1 v. (various pagings) : ill., plates ; 26 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.1973) from the Dept. of Physical and Inorganic Chemistry, University of Adelaide

>Magister Scientiae - MSc / Fuel cells are widely considered to be efficient and non-polluting power source offering much higher energy density. This study is aimed at developing oxygen reduction reactions (ORR) catalysts with reduced platinum (Pt) loading. In order to achieve this aim, monometallic Pd and Pt nanostructured catalysts were electrodeposited on a substrate (carbon paper) by surface limited redox replacement using electrochemical atomic layer deposition (ECALD) technique. Pd:Pt bimetallic nanocatalysts were also deposited on carbon paper. Pd:Pt ratios were (1:1, 2.1 and 3:1). The prepared mono and bimetallic catalysts were characterized using electrochemical methods for the ORR in acid electrolyte. The electrochemical characterization of these catalysts includes: Cyclic Voltammetry (CV) and linear sweep voltammetry (LSV). The physical characterization includes: scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) for Morphology and elemental composition, respectively. The deposition of copper (Cu) on carbon paper was done by applying a potential of -0.05 V at 60s, 90s and 120s. 8x cycles of Pt or Pd showed better electrochemical activity towards hydrogen oxidation reaction. Multiples of eight were used in this work to deposit Pt: Pd binary catalyst. Cyclic voltammetry showed high electroactive surface area for Pt24Pd24/Carbon-paper while LSV showed high current density and positive onset potential. HRSEM also displayed small particle size compared to other Pt:Pd ratios.

In dieser Dissertation wurden das Auftreten und die ökologische Bedeutung Vivianits in Süßwassersedimenten erforscht. Vivianit ist das am weitensten verbreitete reduzierte Eisenphosphatmineral, das sich in Gewässersedimenten bildet. Über die Mechanismen der Vivianitbildung in Sedimenten und die quantitative Rolle des Minerals für die Speicherung von Phosphor ist bisher wenig bekannt. Die neuen Erkenntnisse dieser Arbeit basieren auf der Entwicklung einer neuartigen Methode, die eine direkte Identifikation Vivianits mittels Röntgendiffraktometrie in Sedimenten erlaubte. Es gelang erstmalig, Vivianit in Oberflächensedimenten zu quantifizieren. Die vorliegende Arbeit zeigt, dass Vivianit signifikant, mit 10-40 %, zur Phosphorretention in Süßwassersedimenten beitragen kann. Die Untersuchung der Bildungsbedingungen Vivianits in unterschiedlichen Gewässersedimenten Norddeutschlands zeigte, dass das molare Schwefel zu Eisen Verhältnis des Sediments als ein wichtiger Indikator für die Bedingungen identifiziert, welche die Triebkräfte für die An- und Abwesenheit Vivianits darstellen. Eine Eutrophierung von Gewässern und der damit verbundene Anstieg der Sulfidproduktion kann dabei die Bildung Vivianits beeinträchtigen, und eine Abnahme des Phosphorbindungsvermögens des Sediments zur Folge haben. Die vorliegende Arbeit macht deutlich, dass eine artifizielle Erhöhung des Eisengehaltes des Sediments im Rahmen einer Seenrestaurierung eine Vivianitbildung induzieren kann und so langfristig zu einem erhöhten Phosphorrückhalt führt. Sättigungsberechnungen ergaben, dass ein hinsichtlich Vivianits übersättigtes Porenwasser kein sicheres Indiz für die Anwesenheit des Minerals ist. Die Berechnungen sind nicht in der Lage die kleinskaligen chemischen Bedingungen im Porenraum des Sediments abzubilden. Die Untersuchungen zeigen, dass die Bildung von Vivianit einen wichtigen Prozess der Phosphorbindung in Gewässersedimenten darstellt, der bislang jedoch weitestgehend vernachlässigt wurde. / In this thesis, the occurrence and environmental relevance of vivianite in freshwater sediments were explored. Vivianite is the most common reduced iron phosphate mineral which forms in sedimentary environments. Not much is known about the mechanisms which lead to vivianite formation in surface sediments, and about the quantitative role of vivianite in phosphorus sequestration. The development of a novel sediment preparation technique allowed the direct identification of vivianite by powder X-ray diffraction. Notably, for the first time, vivianite was quantified in surface freshwater sediments. The study examplifies that vivianite can significantly contribute to the phosphorus retention in surface freshwater sediments, accounting for 10-40 % of total sedimentary phosphorus. The exploration of vivianite in different surface freshwater sediments located in northern Germany revealed that the sedimentary sulphur to iron ratio is a valuable indicator for the conditions that are important drivers behind the formation or absence of vivianite. It has been demonstrated that eutrophication and the accompanied increase in sulphide production hampers vivianite formation, leading to a decreased phosphorus binding capacity of sediments through increased sediment sulphidization. The present study also revealed, that an iron addition as a measure of lake restoration can trigger vivianite formation, and significantly increases the long-term phosphorus retention of sediments. Pore water equilibrium calculations demonstrated that supersaturated pore water is not sufficient to predict the occurrence of the mineral in situ. Those calculations often fail to predict the occurrence of vivianite because they do not adequately represent chemical conditions within sediment microenvironments. In summary, the formation of vivianite in aquatic sediments constitutes an important process in phosphorus sequestration which has so far largely been ignored.

