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Catalisadores à base de CuO, Fe2O3 ou CuO-Fe2O3 suportados sobre y-Al2O3, ZrO2 ou ZrO2/y-Al2O3 para a redução de NO com COPires Neto, Nilson do Espírito Santo 31 March 2014 (has links)
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Previous issue date: 2014-03-31 / Universidade Federal de Sao Carlos / NO, NO2 and N2O nitrogen oxides, named NOx, strongly contribute to the air pollution and to minimize their emissions are used catalytic processes. The catalytic reduction of NO with CO has the advantage to simultaneously abate both pollutants. For that reaction are used noble metal based catalysts, but due to their scarcity and high cost, many research have been established to their substitution by transition metal oxides, which have high potential to catalyze that reaction. Those new catalysts beside to be active to the NO reduction with CO, they must be highly selective to N2 formation, stable at high temperatures and especially resistant to the presence of the interfering compounds (O2, SO2 and H2O). In this work were prepared Fe2O3, CuO or Fe2O3-CuO catalysts supported on y-Al2O3, ZrO2 or ZrO2/y-Al2O3. The supports were prepared via synthesis sol-gel using metallics alkoxides as precursors and the active phases introduced by impregnation of Fe(III) or Cu(II) nitrates. The obtained solids were characterized by X-ray diffraction (XRD), nitrogen adsorption/desorption measurements, hydrogen temperature programmed reduction (H2-TPR) and their activity evaluated by the reduction of NO with CO between 100 to 600°C in the presence or absence of SO2, O2 and H2O. The synthesis via sol-gel resulted in y-Al2O3 and ZrO2/y-Al2O3 supports with high specific surface area that allowed adequately distribute the CuO and Fe2O3 oxides, which did not present X ray diffraction peaks. The catalysts were considerably active in the reduction of NO with CO, with the bimetallic ones being slightly more selective to N2 formation. In the presence of SO2, the Fe2O3/y- Al2O3 and Fe2O3/ZrO2/y-Al2O3 catalysts showed more catalytic stability. The presence of O2 led to a significantly NO conversion loss due to the direct CO oxidation by O2. In the presence of H2O or of all the interfering compounds, the NO conversion loss was more pronounced, except the CuO/ZrO2, that was more resistant in the presence of H2O. / Os óxidos de nitrogênio NO, N2O e NO2, denominados de NOx, são fortes causadores da poluição atmosférica e, para minimizar suas emissões utilizam-se processos catalíticos. A redução de NO com CO tem a vantagem de abater simultaneamente ambos poluentes. Nessa reação, são utilizados catalisadores à base de metais nobres, mas, a sua escassez e alto custo têm direcionado pesquisas para a sua substituição por óxidos de metais de transição, os que mostram potencial para essa reação. Além de ativos, esses catalisadores devem ser seletivos à produção de N2, estáveis em altas temperaturas e sobre tudo estáveis na presença dos interferentes O2, H2O e SO2. Neste trabalho foram preparados catalisadores de Fe2O3, CuO ou Fe2O3-CuO suportados em y-Al2O3, ZrO2 ou ZrO2/y-Al2O3. Os suportes foram preparados via sol-gel, utilizando alcóxidos metálicos como precursores e, a introdução das fases ativas, efetuada via impregnação utilizando nitratos de Fe(III) ou Cu(II). Os suportes e catalisadores foram caracterizados por difração de raios X (DRX), fisissorsão de nitrogênio, redução com hidrogênio à temperatura programada (RTP-H2) e a sua atividade avaliada através da redução de NO a N2 com CO, entre 100 e 600°C, na ausência ou presença de interferentes. A síntese sol-gel resultou em suportes y- Al2O3 e ZrO2/y-Al2O3 de alta área superficial, permitindo uma adequada distribuição de CuO e Fe2O3, os que não apresentaram picos de DRX. Os catalisadores foram bastante ativos na redução de NO a N2, com os bimetálicos sendo ligeiramente mais seletivos à formação de N2. Na presença de SO2 os catalisadores Fe2O3/y-Al2O3 e Fe2O3/ZrO2/y-Al2O3 foram mais estáveis. A presença de O2 provocou significativa queda na conversão de NO, favorecendo a oxidação direta do CO. Na presença de H2O ou de todos os interferentes simultaneamente, a queda da conversão de NO a N2 sobre todos os catalisadores analisados foi total, com exceção ao catalisador de CuO/ZrO2, que foi mais resistente na presença de vapor de água.
