A novel free radical-based substitution reaction was developed for grafting aromatic/heteroaromatic compounds to perfluorosulfonic acid polymers (PFSAs). Two proton-exchange membranes perfluorobenzoic acid (PFBA) and perfluorobenzenesulfonic acid (PFBSA)—were synthesized for proton-exchange membrane fuel cells via the free radical-based reaction. The physical properties, in-plane ionic conductivities and fuel cell performance of two membranes were investigated. They exhibited different electrochemical and physical properties, possibly due to the formation of unique dimerized/trimerized structure of –CO2H groups in the PFBA membrane. A free radical-based thermolytic reaction under a high temperature (180 oC)/pressure (1000 psi) condition in the presence of TFA and hydrogen peroxide is first demonstrated. A novel perfluorotetrafluoroaniline (PFTFAn) polymer was synthesized from PFSA and 2,3,5,6-tetrafluoroaniline in one step via the thermolytic reaction. After doping H2SO4 in the PFTFAn polymer, a new conjugated acid membrane (H2SO4-doped PFTFAn) was obtained. The H2SO4-doped PFTFAn membrane displayed better chemical stability and mechanical properties than NafionTM due to the removal of –SO3H groups. The second part of this thesis deals with fluoropolymer-based anion-exchange membranes. A new class of coordinated metal/perfluoropolymer type composite membranes were synthesized and characterized for anion-exchange membrane fuel cells (AEMFCs). A membrane comprised of perfluoro(phenyl-2,2’:6’,2”-terpyridine) polymer, ZrO(ClO4)2 nanoclusters, and 2,2’:6’,2”-terpyridine displayed the highest conductivity of 23.1 mS/cm at 60 oC. The chemical stability test of composite membrane showed no conductivity loss after refluxing in 7 M KOH solution at 120 oC for 2,200 h. A H+ coordinated cage-shape molecule with a benzyl group (Bn-proton cage) was designed and synthesized as a base-stable anion-exchange group. By employing the free radical-based reaction, Bn-proton cage was grafted to a fluoropolymer to yield a stable anion-conductive membrane under alkaline conditions. The third part of this thesis is our design, synthesis and test of ionic liquids for reversible SO2 absorption. Novel di-cationic ionic liquids (DILs) were designed and synthesized for SO2 absorption. DILs were found to have better SO2 absorption capabilities than mono-cationic ionic liquids (MILs). A chloride-based DIL comprised of two N-methylimidazolium cations and a PEG9 (HO-(CH2CH2O)9-H) chain could reversibly uptake 3.710 mole SO2 per mole DIL under ambient conditions. The anion, temperature and water impact on SO2 absorption in DILs was investigated. Although replacing chloride with triflate or tosylate groups led to a reduced SO2 absorption for the DILs, a high selectivity against CO2 was observed in CO2 absorption test.

Cette thèse s’inscrit dans le cadre de synthèses de matériaux innovants contenant des entités cationiques que sont le guanidinium et l’ammonium. Ces entités cationiques confèrent des propriétés intéressantes et fonctionnelles pour chacun des systèmes ioniques suivants : tensio-actifs, liquides ioniques et ionosilices. A cet effet, nous avons procédé à l’étude de deux familles de composés : les sels de guanidiniums et les ionosilices. Pour les sels de guanidiniums, nous avons étudié la formation et les propriétés d’auto-assemblage de tensio-actifs en utilisant différentes techniques de mesures (conductivité, tension de surface et calorimétrie). Ce remarquable synthon moléculaire qu’est le guanidinium a été aussi mis en avant comme liquide ionique pour l’extraction du méthyl orange, du diclofenac et du chromate. Quant aux ionosilices, bien qu’ils présentent aussi des propriétés intéressantes pour l’extraction ionique et l’adsorption de principes actifs, leur mise en forme reste cependant un paramètre clef pour cibler leur application. En effet, la mise en forme des ionosilices en nanoparticules permet l’extension des applications dans le domaine de la nanomedecine. Ainsi, durant cette thèse, des nanoparticules avec des sous-structures ioniques ammoniums sont synthétisées pour la première fois et utilisées comme nano-vecteur pour le relarguage d’un anti-inflammatoire (diclofenac). Par ailleurs, dans le but d’une extraction ionique en flux continu, des matériaux contenant des fonctions ioniques sous forme de monolithe ont été synthétisés à partir de précurseur ammonium par voie sol gel. Ainsi cette thèse nous a permis de trouver les éléments théoriques, illustratifs et expérimentaux des différentes facettes de la formation de matières à base d’unités cationiques aux propriétés remarquables que sont les sels de guanidiniums et les sels d’ammoniums. / This dissertation deals with innovative synthetic materials bearing cationic entities that are guanidinium and ammonium. These cationic entities give interesting and functional properties for each ionic system studied: surfactant, ionic liquid and ionosilica. For this purpose, we investigated two families groups composed of: guanidiniums salts and ionosilica. Regarding guanidiniums salts, we studied the formation and self-assembly behavior of guanidinium surfactants using different measurement techniques (conductivity, surface tension and calorimetry). This remarkable molecular synthon that represents guanidinium was also highlighted as an ionic liquid for the extraction of methyl orange, diclofenac and chromate. As for ionosilicas, although they also have advantageous properties for ion extraction and adsorption of the active ingredients, however their shaping remains a key parameter for targeting their application. In fact, the design of ionosilica material as nanoparticle allows applications extension in the field of nanomedicine. So during this thesis, nanoparticles containing ammonium substructures were synthesized for the first time and used as a nano-vector to deliver an anti-inflammatory drug (diclofenac). Furthermore, with the aim of ionic extraction in continuous flow, materials containing ionic functions as monolith were synthesized from ammonium precursor via sol gel route. This thesis allowed us to find the theoretical, experimental and illustrative elements of the different aspects of materials formation based on cationic entities with remarkable properties that are guanidiniums and ammonium salts.

