Graduation date: 2005

Graduation date: 1999

Increased public awareness, stricter legislation standards, and environmental and health effects associated with water pollution are driving the development of improved wastewater treatment techniques. In order to meet these challenges, a novel and cost effective process has been developed at the University of Manchester to treat water contaminated with dissolved organics by exploiting a combination of adsorption and electrochemical regeneration. Adsorption of organics takes place on the surface of a non-porous and highly electrically conductive graphite adsorbent, followed by anodic electrochemical regeneration leading to oxidation of the adsorbed organic contaminants. The mechanism of degradation of adsorbed organics during electrochemical regeneration is particularly important from the point of view of the breakdown products. Ideally, complete oxidation of the adsorbed organics to CO2 and H2O should occur, but it is also possible that intermediate by-products may be formed. These breakdown products could be released into the water, be released as gases during the regeneration process or may remain adsorbed on the surface of the adsorbent. Information about the breakdown products is an important requirement for the commercial application of the process. This PhD project focused on an investigation of the formation of intermediate oxidation products released into the water (liquid phase) and with the regeneration gases. Phenol was chosen as a model pollutant and a graphite intercalation compound (GIC) adsorbent, Nyex®1000 (Arvia® Technology Ltd) was used. The main oxidation products formed during both batch and continuous adsorption with electrochemical regeneration were 1,4-benzoquinone, maleic acid, oxalic acid, 4-chlorophenol and 2,4-dichlorphenol. These compounds were detected in small concentrations compared to the overall concentration of the phenol removed. Two mechanisms of organic oxidation during electrochemical regeneration of the GIC adsorbents were identified. The first was the complete oxidation of the adsorbed species on the surface of the adsorbent and the second involved the indirect electrochemical oxidation of organics in solution. Breakdown products were found to be formed due the indirect oxidation of organics in solution. The formation of (chlorinated and non-chlorinated) breakdown products was found to be dependant on current density, pH, initial concentration, chloride content and the electrolyte used in the cathode compartment. The concentrations of chlorinated breakdown products can be minimized by using low current density, low initial concentrations, a chloride-free environment and/or treating the water over a number of adsorptions and regeneration cycles. On the other hand, non-chlorinated breakdown products can be minimized by applying higher current density and treating the solution over several cycles of adsorption and regeneration. Therefore, selection of optimum conditions is important to reduce the formation of undesirable breakdown products. The formation of free chlorine during batch electrochemical regeneration was also investigated under a range of operating conditions including the initial concentration of chloride ions, current density and pH. The outcomes of this study have important implications in optimising the conditions for the formation of chlorinated breakdown products and in exploring the role of electrochlorination for water disinfection. Analysis of the regeneration gases has revealed that the main components of the gases generated during the electrochemical regeneration of GIC adsorbents were CO2 and H2O. A preliminary mass balance has suggested that about 60% of the adsorbed phenol was oxidised completely to CO2. However, further work is needed to determine the fate of the remaining phenol. The surface characterization of the GIC adsorbent during adsorption and electrochemical regeneration was carried out using surface techniques including Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, Energy dispersive X-ray spectroscopy (EDS) and Boehm titration. FTIR and Raman spectroscopy were found to be unsuitable for determining the concentration changes at the surface of the adsorbent during adsorption and regeneration. However, Boehm titration has shown that the GIC adsorbent has phenolic, carboxylic and lactonic groups. The concentrations of phenolic groups were found to be higher after phenol adsorption and to decrease during electrochemical regeneration. The results of EDS analysis gave results which were consistent with these observations. Another important aspect of this PhD project was to explore the potential application of adsorption and electrochemical regeneration using GIC adsorbents to water disinfection. A model microorganism E. coli was selected for adsorption and electrochemical regeneration studies under a range of experimental conditions. This study has provided evidence that the process of adsorption and electrochemical regeneration using GIC adsorbents can be used for disinfection of water. Disinfection of water was found to be a combination of two processes: the adsorption of microorganisms followed by their deactivation on the surface; and electrochemical disinfection in solution due to indirect oxidation. The possible disinfection mechanisms involved in these processes include electrochlorination, pH changes and deactivation by direct oxidation of microorganisms. Scanning electron microscopy was found to be a useful tool for investigating changes in surface morphology of microorganisms during adsorption and electrochemical regeneration. The disinfection of a variety of bacteria, fungi and yeasts was tested and evaluated. However, disinfection of protozoa including C. parvum was not demonstrated successfully. It was also demonstrated that the process of adsorption with electrochemical regeneration using GIC adsorbents can be used to simultaneously remove organics and to disinfect microorganisms.