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Optical and magnetic properties of rare earth Doped α-Fe2O3 for future bio-imaging applicationsMathevula, Langutani Eulenda 04 1900 (has links)
Imaging techniques have been developed for decades for the detection of biomolecules in
biomedicine cells, in vitro or in living cells and organisms. The application however, often
constrained by the available probes, whose optical properties may limit the imaging possibilities.
It is very essential to improve the sensitivity of these devices by enhancing efficiency to detection.
Recently, Fe3O4 has been used primarily in cancer theranostic application such as magnetic
resonance imaging (MRI). However, its toxicity towards normal cells has been pointed out by
scientific communities, when they are involved in in vitro (helics) cancer treatment. In this work,
we have chosen to use α-Fe2O3, because it has proven to be less toxic than Fe3O4. Hematite is
antiferromagnetic (AFM) at room temperature with a small canted moment lying within the crystal
symmetry plane. At low temperature, hematite undergoes a magnetic phase transition from weak
ferromagnetic (WFM) to a pure antiferromagnetic configuration (AF), which is known as the
Morin transition. This magnetic property makes it possible for hematite to be applied in imaging
technique. To enhance the optical properties, the α-Fe2O3 is doped with lanthanide ions due to their
unique optical properties. Incorporation of these rare earth ions, enable the α-Fe2O3 to have
enhance luminescence properties.
Imaging techniques have been developed for decades for the detection of biomolecules in
biomedicine cells, in vitro or in living cells and organisms. The application however, often
constrained by the available probes, whose optical properties may limit the imaging possibilities.
It is very essential to improve the sensitivity of these devices by enhancing efficiency to detection.
Recently, Fe3O4 has been used primarily in cancer theranostic application such as magnetic
resonance imaging (MRI). However, its toxicity towards normal cells has been pointed out by
scientific communities, when they are involved in in vitro (helics) cancer treatment. In this work,
we have chosen to use α-Fe2O3, because it has proven to be less toxic than Fe3O4. Hematite is
antiferromagnetic (AFM) at room temperature with a small canted moment lying within the crystal
symmetry plane. At low temperature, hematite undergoes a magnetic phase transition from weak
ferromagnetic (WFM) to a pure antiferromagnetic configuration (AF), which is known as the
Morin transition. This magnetic property makes it possible for hematite to be applied in imaging
technique. To enhance the optical properties, the α-Fe2O3 is doped with lanthanide ions due to their
unique optical properties. Incorporation of these rare earth ions, enable the α-Fe2O3 to have
enhance luminescence properties.
These lanthanide-doped nanoparticles (UCNPs) undergoes up-conversion process which have
remarkable ability to combine two or more low energy photons to generate a singly high energy
photon by an anti-stokes process and hold great promise for bio-imaging. These nanoparticles
exhibit excellent photostability, continuous emission capability and sharp multi-peak line
emission. With near infrared excitation, light scattering by biological tissues is substantially
reduced. α-Fe2O3 have been singly and co-doped with Holmium, Thulium, and Ytterbium by both
sol-gel and microwave methods. The doping of these lanthanides have shown improved
luminescent properties of α-Fe2O3. The up-conversion has been observed from co-doping Thulium
and Ytterbium. This work is a proof of concept to show the up-conversion in α-Fe2O3. However,
the up-conversion intensity is low about 200000 CPS maximum observed, this could be due to the
nature of the host structure quenching the luminescence. There is rather, a need to increase the
intensity for the maximum application to be achieved. / Physics
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Nanoparticules multifonctionelles pour la résonance magnétique et l'imagerie fluorescentePinho, Sonia Luzia Claro 14 December 2011 (has links) (PDF)
Cette thèse décrit une stratégie de synthèse de nouvelles générations des nanoparticules (NPs) pour applications biomédicales, visant à une amélioration de leurs performances pour l'imagerie, le diagnostic thérapeutique. Ces NPs présentent plusieurs fonctionnalités leur permettant de réaliser des tâches multiples. Deux types de sondes bimodales ont été développés et étudiés afin d'évaluer leur potentiel comme agents (1) de contraste en IRM et (2) luminescents. Ces objetscombinent les propriétés des complexes de lanthanide (Ln3+) et celles des NPs de silice ou de type coeur-écorce Fe2O3SiO2 pour une imagerie bimodale. Ces NPs testées sur des cellules vivantes ont permis d'illustrer la preuve du concept aussi bien en IRM avec une augmentation d'intensité des images et un impact significatif sur les relaxivities r1, r2 et r2* qu'en photoluminescence. L'étude du système coeur-écorce a montré que l'influence du contrôle fin de l'écorce autour du noyau d'oxyde de fer a pu être modélisée.