abstract: Biofuel from microbial biomass is a viable alternative to current energy production practices that could mitigate greenhouse gas levels and reduce dependency on fossil fuels. Sustainable production of microbial biomass requires efficient utilization of nutrients like phosphorus (P). P is a limited resource which is vital for global food security. This paper seeks to understand the fate of P through biofuel production and proposes a proof-of-concept process to recover P from microbial biomass. The photosynthetic cyanobacterium Synechocystis sp. PCC 6803 is found to contain 1.4% P by dry weight. After the crude lipids are extracted for biofuel processing, 92% of the intercellular P is found within the residual biomass. Most intercellular P is associated with nucleic acids which remain within the cell after lipids are extracted. Phospholipids comprise a small percentage of cellular P. A wet chemical advanced oxidation process of adding 30% hydrogen peroxide followed by 10 min of microwave heating converts 92% of the total cellular P from organic-P and polyphosphate into orthophosphate. P was then isolated and concentrated from the complex digested matrix by use of resins. An anion exchange resin impregnated with iron nanoparticles demonstrates high affinity for P by sorbing 98% of the influent P through 20 bed volumes, but only was able to release 23% of it when regenerated. A strong base anion exchange resin sorbed 87% of the influent P through 20 bed volumes then released 50% of it upon regeneration. The overall P recovery process was able to recover 48% of the starting intercellular P into a pure and concentrated nutrient solution available for reuse. Further optimization of elution could improve P recovery, but this provides a proof-of-concept for converting residual biomass after lipid extraction to a beneficial P source. / Dissertation/Thesis / M.S. Civil and Environmental Engineering 2012

No description available.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19731号 / 工博第4186号 / 新制||工||1646(附属図書館) / 32767 / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 江口 浩一, 教授 安部 武志, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20708号 / 工博第4405号 / 新制||工||1684(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 江口 浩一, 教授 安部 武志, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

No description available.

No description available.

Landfill leachates are often discharged to wastewater treatment plants (WWTPs) but their highly varied composition makes their treatment in WWTPs difficult. Landfill leachates contain bio-refractory organic matter which easily passes the biological treatment processes at WWTPs and increases the organic matter in the effluent. Leachates also interfere with the UV disinfection process at treatment plants. Another concern is the presence of large amounts of bio-refractory organic nitrogen in the leachates which makes it difficult for WWTPs to meet the tightening total nitrogen requirements. Studies were conducted to evaluate the applicability of anion exchange resins to remove organic matter, UV quenching substance and organic nitrogen from landfill leachates. Leachate samples based on varying age and treatment methods were utilized. The anion exchange resins were found to work effectively for all studied leachates. The resins were found to remove more bio-refractory UV absorbing substances as compared to total organic carbon (TOC), suggesting that anion exchange resins could be employed for removal of UV absorbing substances. Multiple regenerations of the resin showed slight loss in the capacity to remove UV and organic carbon. Fractionation of leachate samples showed effective removal of humic acid (HA) fraction which is responsible for most of UV quenching. The resin was also found to effectively remove the bio-refractory hydrophilic (Hpi) fraction which tends to persist even after HA fraction has bio-degraded. Membrane filtration (1000 Da and 3000 Da Molecular weight cut off) in conjunction with ion exchange resins achieved better removal of organic matter and UV254 absorbing substances. In addition, this also significantly improved the performance of resins. Significant removal of organic nitrogen was also observed using anion exchange though it was less than both UV and TOC. Around 80% removal of organic nitrogen associated with bio-refractory Hpi fraction was achieved using anion exchange suggesting ion exchange as a viable alternative for removing organic nitrogen. / Master of Science

