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The first study project is based on modeling Earth abundant 3d transition-metal methoxide complexes with potentially redox-noninnocent ligands for methane C–H bond activation to form methanol (LnM-OMe + CH4 → LnM–Me + CH3OH). Three types of complex consisting of tridentate pincer terpyridine-like ligands, and different first-row transition metals (M = Ti, V, Cr, Mn, Fe, Co, Ni, and Cu) were modeled to elucidate the reaction mechanism as well as the effect of the metal identity on the thermodynamics and kinetics of a methane activation reaction. The calculations showed that the d electron count of the metal is a more significant factor than the metal's formal charge in controlling the thermodynamics and kinetics of C–H activation. These researches suggest that late 3d-metal methoxide complexes that favor σ-bond metathesis pathways for methane activation will yield lower barriers for C–H activation, and are more profitable catalyst for future studies. Second, subsequently, on the basis of the first project, density functional theory is used to analyze methane C−H activation by neutral and cationic nickel-methoxide complexes. This study identifies strategies to further lower the barriers for methane C−H activation through evaluation of supporting ligand modifications, solvent polarity, overall charge of complex, metal identity and counterion effects. Overall, neutral low coordinate complexes (e.g. bipyridine) are calculated to have lower activation barriers than the cationic complexes. For both neutral and cationic complexes, the methane C−H activation proceed via a σ-bond metathesis rather than an oxidative addition/reductive elimination pathway. Neutralizing the cationic catalyst models by a counterion, BF4-, has a considerable impact on reducing the methane activation barrier free energy. Third, theoretical studies were performed to explore the effects of appended s-block metal ion crown ethers upon the redox properties of nitridomanganese(V) salen complexes, [(salen)MnV(N)(Mn+-crown ether)]n+, where, M = Na+, K+, Ba2+, Sr2+ for 1Na, 1K, 1Ba, 1Sr complexes respectively; A = complex without Mn+-crown ether and B = without Mn+). The results of the calculations reveal that ΔGrxn(e ̶ ) and thus reduction potentials are quite sensitive to the point charge (q) of the s-block metal ions. Methane activation by A, 1K and 1Ba complexes proceeds via a hydrogen atom abstraction (HAA) pathway with reasonable barriers for all complexes with ~ 4 kcal/mol difference in energy, more favorable free energy barrier for the complexes with higher point charge of metal ion. Changes in predicted properties as a function of continuum solvent dielectric constant suggest that the primary effect of the appended s-block ion is via "through space" interactions. Finally, a comprehensive DFT study of the electrocatalytic oxidation of ammonia to dinitrogen by a ruthenium polypyridyl complex, [(tpy)(bpy)RuII(NH3)]2+ (complex a), and its NMe2-substituted derivative (b), is presented. The thermodynamics and kinetics of electron (ET) and proton transfer (PT) steps and transition states are calculated. NMe2 substitution on bpy reduces the ET steps on average 8 kcal/mol for complex b as compared to a. The calculations indicate that N–N formation occurs by ammonia nucleophilic attack/H-transfer via a nitrene intermediate, rather than a nitride intermediate. Comparison of the free energy profiles of Ru-b with its first-row Fe congener reveals that the thermodynamics are less favorable for the Fe-b model, especially for ET steps. The N-H bond dissociation free energies (BDFEs) for NH3 to form N2 show the following trend: Ru-b <Ru-a <Fe-b, indicating the lowest and most favorable BDFEs for Ru-b complex.

