Nitrogen-rich porous organic frameworks show great promise for use as acid-doped proton conducting membranes, due to their high porosity, excellent chemical and thermal stability, ease of synthesis, and high nitrogen content. Aided by very high surface area and pore volume, the material has the ability to adsorb high amounts of H3PO4 into its network, which creates a proton rich environment, capable of facile proton conduction. The morphology and chemical environment, doping behavior, and proton conduction of these materials were investigated. With such high acid-doping, ex-situ studies revealed that under anhydrous conditions, PA@BILP-16 (AC) produced a proton conductivity value of 5.8 x 10-2 S cm-1 at 60 °C and PA@ALP-6 showed a slightly higher value of 5.91 x 10-2 S cm-1 at 60 °C. With such promising results, in-situ experiments with various analogues are scheduled to be conducted in the near future.

Diamond is an important material in many industrial applications (e.g., machining of hard materials, bio-electronics, optics, electronics, etc.) because of its exceptional properties such as hardness, tolerance to aggressive environments, compatibility with human tissues, and high carrier mobility. However, a highly controlled method for growing artificial high-purity diamond on a range of different substrates is needed to exploit these exceptional properties. The Chemical Vapour Deposition (CVD) method is a useful tool for this purpose, but the process still needs to be developed further to achieve better control of growth. In this context, the introduction of dopant species into the gas phase has been shown to strongly influence growth rate and surface morphology. Density Functional Theory (DFT) methods are used to deepen our atomic-level understanding of the effect of dopants on the mechanism for CVD growth on diamond. More specifically, the effect of four dopants (N, P, B and S) has been studied on the important reaction steps in the growth mechanism of diamond. Substitution of N into the diamond lattice has generally been found to disfavour critical reaction steps in the growth of the 100-face in diamond. This negative effect has been related to electron transfer from the N dopant into an empty surface state, e.g., a surface carbon radical. In addition, strong surface stabilization is observed for N substitution in certain sites via a beta-scission reconstruction, with the formation of sp2 carbon. These observations correlate well with observed surface degradation and decrease in growth rate when a high concentration of nitrogen gas is introduced into the CVD growth process. The effect of co-adsorbed P, S and B onto the diamond surface has also been investigated for two reaction steps: CH3 adsorption and H abstraction. While P and B are observed to influence these reaction steps, the effect of S is rather limited.

The unique features of the Spark plasma sintering (SPS) were used to investigate the sintering and deformation behaviour of titanium and titanium–titanium diboride composites, and to control the sintering and grain growth of ferroelectric Na0.5K0.5NbO3 (NKN) and of hydroxyapatite (HAp). In the SPS the samples experience a temperature different from that recorded by the thermocouple (pyrometer) used and this temperature difference has been estimated for Ti and NKN.   Sintering and deformation of titanium was investigated. Increasing heating rate and/or pressure shifted the sintering to lower temperatures, and the sintering and deformation rates changed when the α→β phase transition temperature was passed. Fully dense Ti/TiB2 composites were prepared. The Ti/TiB2 composites could be deformed at high temperatures, but the hardness decreased due to the formation of TiB.    The kinetic windows within which it is possible to obtain fully dense NKN and HAp ceramics and simultaneously avoid grain growth are defined. Materials have a threshold temperature above which rapid and abnormal grain growth takes place. The abnormal grain growth of NKN is due to a small shift in the stoichiometry, which in turn impairs the ferroelectric properties. Fully transparent HAp nanoceramics was prepared, and between 900 and 1050 oC elongated grains are formed, while above 1050 oC abnormal grain growth takes place.NKN samples containing grains of the sizes 0.35–0.6 µm yielded optimum ferroelectric properties, i.e. a high remanent polarization (Pr = 30 µC/cm2) and high piezoelectric constant (d33= 160 pC/N). The ferroelectric domain structure was studied, and all grains exhibited a multi-domain type of structure. / At the time of doctoral defense the following articles were unpublished and had a status as follows: Article 4: Manuscript; Article 5 : Manuscript