Long lived radioactive species such as ¹²⁹I⁻ and ⁹⁹TcO₄⁻ are formed as by-products of nuclear fission. These species have extremely long half-lives (1.5 million and 211,000 years respectively), are biologically assimilating and due to their anionic nature, can move freely within a geosphere. Historical disposal methods for active species are no longer considered acceptable to the general public and other ways in which to treat the waste are being explored. One remove and concentrate method to remove radioactive species from the biosphere is using alkaline-resistant materials which trap active species that can be encapsulated in a high pH concrete matrix. Layered hydroxides and layered double salts which consist of positively charged layers between which exchangeable anions and water molecules lie are good candidates for these materials due to the basic conditions in which they form. The synthesis, anion exchange properties and stability of copper, lanthanum, nickel and zinc hydroxysalts have been investigated. The structures consist of layers of edge-sharing metal hydroxide octahedra together with an interlayer space containing the anion and in some cases water molecules. Products were characterised by powder X-ray diffraction and vibrational spectroscopy to confirm the identity of structure of the material formed and the anion incorporated. Only Cu2(OH)3(NO3), Cu2(OH)3(OAc).H2O, Ni2(OH)3(NO3) and Zn5(OH)3(NO3).2H2O consistently exhibited exchange capabilities with iodide as the target anion. In terms of exchange rate and efficiency, copper hydroxyacetate is a more suitable precursor as equilibrium is achieved in 10 mins; whereas other LHS containing nitrate as the occupying require longer than 1 day to reach equilibrium. Cu2(OH)3(Ac).H2O has been shown to easily exchange acetate for monovalent anions X- (X = Ha-, NO3-, ClO4-, IO4-, SbO3-, OH-). Exchange reactions with ReO4- (used as a surrogate to TcO4-) and trigonal pyramidal monovalent anions (such as IO3-) were unsuccessful. Exposure to divalent anions (CO32-, Cr2O42-, SeO3-) resulted in no interaction whereas exposure to trivalent PO43- forms Cu3(PO4)2. Quantitative analysis has shown that, contrary to XRPD and FTIR data, full exchange of acetate for an equimolar amount of iodide within a Cu2(OH)3+ framework does not occur with 100% efficiency. Activity counting, gravimetric analysis and ion specific probe analysis suggested that only ~92-93% exchange occurs. The stability of TcO4- and I- analogues with respect to pH has been investigated. Activity counting has shown that even in pH 9.5 solution, 57-73% of 125I- and 99TcO4- immobilised with a Cu2(OH)3+ framework is leached into solution after 16 days. Exposure of Cu2(OH)3I to high carbonate, nitrate and chloride environments shows a progressive loss of iodide into solution as the anionic radius of the incoming anion decreases and the concentration of the incoming anion increases. In the case of chloride and nitrate incoming anions, only a 2:1 chloride to iodide ratio is need for full exchange whereas a ratio of 10:1 nitrate to iodide is required. In situ ion exchange experiments at Diamond allowed the exchange of the hydroxyacetate material to be investigated in flow experiments showing similar facile exchange as demonstrated under batch conditions. Rietveld refinements on deuterated samples of halide analogues of the materials have allowed accurate structure determinations for the first time (Cu2(OD)3Cl - a = 5.726Å, b = 6.125 Å, c = 5.634 Å, β = 93.100°, Cu2(OD)3Br - a = 6.085 Å, b = 6.144 Å, c = 5.650 Å, β = 93.593°, Cu2(OD)3I - a = 6.587 Å, b = 6.179 Å, c = 5.680 Å, β = 95.044°). As the size of the halide increases, the hydroxide coordination alters reflecting to changing sigma/pi donor capability of the halide.