The selective catalytic oxidation of NH3 (NH3 -SCO) into N2 and H2O is an efficient technology for NH3 abatement in diesel vehicles. However, the catalysts dedicated to NH3 -SCO are still under development. One of the groups of such catalysts constituted transition metal-based catalysts, including hydrotalcite-derived mixed metal oxides. This class of materials is characterized by tailored composition, homogenously dispersed mixed metal oxides, exhibiting high specific surface area and thermal stability. Thus, firstly, we give a short introduction to the structure and composition of hydrotalcite-like materials and their applications in NH3 -SCO. Secondly, an overview of other transition metal-based catalysts reported in the literature is given, following a comparison of both groups. The challenges in NH3 -SCO applications are provided, while the reaction mechanisms are discussed for particular systems

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O processo Humifert é uma alternativa para produção de compostos fertilizantes fosfatados, com solubilização mais lenta do que os fertilizantes tradicionais, resultando em um tempo de nutrição da planta maior. No processo, utilizam-se rochas fosfáticas com algum tipo de limitação para o aproveitamento normal, seja pelos teores menores, seja por dificuldades de tratamento industrial dos minérios, além de materiais orgânicos. O objetivo deste trabalho foi melhorar o equipamento existente no Instituto de Geociências, para tornar possível condições de produção de NOx, no Processo Humifert, capaz de produzir um teor de fósforo disponibilizado em condições controladas de processo. Empregando-se planejamento estatístico de experimentos foi possível selecionar as variáveis de entrada mais importantes ao processo (agitação da mistura de rocha fosfática, matéria orgânica e umidade, A codificada; temperatura de oxidação da amônia, B codificada; umidade da mistura, C codificada; porosidade da placa difusora, D codificada; vazão do ar auxiliar, E codificada). A análise estatística, também, permitiu construir modelos de regressão nos quais as influências das variáveis de processo foram sentidas na solubilidade do fósforo nos extratores: ácido cítrico, solução 2% (Pácido cítrico); água, (Págua); citrato neutro de amônio mais água, (PCNA+água). Estas últimas variáveis aqui denominadas de variáveis de saída ou de resposta. A manipulação dos referidos modelos permite obter o fertilizante de acordo com as necessidades da cultura e do solo. O estudo, também, permitiu concluir que a maior quantidade de fósforo disponível nos compostos organofosfatados foi o solúvel em ácido cítrico, portanto, a maior quantidade de compostos gerados encontra-se na melhor condição de disponibilidade pela planta. / Humiphert process is an alternative used for producing phosphated compound fertilizers with a slower solubilization when compared to other traditional fertilizers, resulting in a longer period of plant nutrition. During the process, phosphatic rocks are used along with some sort of limitation according to the normal development, both by their lower content percentage and by treatment of difficulties of industrial ores, besides organic materials. This work aim to improve an equipment existing at the Instituto de Geociências in order to find out the best process condition to produce NOX in Humifert process. This way, the process is able to produce an available phosphorus content under process conditions controlled. The process variables were select by using of experimental design. These variables were: agitation of phosphatic rock mixture (rock, organic material and humidity), A coded; ammonia oxidation temperature, B coded; humidity of mixture, C coded; porosity of the diffusing board, D coded; auxiliary air, E coded. Statistical analysis also allowed to build regression models in which the influences of process variables were felt in the solubility of phosphorus in the extractors: 2% solution of citric acid (Pacid Citric), water (Pwater); ammonium neutral citrate plus water (PCNA + water). These last variables here called output variable or response. The manipulation of these models allows to obtain the fertilizer according to the needs of the crop and soil. The study still conclude that the greater amount of available phosphorus in compound was soluble in citric acid, therefore, a greater amount of compounds generated is in the best condition of availability for the plant. The study still conclude that the greater amount of available phosphorus in the organophosphated compounds were soluble in citric acid. Therefore, the greater amount of compounds generated is in the best condition of availability for the plant.