In this dissertation, I report my thesis work on studying surface electron dynamics for intercalated graphene on a metal template using both experimental and theoretical methods. A general description of the research motivation is summarized in the first Chapter. The experimental and theoretical techniques involved in this thesis research are introduced in Chapter 2. In Chapter 3 and Chapter 4, the key findings of this thesis work are reported. These findings concern two novel surface electronic phenomena in oxygen intercalated-graphene on Ir(111) interface. The first phenomenon was the observation of strongly excited image potential states (IPS) in a well-defined quasi-free-standing graphene (QFG) at an oxygen-intercalated Gr/Ir interface. Specifically, the interfaces were synthesized to form Gr/Ir and QFG (Gr/O/Ir) by oxygen intercalation. The syntheses were monitored by low-energy-electron-diffraction (LEED). Our research succeeded in exciting and measuring IPSs on both interfaces by angle-resolved two-photon-photoemission (AR-2PPE) and then the increasing of the IPS binding energy of 0.17 eV following the oxygen intercalation. Finally, our work proposed a theoretical model based on density-functional-theory (DFT) calculations and effective potential models to simulate the surface potential variations in the presence of the intercalated oxygen and its influence on IPSs. The energy shift could be understood by an approximation considering only the out-of-plane chemical and structural modulations. In addition, the results of the model are in strong agreement with the measured IPS band structures. The agreement enables us to attribute the IPS binding energy shift to two potential modulations: a deepened and widened interfacial potential well due to the presence of oxygen intercalants and an increased graphene-Ir interlayer distance. The second phenomenon investigated was a non-dispersive unoccupied band at the Brillouin Zone (BZ) center, which was observed only for Gr/O/Ir but not for Gr/Ir interface. The unoccupied state is approximately 2.6 eV above Fermi energy and was discovered by AR-2PPE. The existence of the non-dispersive band inspired us to undertake a careful examination of the in-plane structural modulation induced by oxygen intercalants. LEED measurements confirm the presence of an in-plane 2$\times$2 periodicity of the intercalated oxygen in QFG. This periodicity can provide periodic perturbation to QFG and can generate the flat unoccupied state due to zone-folding effects from the BZ edge. Angle-resolved photoemission measurements and DFT-based calculations were used to compare the measured Gr/O/Ir states to that of Gr/Ir and O/Ir, providing solid evidence for this zone-folding interpretation. The realization of mixing bands between high symmetry points in BZ by zone-folding in Gr/O/Ir demonstrates a pathway for engineering the graphene electronic structure and its two-photon optical excitation via other ordered intercalants. In addition, a separate but related collaboration work on the phase-transition and electronic-structure evolution in W-doped \ce{MoTe2} is documented in Chapter 5. In this work, I contributed expertise in photoemission to study the critical dopant stoichiometry responsible for the phase transition.

Graduation date: 1996

Efficient and economic treatment of low concentration organic pollutants in water, wastewater or industrial process streams is normally very difficult to achieve. Activated carbon has been widely used for contaminant adsorption, but there are problems associated with its regeneration. In this work, a novel, non-porous, highly-conducting graphite intercalation compounds material (GIC) is used. The use of such an adsorbent can significantly reduce the time required to achieve both equilibrium and electrochemical regeneration. This character allows the design of an innovative treatment process that can adsorb contaminants and electrochemically regenerate itself simultaneously within a single unit. A novel liquid-lift reactor for water treatment by an adsorption and electrochemical regeneration process is developed in this work. Batch experiments are carried out to determine the adsorption kinetics and equilibrium isotherm of adsorption Acid Violet 17 onto the GIC adsorbent. The experimental kinetic data are analyzed using the pseudo-first order, pseudo-second order, intra-particle diffusion and three-stage kinetic models. The linear pseudo-second order model offers the highest r2 correlation coefficient. The experimental isotherm data are analyzed using Langmuir, Freundlich and Tempkin isotherm models. The non-linear Langmuir model gives the highest r2 correlation coefficient. High regeneration efficiency (more than 90%) over a number of cycles is obtained by passing a charge of 6.4 C g-1 of the GIC adsorbent, at a current density of 5 mA cm-2 using a batch, sequential adsorption (60 min) and electrochemical regeneration (30 min) process. The simultaneous adsorption and regeneration process indicates that 100 % AV 17 can be removed in 60 min (4L of 100 mg L-1 AV 17 solution, 140g of the GIC adsorbent, current density of 5mA cm-2). The flow behaviour in the electrochemical reactor has been studied using a pulse tracer technique. The residence time distribution shows that the flow behaviour in the liquid-spouted reactor can be regarded as a plug flow in series with a continuous stirred tank reactor. For the batch adsorption system, a “parallel adsorption barren well hypothesis” is proposed in this thesis. For the batch simultaneous adsorption and electrochemical regeneration system, a multi-parameter model is proposed in this thesis.