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Redução de NO com CO sobre catalisadores de CuO, Fe2O3 e CuO-Fe2O3 suportados em TiO2, ZrO2 e TiO2-ZrO2: Efeito do vapor de água na atividade e seletividade a N2Castelblanco, William Nova 26 April 2013 (has links)
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Previous issue date: 2013-04-26 / Financiadora de Estudos e Projetos / The combustion of petroleum fuels produces large emissions of NOX, SOX and other strong atmospheric pollutants. The abatement of NOX can be achieved by the nonselective catalytic reduction of NO with CO, for that, supported noble metals have been the most commonly used, with high cost as disadvantage. Transition metal oxides show good activity for this reaction, however, they have poor performance in the presence of SO2, O2 and water steam. Thus, this study aimed to prepare, characterize and evaluate catalysts based on CuO, Fe2O3 and CuO-Fe2O3 supported on TiO2, ZrO2 and their mixtures, in the reduction of NO to N2 with CO in the presence or absence of water steam. XRD data, N2 adsorption and H2-TPR showed that mixed oxides and their catalysts, prepared by sol-gel in-situ, presented specific surface areas between 30 to 60 m2/g, with Cu or Fe species highly distributed, having the last greater interaction with titanium. Rietveld refinement showed preferential formation of zirconium titanate, then showing a close interaction of these species in the mixed supports. All catalysts were highly active in the reduction of NO to N2. At temperatures below 500 °C a CuO catalysts were more active and selective for the formation of N2 than Fe2O3, with the formation of N2O being favored with the increase of zirconium in the support. At 600 °C, the high conversion of NO to N2 on CuO was not influenced by the content of TiO2 in the support. Also at 600 °C, an increasing in the content of titanium in the Fe2O3 catalysts resulted in a significant drop in the conversion of NO to N2. The presence of water steam during the reduction of NO with CO at 600 °C caused a significant decrease in the conversion of NO to N2 and CO to CO2 on the CuO catalyst on the support with higher titanium content. The water steam completely eliminates the activity for the reduction of NO to N2 on Fe2O3 catalysts, but keeping a high conversion of CO to CO2. The CuO and CuO-Fe2O3 catalysts on zirconium-rich supports showed high potential for the abatement of NOX in the presence of water steam at temperatures above 500 ºC. / A combustão de derivados do petróleo gera grandes emissões de NOX, SOX e outros fortes poluentes da atmosfera. O abatimento de NOX pode ser realizado por meio da redução catalítica não seletiva com CO, onde os metais nobres suportados têm sido os mais empregados, com a desvantagem de seu elevado custo. Óxidos de metais de transição apresentam boa atividade nessa reação, no entanto, têm baixo desempenho na presença de SO2, O2 e vapor de água. Assim, este trabalho teve como objetivo preparar, caracterizar e avaliar catalisadores a base de CuO, Fe2O3 e CuO-Fe2O3 suportados em TiO2, ZrO2 ou suas misturas, na redução de NO a N2 com CO na presença ou ausência de vapor de água. Dados de DRX, adsorção de N2 e RTP-H2 mostraram que os suportes mistos e seus catalisadores, que foram preparados via síntese sol-gel in-situ, apresentaram áreas superficiais específicas entre 30 e 60 m2/g, com as espécies de Cu ou Fe altamente distribuídas, tendo essas últimas maior interação com a titânia. Refinamento de Rietveld mostrou formação preferencial de titanato de zircônia, evidenciando a estreita interação dessas espécies nos suportes mistos. Todos os catalisadores foram altamente ativos na redução de NO a N2. Em temperaturas inferiores 500 ºC os catalisadores de CuO foram mais ativos e seletivos à formação de N2 que o Fe2O3, com a formação de N2O sendo favorecida com o aumento de zircônia no suporte. A 600 ºC, a alta conversão de NO a N2 sobre CuO não foi