Made available in DSpace on 2014-12-17T15:05:04Z (GMT). No. of bitstreams: 1 RogerioGA_DISSERT.pdf: 8092447 bytes, checksum: 8092c9fc8e1a9696dd331b3c086d01ac (MD5) Previous issue date: 2013-09-05 / The National Program of Professional Education Integration with Basic Education for Youngsters and Adults (PROEJA) Technical Professional Education Ensino M?dio has opened a new chapter in the history of education in Brazil, making possible the integration of basic education and professional education. This new form of education, which is still in its early implementation, presents a series of challenges to be overcome. Specifically about the teaching of Chemistry, didactic material to match PROEJA s specific needs is practically inexistent. Thus, this work has the purpose of developing didactic material for the teaching of Chemistry for Professional and Technological Education of Youngsters and Adults in the courses of Electronics, Technical Electronics and Maintenance and Support for Computing at Instituto Federal de Educa??o,Ci?ncia e Tecnologia do Rio Grande do Norte. This material aims at working chemical concepts of oxi-reduction reactions through a theme approach following Freire s conceptions for the teaching of Youngsters and Adults / O Programa Nacional de Integra??o da Educa??o Profissional com a Educa??o B?sica na Modalidade de Educa??o de Jovens e Adultos - Educa??o Profissional T?cnica de N?vel M?dio / Ensino M?dio (PROEJA) abriu um novo cap?tulo na hist?ria da educa??o de jovens e adultos, possibilitando a integra??o da educa??o profissional ? educa??o b?sica. Essa modalidade de educa??o, que ainda se encontra em fase inicial de implementa??o, apresenta uma s?rie de desafios a serem superados. No caso espec?fico de ensino de Qu?mica, ? praticamente inexistente material did?tico elaborado para atender ?s especificidades dos alunos do PROEJA. Nesse sentido, tivemos como prop?sito, no presente trabalho, o desenvolvimento de um material did?tico para o ensino de Qu?mica na Educa??o Profissional e Tecnol?gica de Jovens e Adultos nos cursos de eletr?nica, eletrot?cnica e manuten??o e suporte em inform?tica oferecidos pelo Instituto Federal de Educa??o,Ci?ncia e Tecnologia do Rio Grande do Norte. Esse material did?tico tem como objetivo trabalhar o conceito qu?mico de rea??es de oxirredu??o atrav?s de uma abordagem tem?tica seguindo as concep??es freireanas para Educa??o de Jovens e Adultos