This research is aimed at synthesizing millimeter-scale carbon nanotube arrays (CNTA) by conventional chemical vapor deposition (CCVD) and water-assisted chemical vapor deposition (WACVD) methods, and exploring their application as catalyst supports for electrochemical supercapacitors. The growth mechanism and growth kinetics of CNTA under different conditions were systematically investigated to understand the relationship among physical characteristics of catalyst particles, growth parameters, and carbon nanotube (CNT) structures within CNTAs. Multiwalled CNT (MWCNT) array growth demonstrates lengthening and thickening stages in CCVD and WACVD. In CCVD, the lengthening and thickening were found to be competitive. By investigating catalyst particles after different pretreatment conditions, it has been found that inter-particle spacing plays a significant role in influencing CNTA height, CNT diameter and wall number. In WACVD, a long linear lengthening stage has been found. CNT wall number remains constant and catalysts preserve the activity in this stage, while MWCNTs thicken substantially and catalysts deactivate following the previously proposed radioactive decay model in the thickening stage of WACVD. Water was also shown to preserve the catalyst activity by significantly inhibiting catalyst-induced and gas phase-induced thickening processes in WACVD. Mn3O4 nanoparticles were successfully deposited and uniformly distributed within millimeter-long CNTAs by dip-casting method from non-aqueous solutions. After modification with Mn3O4 nanoparticles, CNTAs have been changed from hydrophobic to hydrophilic without their alignment and integrity being destroyed. The hydrophilic Mn3O4/CNTA composite electrodes present ideal capacitive behavior with high reversibility. This opens up a new route of utilizing ultra-long CNTAs, based on which a scalable and cost-effective method was developed to fabricate composite electrodes using millimeter-long CNTAs. To improve the performance of the composites, -MnO2 nanorods were anodically pulse-electrodeposited within hydrophilic 0.5 mm-thick Mn3O4 decorated CNTAs. The maximum gravimetric capacitance for the MnO2 nanorods/CNTA composite electrode was found to be 185 F/g, and that for -MnO2 nanorods was determined to be 221 F/g. After electrodeposition, the area-normalized capacitance and volumetric capacitance values were increased by a factor of 3, and an extremely high area-normalized capacitance of 1.80 F/cm2 was also achieved for the MnO2 nanorods/CNTA composite. / Materials Engineering

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Oxyborate minerals can represent the most important sink for boron in silica-undersaturated mineralised systems such as those of the Långban-type. Yet, their distribution, characteristics and parageneses are still not completely known. In order to test the hypothesis that the chemical compositions of oxyborates are essentially reflecting their local environments, the present study was set up. Additional observations regarding their assemblages, textures and structure would allow for a broader understanding of their formation and paragenetic interrelationships. A representative selection of Mg-(Fe-Mn) oxyborates and associated minerals have been characterised using optical microscopy, field emission electron probe microanalysis (FE-EPMA) with wavelength dispersive spectroscopy (WDS), and Raman spectroscopy. The studied samples are from a suite of carbonate-hosted Fe-Mn oxide deposits in the western part of the Palaeoproterozoic Bergslagen ore province, in south central Sweden and include the minerals blatterite [(Mn2+,Mg)35(Mn3+,Fe3+)9Sb5+3(BO3)16O32], fredrikssonite [Mg2(Mn3+,Fe3+)BO5], chemically variable ludwigites [c. (Mg,Fe2+)2Fe3+BO5], orthopinakiolite [(Mg,Mn2+)2Mn3+BO5] and pinakiolite [(Mg,Mn2+)2(Mn3+,Sb5+)BO5]. The results show a correlation between the cation distribution in the oxyborates fredrikssonite, ludwigite, orthopinakiolite as well as pinakiolite, and their associated metal oxides consisting of hausmannite and spinel group minerals. This combined with the textural relationships of the phases suggests that the bulk contents of magnesium, manganese and iron in the oxyborates were sequestered from these pre-existing metal oxides. The chemically broad range of hausmannite and spinel group minerals associated with specifically fredrikssonite and ludwigite agrees with their more frequent general occurrence, compared to orthopinakiolite and pinakiolite. Raman spectroscopy verified the structural character of the studied oxyborates and indicates a potential connection between the presence of manganese and whether local BO33- ions are allowed to be positioned in symmetry sites which result in a split E´ mode. The results from this study contribute to the understanding of this family of minerals and their