for highly selective CO2 capture. BIPLP-1 was synthesized via a condensation reaction between 2,6-pyridinedicarboxaldehyde and 1,3,5-tris(4-aminophenyl)benzene, wherein the bis(imino)pyridine linkages are formed in-situ during polymerization. The functionalization of the polymer with Cu(BF4)2 was achieved by treatment of the polymer with a solution of Cu(BF4)2 via complexation of copper cations with bis(imino)pyridine moieties of the polymer. BF4- ions can act Lewis base and CO2 can act as a Lewis acid; and therefore, the functionalized polymer shows high binding affinity for CO2 due to this Lewis acid-based interaction. The functionalization of the pores with Cu(BF4)2 resulted in a significant enhancement in CO2 binding energy, CO2 uptake capacity, and CO2 selectivity values. Due to high reactivity of bis(imino)pyridines toward transitions metals, BIPLP-1 can be post-synthetically functionalized with a wide variety of inorganic species for CO2 separation and catalytic applications.