O processo Humifert é uma alternativa para produção de compostos fertilizantes fosfatados, com solubilização mais lenta do que os fertilizantes tradicionais, resultando em um tempo de nutrição da planta maior. No processo, utilizam-se rochas fosfáticas com algum tipo de limitação para o aproveitamento normal, seja pelos teores menores, seja por dificuldades de tratamento industrial dos minérios, além de materiais orgânicos. O objetivo deste trabalho foi melhorar o equipamento existente no Instituto de Geociências, para tornar possível condições de produção de NOx, no Processo Humifert, capaz de produzir um teor de fósforo disponibilizado em condições controladas de processo. Empregando-se planejamento estatístico de experimentos foi possível selecionar as variáveis de entrada mais importantes ao processo (agitação da mistura de rocha fosfática, matéria orgânica e umidade, A codificada; temperatura de oxidação da amônia, B codificada; umidade da mistura, C codificada; porosidade da placa difusora, D codificada; vazão do ar auxiliar, E codificada). A análise estatística, também, permitiu construir modelos de regressão nos quais as influências das variáveis de processo foram sentidas na solubilidade do fósforo nos extratores: ácido cítrico, solução 2% (Pácido cítrico); água, (Págua); citrato neutro de amônio mais água, (PCNA+água). Estas últimas variáveis aqui denominadas de variáveis de saída ou de resposta. A manipulação dos referidos modelos permite obter o fertilizante de acordo com as necessidades da cultura e do solo. O estudo, também, permitiu concluir que a maior quantidade de fósforo disponível nos compostos organofosfatados foi o solúvel em ácido cítrico, portanto, a maior quantidade de compostos gerados encontra-se na melhor condição de disponibilidade pela planta. / Humiphert process is an alternative used for producing phosphated compound fertilizers with a slower solubilization when compared to other traditional fertilizers, resulting in a longer period of plant nutrition. During the process, phosphatic rocks are used along with some sort of limitation according to the normal development, both by their lower content percentage and by treatment of difficulties of industrial ores, besides organic materials. This work aim to improve an equipment existing at the Instituto de Geociências in order to find out the best process condition to produce NOX in Humifert process. This way, the process is able to produce an available phosphorus content under process conditions controlled. The process variables were select by using of experimental design. These variables were: agitation of phosphatic rock mixture (rock, organic material and humidity), A coded; ammonia oxidation temperature, B coded; humidity of mixture, C coded; porosity of the diffusing board, D coded; auxiliary air, E coded. Statistical analysis also allowed to build regression models in which the influences of process variables were felt in the solubility of phosphorus in the extractors: 2% solution of citric acid (Pacid Citric), water (Pwater); ammonium neutral citrate plus water (PCNA + water). These last variables here called output variable or response. The manipulation of these models allows to obtain the fertilizer according to the needs of the crop and soil. The study still conclude that the greater amount of available phosphorus in compound was soluble in citric acid, therefore, a greater amount of compounds generated is in the best condition of availability for the plant. The study still conclude that the greater amount of available phosphorus in the organophosphated compounds were soluble in citric acid. Therefore, the greater amount of compounds generated is in the best condition of availability for the plant.