The role of sodium chloride (NaCl) particles and ammonium sulfate ((NH4)2SO4) particles on the initial atmospheric corrosion of copper and zinc was investigated under in situ and ex situ conditions using microgravimetry, FTIR spectroscopy, ion chromatography, scanning electron microscopy with x-ray microanalysis and the scanning Kelvin probe. For the first time, in situ infrared spectra were collected on a micron level during particle induced atmospheric corrosion using a recently developed experimental set-up for in situ FTIR microspectroscopy. Lateral distribution of corrosion and reaction products on copper and zinc surfaces was determined and could be connected with the mechanisms of the initial particle induced corrosion. The recently discovered secondary spreading effect from NaCl electrolyte droplets on metal surfaces was studied under in situ conditions and the effect of CO2 on the spreading process was elaborated. The ambient level of CO2 (350 ppm, 1 ppm = 10-6 volume parts) results in a relatively low secondary spreading effect, whereas the lower level of CO2 (<5 ppm) causes a much faster secondary spreading effect over a large area. At low CO2 concentration alkaline conditions will prevail in the cathodic area, leading to large changes in the surface tension at the oxide/electrolyte interface in the peripherical parts of the droplet. This induces a surface tension driven convective flow of electrolyte from the NaCl droplet. The continuous growth of the secondary spreading area at low CO2 concentration is possible due to the galvanic coupling with the droplet leading to transport of sodium ions to this region and maintenance of the alkaline conditions. At 350 ppm CO2, carbonate formation in the secondary spreading area results in lowering of the pH, increasing the surface tension of the oxide/electrolyte interface and inhibiting the secondary spreading. CO2 strongly affects the NaCl-induced atmospheric corrosion rate of copper. The overall influence of CO2 and NaCl depends on at least three identified mechanisms. At low NaCl particle density, CO2 affects the secondary spreading effect from the electrolyte droplet. This leads to a larger effective cathodic area at low CO2 concentration and a higher corrosion rate. The more alkaline surface electrolyte present at low CO2 concentration also affects the formation of corrosion products and the amount of soluble copper chloride. Whereas the presence of larger amounts of soluble chloride tends to increase the corrosion rate, the formation of CuO results in a more protective surface film which decreases the corrosion rate. This effect was observed at higher NaCl particle densities, where the secondary spreading areas overlapped with adjacent NaCl particle clusters. The formation of CuO leads to lower corrosion rates compared to ambient CO2 concentration in which this phase was not formed. For zinc, the formation of a more protective corrosion product layer was not observed and the corrosion rate is generally higher for low than for ambient CO2 concentration. The presence of NaCl particles on the metal surfaces strongly affects the SO2 interaction with the metal surfaces. The oxidation of S(IV) turned out to be fast at the area of the NaCl-containing electrolyte droplet, both for copper and zinc. On copper surfaces, both sulphate (SO4 2-) and dithionate (S2O6 2-) ions formed which is consistent with a copper catalysed reaction route for sulfite oxidation including the formation of a Cu(II)–sulfito complex as an important step. For zinc, a surface mediated sulfite oxidation process leads to rapid formation of sulphate in the electrolyte droplet area. The presence of SO2 strongly inhibits the secondary spreading due to the decrease in pH induced by absorption of SO2 in the cathodic areas. The presence of gaseous oxidants, such as NO2 and O3, has previously been considered as an important prerequisite for the oxidation of sulfite on copper. The results obtained here suggest that the formation of local electrochemical cells induced by deposited NaCl particles could be another important route for S(IV)- oxidation to sulfate formation. On copper, SO2 was also found to promote the formation of less soluble copper chlorides, such as paratacamite (Cu2(OH)3Cl) and nantokite (CuCl). The electrolyte droplet was dried after 24 hours of exposure due to the formation of less soluble paratacamite (Cu2(OH)3Cl) and nantokite (CuCl) and led to a decrease in the corrosion rate. Thus, SO2 alone promotes the corrosion rate of copper, whereas in the presence of NaCl particles the corrosion rate of copper may slow down due to the formation of insoluble copper chloride compounds. The lateral distribution of corrosion products after exposure of NaCl contaminated copper and zinc surfaces to humid air with gaseous pollutants is a result of the formation of local electrochemical cells at the particles and concomitant differences in chemical composition and pH. For (NH4)2SO4 deposited copper and zinc surfaces the corrosion effects increase with the amount of pre-deposited particles and with the exposure time. On copper, the size of the particles affects the corrosion rate, smaller particles resulting in a higher corrosion rate than larger particles at equal amount of deposition. The formation of Cu2O was the dominant corrosion product after exposure longer than 10 days. (NH4)2SO4 particles result in enhanced Cu2O formation on copper due to a reaction sequence involving catalysis by NH3. The corrosion of copper by (NH4)2SO4 particles was much larger than that induced by NaCl particles. However, for zinc, the (NH4)2SO4 particles lead to smaller corrosion effects than those of NaCl particles. For both particles, significant corrosion attack was observed at relative humidity (RH) lower than the deliquescence point of the salts. / QC 20101001