influenciada pelo conteúdo de TiO2 no suporte. Nessa temperatura, o aumento do teor de titânia provocou nos catalisadores de Fe2O3 uma queda significativa na conversão de NO a N2. A presença de vapor de água durante a redução de NO com CO a 600 ºC provocou sobre CuO queda significativa da conversão de NO a N2 e de CO a CO2 sobre o suporte com maior conteúdo de titânia. Nos catalisadores de Fe2O3 puro, o vapor de água anulou completamente a atividade para a redução de NO a N2, mas manteve-se a conversão de CO a CO2. Os catalisadores de CuO e CuO-Fe2O3 sobre suporte contendo alto teor de zircônia apresentaram alto potencial para o abatimento de NOx na presença de vapor de água em temperaturas superiores a 500 ºC.
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Catalisadores de Fe2O3, NiO e Fe2O3 - NiO Suportados in situ em Ce0,5Zr0,5O2 e Ce0,2Zr0,8O2 – Avaliação na Redução de NO com COSouza, Bruna Gonçalves de 28 March 2014 (has links)
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Previous issue date: 2014-03-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / The increasing use of fossil fuels in combustion enginees and power generation plants
has caused a large increase in the emission of sulfur oxides, nitrogen oxides (NOx)
and carbon monoxide into the atmosphere which creates serious environmental
problems. Catalytic processes are used in the abatement of NOx and a promising
alternative is the reduction of NOx using CO as reducing agent on catalysts containing
supported transition metal oxides. Taking this into account, the aim of this study was
to prepare catalysts based on Fe2O3, NiO or Fe2O3-NiO supported on ceria-zirconia
(molar ratios Ce:Zr equal to 1:1 and 1:4), incorporating the metal precursor salt in the
sun of the support (in situ addition). The results of XRD data, Rietveld refinement and
TEM indicated the formation of a solid solution CeO2-ZrO2 with cubic structure fluorite
type; furthermore, it was not observed diffraction peaks of intense X-ray of Fe or Ni
oxide as a consequence of a proper distribution of these oxides in the supports. The
addition of Fe2O3 and/or NiO led to a decrease of the average crystallite size, causing
an increase in SBET of the catalysts compared to the pure support. N2 physisorption
measurements showed that the catalysts showed significant mesoporosity, which was
attributed to the addition of Tween 80 during the sol-gel preparation, moreover, RTPH2
results confirm that the Fe2O3 reduction occurs at lower temperatures in the
presence NiO. In addition, the catalysts showed satisfactory performance in the
reduction of NO to N2 with CO, suggesting that the sol-gel method is adequate in their
preparation. Furthermore, the catalyst 0,90Fe - 1Ce:1Zr reached the highest values of
CO conversion to CO2 and NO to N2 at lower temperatures. The Fe2O3 catalysts were
more selective to N2 formation compared to those containing NiO. In conclusion, the
conversion NO to N2 was significantly affected when in contact with O2 and H2O
interferences; however, this conversion did not change significantly in the presence of
SO2. The catalysts showed a more significant reduction in conversion of NO to N2 when
evaluated in the simultaneous presence of O2, SO2 and H2O. / O crescente uso de combustíveis fósseis em motores de combustão e usinas de
geração de energia vem causando um grande aumento na emissão de óxidos de
enxofre, óxidos de nitrogênio (NOx) e monóxido de carbono na atmosfera, o que gera
sérios problemas ambientais. No abatimento de NOx, em particular, utiliza-se
processos catalíticos e uma alternativa promissora é a redução dos NOx utilizando CO
como agente redutor sobre catalisadores à base de óxidos de metais de transição
suportados. Nessa direção, a pesquisa teve por objetivo preparar catalisadores à base
de Fe2O3, NiO ou Fe2O3-NiO suportados em céria-zircônia (proporções molares entre
Ce e Zr iguais a 1:1 e 1:4), incorporando o sal precursor do metal no sol do suporte