In recent years considerable interest has been shown in the diversity of ammonia-oxidizing bacteria in soil communities. The majority of the research has been carried out in Northern Europe where soils have received high atmospheric inputs of nitrogen over the past two centuries. In contrast, although much work has been conducted on nitrogen cycling processes in nitrogen limited forest ecosystems in western North America, no studies have examined the characteristics of ammonia-oxidizing communities in those environments. I was interested in measuring nitrification potential along a high-elevation temperate meadow-to-forest gradient, and characterizing the ammonia-oxidizing communities along that gradient using both molecular and culturing methods. Two experimental sites (Lookout and Carpenter) were chosen in the H.J. Andrews Experimental Forest, located in the western Cascade Range of Oregon, at elevations of approximately 1500 meters. Although nitrification potential rates (NPRs) between sites were not significantly different (P=0.544), variation was observed both within and between sites for specific vegetation types. NPRs were significantly lower in forest (F) soil samples than in meadow (M) soil samples, averaging 5 and 2% of meadow NPRs at Lookout and Carpenter, respectively. In meadow soil samples, most probable number (MPN) population densities of ammonia-oxidizers ranged from 0.6 to 2.6 x 10⁴ cells gram⁻¹ of oven dry soil and 0.9 x 10³ to 1.1 x 10⁵ cells g⁻¹ OD soil at Lookout and Carpenter, respectively. In forest soil samples, population densities ranged from undetectable to 1.1 x 10⁴ cells g⁻¹ OD soil, and 0.9 x 10² to 2.3 x 10³ cells g⁻¹ OD soil at Lookout and Carpenter, respectively. Microbial community DNA was amplified using primers to the ammonia monooxygenase subunit A. Terminal restriction fragments polymorphism analysis with three different restriction enzymes (CfoI, TaqI, and AluI) revealed community profiles dominated by Nitrosospira species. One fragment from CfoI (66 bp) and one fragment from AluI (392-bp) were prominent in 47 soil samples from both sites, and represented between 32 to 100% of the Genescan fragment analyses of PCR products. A full length fragment from AluI digests (491-bp), and three fragments from CfoI (68, 100, and 135- bp) were found sporadically in fewer soil sample T-RFLPs, and within those samples represented smaller percentages of total peak areas. The CfoI 135-bp fragment length was associated primarily with M and meadow/forest (M/F) soils where it was observed in approximately 58 and 100% of the respective transect locations. Eight isolates recovered from soil samples were analyzed using the same molecular methods as the field samples. The T-RFLP patterns of the isolates corresponded with many of those found in the community fingerprints. Four unique amoA sequences were identified among these isolates, including one that possessed the dominant T-RFLP amoA fingerprint in soil samples. This sequence shared 99.8% similarity with Nitrosospira sp. Ka4, a cluster 4 ammonia oxidizer isolated in Norway. Sequence analysis phylogenetically associated the other three isolates (with unique amoA sequences) near Nitrosospira sp. Nsp 1 and Nitrosospira briensis, both cluster 3 ammonia oxidizers. Cloning and sequencing of soil DNA confirmed that ammonia oxidizers with these amoA sequences were present in the soil samples. Two additional amoA sequences were identified in clones that were 95% similar and paraphylogenetically positioned between representatives of clusters 3 and 4. So far, these sequences have not been found in any of the isolates analyzed. / Graduation date: 2003

Miljöriskbedömningar av förorenade områden i Sverige har traditionellt sett främst bedömt saneringsbehovet genom att mäta totalhalter av föroreningarna. Halterna jämförs sedan med riktvärden för att avgöra om de utgör en risk för något av skyddsobjekten. Oftast blir markmiljön det skyddsobjekt som har lägst riktvärde och därmed avgör saneringsbehovet. Kritik har riktats mot att andra faktorer än föroreningshalter borde mätas för att bedöma markkvalitet då den kan vara hög oavsett föroreningssituation. Det är inte heller självklart att en sanering leder till en förbättring av markekosystemet. I Sverige har över 85 000 områden identifierats som potentiellt eller konstaterade förorenade områden. För att förbättra riskbedömningar behövs bättre vägledning om vad som ska ingå i riskbedömningar och för det behövs kunskap om vad som påverkar markfunktionerna.I det här examenarbetet har nitrifikationspotentialen, också kallat ammoniakoxidation, bestämts för 50 jordprover från fastigheten Skönsmon 2:12 i Sundsvalls kommun med hjälp av ISO metoden 15685. Tidigare industriverksamheter på fastigheten har lett till att marken är förorenad med bland annat tungmetaller och polycykliska aromatiska kolväten. Markens förmåga att utföra nitrifikation är en viktig markfunktion för att säkerställa en god markkvalitet. Men vilka markfaktorer