Phenol is highly reactive toward electrophilic aromatic substitution. By this general approach, many groups can be appended to the ring, via halogenation, acylation, sulfonation, and other processes. Phenol contains the hydroxyl group (–OH), which is a strongly activating ortho/para directing group in aromatic electrophilic substitution (AES). AES gives a mixture of ortho-and para isomers, which must be separated. The strong directing ability of phenol can also result in multiple substitutions on the aromatic ring which could be a major concern in the regiospecific synthesis of phenols. AES and Directed ortho--Metalation (DoM) are the only ways to directly substitute a proton on an aromatic ring and to synthesize regiospecifically substituted phenols. Phenol is a versatile precursor to a large collection of drugs, most notably aspirin, but also many herbicides and pharmaceuticals. AES reactions are useful in regiospecific synthesis as a way of introducing many reactive groups on the benzene ring and also help us to design a suitable method for synthesizing compounds in an efficient manner. Dimethylbenzylamine products are obtained as a result of the reaction of phenols with Eschenmoser’s salt (N,N-Dimethylmethyleneiminium iodide). This approach enables us to prepare regiospecifically ortho substituted phenols by using the AES protocol. We have discovered that Eschenmoser’s salt has the ability in basic medium containing triethylamine (TEA) to remove the proton and bond to the aromatic ring exclusively in ortho position to the –OH substituent. Our research work focused on efforts to render isolated products with minimum impurities, greener and more atom economical by use of limiting reagent in the reactions. For the purpose of evaluation of the obtained compounds and intermediates we use Gas Chromatography (GC), Gas Chromatography coupled with Mass Spectrometry (GC-MS) and Nuclear Magnetic Resonance (NMR). Our future work is to synthesize novel benzoheterocyclic compounds from the ortho-derivatised phenols as well as multi-substituted aromatic compounds. The dimethylamino methyl group can act as a directing group in the ortho-lithiation process; subsequent ortho--metalation and treatment with electrophiles generates 1,2,3- trisubstituted phenolic derivatives. Thus, phenolic precursors can be transformed into numerous derivatives which can be used in the chemical, agricultural and pharmaceutical industries.

Carbon dioxide removal from flue gases of power plants is critical for reduction of greenhouse gas emissions implicated in global warming. Metal Organic Frameworks (MOFs) promising potential applications in carbon dioxide capture due to their unique structural properties such as high porosity and high thermal stability. These MOFs have application in separation processes and gas storage. By the assembly of the organic ligands and metal oxide clusters, porous MOFs can be synthesized. The use of s-block metals such as calcium, magnesium and rubidium in porous materials is appealing because their ionic binding characters with organic ligands will general flexible MOFs. The bonding interaction of s-block metal centers with carboxylate oxygen atoms is mainly ionic in nature due to large differences in electronegativity. The s-block elements can form low density frameworks which could increase the gas uptake capacity of small molecules. This work focuses on synthesis of new metal organic frameworks (MOFs) using s-block metals. Different types of the carboxylic ligands were utilized for synthesis of MOFs. Four new calcium or rubdium metal organic frameworks, [Ca3(btc)2(H2O)12] (1) and [Ca2(btc)(pzc)(H2O)3] (2) (btc=benzene-1,3,5-tricarboxylate, pzc = pyrazine-2- carboxylate), [Ca(Hbtc)(H2O)]•H2O (6), and [Rb(Hbdc)] (7) have been synthesized using the hydro/solvothermal method and have been characterized using X-ray diffraction, IR, UV-vis, TGA and fluorescence analysis. The structures of compounds 1, 6 and 7are three-dimensional frameworks while that of compound 2 is a double layered network.

Heavy metal contamination is a serious concern throughout the world. Increased concentrations in drinking water have many negative impacts on human health. Limestone is an inexpensive and simple media for removing high concentrations of heavy metals from drinking water supplies. Ferric based media is commonly used to remove zinc, cadmium, lead, arsenic and other heavy metals. The drinking water standards set by the US EPA for cadmium, zinc and arsenic are 0.005 mg/L, 5 mg/L and 0.010 mg/L respectively. Bangladesh, parts of India, China and the United States have high concentrations of arsenic in drinking water. Although many technologies exist for heavy metal removal, most of these are complicated and are associated with high costs making them ineffective and unfavorable to be used in impoverished areas. We propose a novel method that combines the benefits of limestone with the capacity of ferric media in an iron-coated limestone based material. Samples of water with various concentrations of zinc and cadmium were prepared and batch tests were performed using both uncoated and iron coated limestone and are compared in removal efficiency. Kinetics studies showed that zinc is removed to a maximum level after 24 hours, while cadmium takes only 15 minutes. The effect of pH on removal of heavy metals was also studied. Metals are analyzed using Inductively Coupled Plasma Emission Spectroscopy (ICP-ES). Limestone is readily available and is also easy to coat with iron, making this material a cost effective and affordable method to be used by developing countries.