potential diversity in mineralised systems, and form a fundamental prerequisite for their potential application for boron isotope studies. / Mineral är kemiska föreningar eller rena grundämnen som har en väldefinierad kemisk sammansättning, ordnad kristallstruktur och är bildade av geologiska processer. Oxyborater är en typ av sådana föreningar vilka innehåller grundämnena bor och syre samt olika kombinationer av metalliska grundämnen. Oxyboratmineral kan bland annat bildas i och omkring malmfyndigheter där grundämnet kisel är ovanligt eller icke förekommande, och kan utgöra de viktigaste borföreningarna i vissa sådana miljöer. Genom att bättre förstå denna typ av mineral och de kemiska och bildningsmässiga samband som finns mellan dem och andra föreningar kan vi få en större kunskap om hur de bildas, samt hur olika grundämnen kan omfördelas i sådana geologiska system. I denna studie har ett representativt urval av oxyborater undersökts med hjälp av mikroskopi och mikrokemiska samt spektroskopiska metoder för att testa huruvida deras kemiska sammansättning är direkt kopplad till den lokala miljön. De studerade proven kommer från karbonatbundna mineraliseringar i den västra delen av malmprovinsen Bergslagen i södra Mellansverige. De mineral som undersökts närmre är oxyboraterna blatterit, fredrikssonit, ludwigit, ortopinakiolit och pinakiolit. Resultaten visar på direkta kemiska samband mellan uppträdandet av fredrikssonit, ludwigit, ortopinakiolit samt pinakiolit, och de lokalt bergartsbildande mineral som de samexisterar med. Den breda kemiska fördelningen hos de metall- och syreföreningar som finns i samma omgivning som fredrikssonit och ludwigit förklarar också varför dessa två oxyborater generellt är mera vanligt förekommande än ortopinakiolit och pinakiolit. De spektroskopiska analyserna verifierar den tidigare klassificeringen av de studerade oxyboraterna samt visar på ett möjligt samband mellan innehållet av metallen mangan, samt hur grundämnet bor förekommer i deras kristallstruktur. Resultaten från denna studie bidrar med en kombination av nya kemiska, paragenetiska och spektroskopiska data samt ökar förståelsen av dessa värdmineral för grundämnet bor i malmfyndigheter med låg eller ingen kiselhalt. Resultaten ger även en insikt i hur den kemiska sammansättningen potentiellt kan påverka kristallstrukturen hos dessa oxyborater.

Metal oxide-facilitated transformation is likely an important degradation pathway of antibacterial agents at soil-water interfaces. Phenolic disinfectants (triclosan and chlorophene), fluoroquinolones (FQs), and aromatic N-oxides are of particular concern due to their widespread usage, potential toxicity and frequent detection in the environment. Results of the present study show that the above antibacterial agents are highly susceptible to metal oxide-facilitated oxidation. The interfacial reactions exhibit complex reaction kinetics, which are affected by solution pH, the presence of co-solutes, surface properties of metal oxides, and structural characteristics of antibacterial agents. Adsorption of the antibacterial agents to Mn and Fe oxide surfaces generally proceeds faster than oxidation reactions of these compounds by Mn and Fe oxides, especially in the case of Fe oxides. Reaction intermediates and end products are identified by GC/MS, LC/MS and/or FTIR. Structurally-related model compounds are examined to facilitate reaction site and mechanism elucidation. On the basis of experimental results and literature, reaction schemes are proposed. In general, the antibacterial agent is adsorbed to the oxide surface, forming a precursor complex. Electrons are transferred within the precursor complex from the antibacterial agent to the oxide, followed by releasing of the radical intermediates which undergo further reactions to generate oxidation products. The precursor complex formation and electron transfer are likely rate-limiting. For triclosan, phenoxy radicals are critical intermediates to form oxidation products through three pathways (i.e., radical coupling, further oxidation of the radical, and breakdown of an ether bond within the radical). The first two pathways are also operative in the oxidation of chlorophene. For FQs, oxidation generates radical intermediates that are most likely centered on the inner N in the piperazine ring. The radical intermediates then undergo three major pathways (i.e., radical coupling, N-dealkylation, and hydroxylation) to yield a variety of products. For aromatic N-oxides, a N-oxide radical intermediate is generated upon oxidation by MnO2, followed by the loss of oxygen from the N-oxide moiety and the formation of a hydroxyl group at the C-atom adjacent to the N-oxide moiety. Overall, a fundamental understanding of the reaction mechanisms between three classes of antibacterial agents and metal oxides has been obtained.