som i störst utsträckning påverkar ammoniakoxidationen är inte helt klarlagt, liksom hur olika typer av miljöföroreningar påverkar nitrifikationen. Detta behöver klargöras för att kunna bedöma om ISO-metoden 15685 är ett lämpligt verktyg för markekologiska riskbedömningar av förorenade områden. Nitrifikationsanalysen på de 50 jordproverna har därför jämförts med data över föroreningshalter, markparametrar samt mängden ammoniakoxiderande bakterier och arkéer. Resultatet visar att nitrifikationen på den här lokalen främst påverkas av markparametrarna: totalkväve, organiskt material samt ”tillgänglig” fosfor och i mindre utsträckning av föroreningsnivåerna. Detta betyder att det vid undersökningar av hur föroreningar påverkar nitrifikationen måste finnas referensprover med liknande markkvalitet att jämföra med. Den potentiella nitrifikationen visar också stark korrelation till populationen ammoniakoxiderande bakterier vilket indikerar att de står för det största bidraget till ammoniakoxidationen i marken. / Environmental risk assessment of contaminated sites in Sweden has traditionally mainly assessed the need of remediation by measuring the total concentrations of pollutants. The pollution levels are then compared with guideline values to determine if they represent a risk to any of the protected targets. Most often, the soil environment is the protection target with the lowest guideline value and thus determines the need for remediation.There has been some criticism about using total concentration of pollutants as the only method of assessing soil quality, since soil quality may be high regardless of the situation of the polluted area. In addition, it is not clear if the remediation will always lead to an improvement of the soil quality. In Sweden, more than 85,000 sites have been identified as potential or confirmed contaminated areas. In order to improve risk assessments, better guidance is needed regarding what information should be included. This requires knowledge of which factors are affecting the soil functions.In this thesis, potential nitrification has been determined for 50 soil samples from the property Skönsmon 2:12 in the municipality of Sundsvall using ISO standard 15685. Previous industrial activities on the property have resulted in the soil being contaminated with, for instance, heavy metals and polycyclic aromatic hydrocarbons. The ability of the soil to perform nitrification is an important soil function to ensure good soil quality. However, it is not entirely clear which soil factors affect nitrification to the greatest extent, nor how different types of environmental pollution affect nitrification. This needs to be clarified in order to assess whether ISO 15685 is an appropriate tool for soil ecological risk assessments of contaminated sites. The nitrification data of the 50 soil samples have therefore been compared with data of pollutants, soil parameters, and the amount of ammonia oxidizing bacteria and archaea. This study showed that ammonia oxidation at this site is mainly affected by the soil parameters total nitrogen, organic matter, and “available” phosphorus content, but to a lesser extent of the pollutant levels. This means that when examining how pollutants affect nitrification, reference samples with similar soil quality must be included for comparison. The potential nitrification showed a strong correlation with the population of ammonia oxidizing bacteria, which indicates that they account for the biggest contribution to ammonia oxidation in the soil.

Philosophiae Doctor - PhD / Ammonia has attracted attention as a possible fuel for direct fuel cells since it is easy to handle under low pressure, costs only slightly higher than methanol and can easily be cracked down into hydrogen and nitrogen. At low temperature, ammonia oxidation on noble metal electrodes is a sluggish reaction and efficient catalysts are required to convert ammonia to nitrogen and hydrogen at reasonable reaction rates. In this thesis, I present polycrystalline and oriented nanoalloys synthesised at room temperature in aqueous media and their catalytic effects on the oxidation of ammonia. The electro-oxidation of ammonia on palladium-goldsilver (PdAuAgNPs) ternary nanoalloys was systematically studied in alkaline solution of potassium hydroxide (KOH) by cyclic voltammetry (CV). The PdAuAg nanoalloys