In the pursuit of lower cost intumescent flame retardant (IFR) systems, the compound expandable graphite (EG) was identified. This compound delivers high flame retardant performance but provides non-uniform thermal shielding when exposed to open flame from below due to negative gravitational effects. It was theorised that this may be remedied either through ion exchange of the interstratified ions with low glass transition ions or through use in binary systems with other compounds. Two classes of commercial EG were identified, namely a low and a high expansion onset temperature EG compound. Extensive characterisation of each EG compound was undertaken to assess its composition, expansion mechanisms and onset temperatures in order to identify compatible compounds for binary use. The susceptibility of each compound to ion exchange was also assessed. An industrial IFR ethylenediamine phosphate (EDAP) and a novel flame retardant were synthesised for assessment in binary use with EG. Coupled with the above study, this project developed two novel fire testing techniques as low cost alternatives to well-established fire testing methods such as cone calorimetry. The first technique involved an open flame fire testing method which allowed vertical or horizontal testing. Digital and infrared (IR) video recording during operation facilitated comparison of multiple performance indicators further strengthening this method. The second technique allowed assessment of the mass loss resistance of each compound during laser pyrolysis. Characterisation of the EG compounds allowed development of structural models to describe each compound and explain the mechanisms of their expansion and gaseous release. Exhaustive ion exchange testing did not deliver favourable results, necessitating the pursuit of compounds for binary use with EG. A novel IFR was synthesised by neutralising 3,5-diaminobenzoic acid hydrochloride salt with ammonium dihydrogen phosphate. This compound, which melts at 257 °C, decomposes concurrently to release carbon dioxide gas which promotes intumescent charring. The flame retardant performance of this compound and EDAP as primary flame retardants and in combination with expandable graphite was evaluated. As a proof of concept, the novel compound was tested as a primary flame retardant using cone calorimetry after which its utility in binary systems with low temperature expandable graphite was tested. Substantial decreases in peak heat release rate (pHRR) and flame out time were achieved for all binary systems. This success led to testing of a number of combinations of low and high expansion onset EG and the other IFRs to identify the highest performing combination, which proved to be the 10-10 EDAP-EG system. Combinations of EG and the novel compound also showed excellent results. The novel fire testing techniques proved effective in identifying high performance combinations and showed comparable trends to those measured in cone calorimetry, at a greatly reduced cost and material requirement. IR analysis of open flame fire testing indicated increases in the temperatures required for ignition and burn through of the substrate. Observations, corroborated by optical video, showed that cohesive and uniform thermal shielding was achieved in all binary systems tested. This study illustrates that systems of 10% EG combined with either 10% DABAP or 10% EDAP are both the most economical binary systems tested but are extremely high performance systems as well. Both of these systems delivered excellent results while being more economic than the widely used industrial system with a 25-30% EDAP loading. It is recommended that these compounds be considered for industrial use. Furthermore, the effective fire testing techniques developed in this study may be utilised in future fire testing to identify high performance compounds at a lower cost prior to further assessment through methods such as cone calorimetry. / Thesis (PhD)--University of Pretoria, 2017. / Chemical Engineering / PhD / Unrestricted