Extractants and extraction methodologies play a vital role in many industrial processes, from the concentration of precious metals from ores to the separation of longlived nuclei from radioactive waste as well as the removal of heavy metals from soils and water for remediation. The vast majority of extractants rely on the use of nitrogen, oxygen, sulfur or selenium as Lewis base donor atoms to form coordination complexes with the metal ions of interest. These extractants often make use of the chelate effect and/or the macrocyclic effect in order to form stable complexes. Some of the best known types of chelate extractants include polyaminopolycarboxylic acids (N and O donors), polyamines (N donors), dithiocarbamate (S donors) and aminopolythias (N and S donors). The most extensively investigated types of macrocycles include crown ethers (O donors), thia crowns (S donors), aza crowns (N donors) and thiacrown ethers (S and O donors). A conspicuous omission from the list of donor atoms is phosphorus. It is noted that phosphorus has been employed as a backbone atom in the development of extractants, primarily in phosphonates, phosphates and phosphine oxides. The omission of phosphorus is interesting from two points. First, many of the precious and heavy metal ions of interest (Pd2+, Ag+, Pt2+, Pb2+, Cd2+and Hg2+) can be classified as soft Lewis acids, according to Pearson’s HSAB theory. The relative softness of phosphorus as a Lewis base as compared to oxygen and nitrogen indicates that phosphorus would be a very good donor atom toward these soft metal cations. Secondly, chelating agents containing phosphorus donors form stable complexes with transition metal cations in a variety of oxidation states due to their versatile bonding capability. The !-donor characteristics of the phosphine donor coupled with the ability to " accept from filled or partially filled d orbitals of the metal cations result in strong phosphine-metal bonds.

Heterocyclic organic and organometallic compounds (e.g. polypyrrole), and their derivatives, have been of great interest for conductive polymers due to their novel properties and environmental stability as compared to non-aromatic analogs (e.g. polyacetylene). Our current interests focus upon the potential role of pyridazines in next generation electronic devices that utilize organics as the semiconducting material. Pyridazines, 6-membered aromatic rings with two adjacent nitrogens, are promising candidates for a variety of materials and commercial applications. These molecular electronic materials posses several advantages over traditional inorganic semiconducting materials including lower cost of production, higher processibility, and the ability to function on flexible substrates (so called “plastic electronics”). These compounds offer new materials suitable for a variety of real world applications such as Organic Light Emitting Diodes (OLEDs) and Organic Photovoltaic Cell (OPVs). Our recent efforts has been focused on the synthesis of a variety of 5,6-fused ring pyridazines. These fused heterocycles will serve as synthetic models and building blocks for potential organic or organometallic conducting polymers. Our work is focused on the synthesis of pyridazines and their organometallic rhenium complexes and polymer research. Several aryl-substituted 5,6-fused ring pyridazines have been synthesized and characterized. A pyridazyl complexe of rhenium was synthesized in three steps beginning with a 5,6-fused pyridazine. Off-metal synthesis and characterization of [Re(CO)3{1,2-C5H3(CC6H5N)(CC6H5N)}] and some aryl-substituted pyridazines (1,2-C5H3(CRNH)(CRN); R = C6H5, C4H3S, C8H5S) are reported herein.

Zirconia is one of the most promising column packing materials for High Performance Liquid Chromatography (HPLC). The perfect HPLC support material should be energetically homogenous, have a high surface area on which different chemical species can reversibly attach and be physically and chemically stable over a wide range of pH, temperature and solvent conditions. Most existing supports do not have all of these properties. This project is also focused on a proteomics study. Zirconia, hafnium oxide and titanium oxide which are some of the more promising materials currently available, can be used for the separation and analysis of phosphorylated proteins. Adenosine triphosphate, Adenosine diphosphate and Adenosine monophosphate were used as prototypes for phosphorylated proteins. Separation, absorption, fluorescence and SEM studies were performed to determine the adsorption of Adenosine phosphates species at a particular pH on Zirconia. Zirconia was also used for the purification of Fibrinogen Growth Factor (FGF) protein, which are a family of growth factors involved in angiogenesis, wound healing, and embryonic development. The sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) technique was used to analyze the off-column purification and separation of this protein. This research suggests that, at acidic conditions, adenosine monophosphate has more favorable absorption on the Zirconia surface. On the other hand, the separation study suggests that basic conditions are more favorable for the absorption of ATP, ADP and AMP when mixed together on Zirconia 500. Furthermore, it was found that Zirconia is a very promising material for the purification of FGF protein.