were prepared through a facile synthesis with ascorbic acid as a reductant and polyvinylpyrrolidone (PVP) as a stabilising agent from aqueous solutions of PdCh/HAuCI4.3H20/AgN03 mixtures. UV-visible spectroscopy was used to confirm the complete reduction of the metal ions; absorption peaks observed at 260 nm, 285 nm and 420 nm for Ag", Au3+ and Pd2+ ions respectively, disappeared after reduction indicating a complete reduction of the metal ions to zero-valent nanoparticles. High resolution transmission electron microscopy (HR TEM) revealed the formation of crystalline nonaggregated 25-35 nm sized nanoalloys. The elemental composition of the nanoalloys measured using energy dispersive X-ray spectroscopy (EDX) showed the presence of the three elements; Pd, Au and Ag. The well-dispersed non-agglomerated PdAuAg nanoalloys exhibited a reduced overpotential and a 33%, 400%,82% and 54% increase in current density for ammonia electro-oxidation compared to Pd, PdAg, PdAu nanoparticles and bare Pt electrode, respectively. The much improved current density of the well-dispersed PdAuAg nanoalloys is attributed to the increased electrochemically active surface area of the nanoalloys. This electro catalytic behaviour of the PdAuAg nanoalloys for ammonia oxidation in KOH solutions provides a promising route for development of low-cost and high performance electro catalyst for electro-oxidation of ammoniaMoreover, ammonia oxidation on platinum surfaces has been found to be a very structure sensitive reaction which takes place almost exclusively on Pt(100) surfaces. I report for the first time the preparation of sodium polyacrylate-capped Pt(100)Pd, pte 1OO)Au, pte 1OO)Ir, Pt(IOO)Rh, Pt(100)PdAu, Pt(100)IrAu, Pt(IOO)PdIr and Pt(IOO)RhAu nanoalloys. The reduction of the metal ions to nanoparticles was confirmed by UV-visible spectroscopy while the shapes and the structures of the nanoparticles were studied using HRTEM and CV. HRTEM analysis showed well distributed non-agglomerated 5-20 nm semi-spherical and cubic nanoalloys with lattice fridges on their surfaces indicating the crystalline nature of the nanoalloys. Pt(100) nanoalloy systems showed particles with triangular and cubic shapes. The existence of the preferentially cubic shaped nanoparticles in the samples indicated that the nanoalloys had some (100) sites orientation/a significant amount of (100) sites at their surfaces. The CV of the nanoparticles in the hydrogen adsorption/desorption region (-200 mV to 100 mV vs. Ag! AgCl) was used to obtain qualitative information about the surface structure of the nanoparticles. The voltammogram of oriented Pt(100) nanoparticles showed very clearly the presence of adsorption states associated with (110) sites, (100) domains and (l00) sites at -131 mV, -34 mV and 29 mV, respectively. The companson of this voltammetric profile with that obtained for a Pt(100) single crystal electrode clearly points out that the synthesised Pt nanoparticles have a high density of (100) sites. However, the peak that was observed at 29 mV in the CV of Pt(100) nanoparticles was not present in the vo ltammo grams of the Pt(100) nanoalloy systems confirming the formation of the nanoalloys. The results reported in this work demonstrate the importance of controlling the intrinsic structural properties of Pt nanoparticles; in terms of nature of the active sites and the effect of adding adatoms (such as Au, Pd, Rh, Ir) in order to understand their catalytic properties. The electrochemical activities of these nanoparticles for ammonia oxidation in basic medium showed an increase of over 100% current density compared to Pt electrode. Pt(lOO)RhAu nanoalloys showed the highest catalytic properties while Pt(lOO)PdAu had the lowest as shown in the trend: Pt(lOO)RhAu > Pt(lOO)PdIr > Pt(lOO) > Pt(lOO)IrAu > Pt(lOO)Pd> Pt(lOO)Rh > Pt(lOO)Au > Pt(lOO)Ir > Pt(lOO)PdAu. The synthesised oriented nanoalloys were further interrogated towards the oxidation of hydrazine as a fuel for hydrazine fuel cells. The oriented Pt(lOO) nanoparticles and Pt(lOO) nanoalloy systems exhibited over 1000% increase in current density and reduced oxidation overpotential compared to bare glassy carbon electrode. These excellent catalytic properties are attributed to the increased surface area and the presence of (100) sites which favour the oxidation of hydrazine.

No description available.