The strength and success of the hydrogen economy relies heavily on the storage of hydrogen. Storage systems in which hydrogen is sequestered in a solid material have been shown to be advantageous over storage of hydrogen as a liquid or compressed gas. Many different types of materials have been investigated, yet the desired capacity and uptake/release characteristics required for implementation have not been reached. In this work, porphyrin aggregates were investigated as a new type of material for hydrogen storage. The building blocks of the aggregates are porphyrin molecules that are planar and can assume a face to face arrangement that is also known as H-aggregation. The H-aggregates were formed in solution, upon mixing of aqueous solutions of two different porphyrins, one carrying positively charged and the other one carrying negatively charged functional groups. The cationic porphyrin used was meso-tetra(4- N,N,N-trimethylanilinium) porphine (TAP) and it was combined with four different anionic porphyrins, meso-tetra(4-sulfonatophenyl)porphine (TPPS), meso-tetra(4-carboxyphenyl) porphine (TCPP), Cu(II) meso-tetra(4-carboxyphenyl) porphine, and Fe(III) meso-tetra(4- carboxyphenyl) porphine. The force of attraction that held two oppositely charged porphyrin molecules together was electrostatic attraction between the peripheral groups. Solid state aggregates were successfully isolated either by solvent evaporation or by centrifuging and freeze drying. TCPP-TAP and Cu(II)TCPP-TAP aggregates were shown to interact with hydrogen starting from 150 °C up to 250 °C. The uptake capacity was about 1 weight %. Although this value is very low, this is the first observation of porphyrin aggregates absorbing hydrogen. This opened the way for further research to improve hydrogen absorption properties of these iv materials, as well as other materials based on this model. Two other materials that are also based on planar building blocks were selected to serve as a comparison to the porphyrin aggregates. The first of those materials was metal intercalated graphite compounds. In such compounds, a metal atom is placed between the layers of graphene that make up the graphite. Lithium, calcium and lanthanum were selected in this study. Theoretical hydrogen capacity was calculated for each material based on the hydriding of the metal atoms only. The fraction of that theoretical hydrogen capacity actually displayed by each material increased from La to Ca to Li containing graphite. The weight % hydrogen observed for these materials varied between 0.60 and 2.0 %. The other material tested for comparison was KxMnO2, a layered structure of MnO2 that contained the K atoms in between oxygen layers. The hydrogen capacity of the KxMnO2 samples was similar to the other materials tested in the study, slightly above 1 weight %. This work has shown that porphyrin aggregates, carbon based and manganese dioxide based materials are excellent model materials for hydrogen storage. All three materials absorb hydrogen. Porphyrin aggregates have the potential to exhibit adjustable hydrogen uptake and release temperatures owing to their structure that could interact with an external electric or magnetic field. In the layered materials, it is possible to alter interlayer spacing and the particular intercalates to potentially produce a material with an exceptionally large hydrogen capacity. As a result, these materials can have significant impact on the use of hydrogen as an energy carrier.

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第24853号 / エネ博第462号 / 新制||エネ||87(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 野平, 俊之, 教授 萩原, 理加, 教授 佐川, 尚 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

Les travaux de recherche effectués lors de cette thèse s'articulent autour de matériaux graphène. Une méthode est développée pour produire graphène en masse avec solution de graphenure. Les études effectuées les solutions de graphenure sont basées sur les composés d'intercalation du grpahite (GICs) synthétisé avec du potassium et l'exfoliation de GIC dans un solvant organique. Différentes techniques d'analyse ont été employées pour caractériser les graphène produits. Afin de tirer parti des propriétés électriques du graphène, les solutions de graphenure ont ensuite été utilisées pour produire des films transparents conducteurs. Des traitements de recuit à sous atmosphère d'argon ont été effectués pour améliorer les propriétés électriques du film. Les résultats de caractérisation montrent que l'élimination des groupes fonctionnels contenant des atomes d'oxygène et l'amélioration structurale peuvent largement améliorer les propriétés électriques des films de graphène avec ce traitement de recuit. / The graphene is promising materials in future industrial applications due to its excellent properties. In recent years, different production methods have been developed in order to pave the way for applications. One topic of this thesis focuses on graphenidesolutions, which provide an efficient route to produce graphene. Using this method, graphite intercalation compounds(GICs)can be exfoliated into negativelz charged grapheme organic solvent under inert atmosphere. Withits high conductivity and bendable feature, one of the promising applications of graphene is flexible transparent conductive films. The second main topic of this thesis consists in applying produced graphene to produce transparent conductive films.With mild thermal treatments, the electrical properties of graphene film can be largely improved.