(adição in situ). Dados de DRX e MET indicaram a formação de uma solução sólida
CeO2-ZrO2 com estrutura cúbica tipo fluorita, não se observando picos de difração de
raios X intensos dos óxidos de Fe ou Ni, o que foi interpretado como uma
consequência de uma adequada distribuição desses óxidos nos suportes. Os
resultados do refinamento de Rietveld confirmaram os dados de DRX, indicando uma
composição mássica baixa para os óxidos de Fe e/ou Ni. A adição de Fe2O3 e/ou NiO
levou à uma diminuição do tamanho médio de cristalitos, causando um aumento na
SBET dos catalisadores em relação ao suporte puro. Medidas de fisissorção de N2
mostraram que os catalisadores apresentaram mesoporosidade considerável, que foi
atribuída à adição de Tween 80 durante a preparação sol-gel, além do mais,
resultados de RTP-H2 corroboraram que a redução de Fe2O3 ocorre em temperaturas
menores quando na presença de NiO. Os catalisadores apresentaram comportamento
satisfatório na redução de NO a N2 com CO, indicando que o método sol-gel se
mostrou adequado na sua preparação, sendo o sólido 0,90Fe - 1Ce:1Zr o que atingiu
maiores valores de conversão de CO a CO2 e de NO a N2 em menores temperaturas.
Em comparação aos catalisadores de NiO, os de Fe2O3 foram mais seletivos à
formação de N2. Quando em contato com os interferentes O2 e H2O, a conversão NO
a N2 foi consideravelmente afetada e na presença de SO2, essa conversão não se
alterou significativamente. Quando avaliados na presença simultânea de O2, SO2 e
H2O, os catalisadores apresentaram quedas de conversão de NO a N2 mais
consideráveis.
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Surface- and tip-enhanced Raman spectroscopy reveals spin-waves in iron oxide nanoparticlesRodriguez, Raul D., Sheremet, Evgeniya, Deckert-Gaudig, Tanja, Chaneac, Corinne, Hietschold, Michael, Deckert, Volker, Zahn, Dietrich R. T. 03 June 2015 (has links) (PDF)
Nanomaterials have the remarkable characteristic of displaying physical properties different from their bulk counterparts. An additional degree of complexity and functionality arises when oxide nanoparticles interact with metallic nanostructures. In this context the Raman spectra due to plasmonic enhancement of iron oxide nanocrystals are here reported showing the activation of spin-waves. Iron oxide nanoparticles on gold and silver tips are found to display a band around 1584 cm−1 attributed to a spin-wave magnon mode. This magnon mode is not observed for nanoparticles deposited on silicon (111) or on glass substrates. Metal–nanoparticle interaction and the strongly localized electromagnetic field contribute to the appearance of this mode. The localized excitation that generates this mode is confirmed by tip-enhanced Raman spectroscopy (TERS). The appearance of the spin-waves only when the TERS tip is in close proximity to a nanocrystal edge suggests that the coupling of a localized plasmon with spin-waves arises due to broken symmetry at the nanoparticle border and the additional electric field confinement. Beyond phonon confinement effects previously reported in similar systems, this work offers significant insights on the plasmon-assisted generation and detection of spin-waves optically induced. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.
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Interaction of Water with the Fe2O3(0001) SurfaceOvcharenko, Roman 29 June 2018 (has links)
Diese Arbeit ist eine umfassende und systematische Untersuchung der Adsorption von Wasser auf der Fe2O3(0001)-Oberfläche. Sie deckt eine Vielzahl der Probleme auf, die während des Anfangs der Wasseradsorption auf den Übergangsmetalloxidoberflächen auftreten. Dazu gehören die Stabilität der reinen Oberfläche, die Rolle der Oberflächendefekte, der Einfluss der kristallographischen und elektronischen Strukturen, die elementare Kinetik der adsorbierten Arten von Wasser auf der Oberfläche, die Eigenschaften bei niedrigem und hohem Bedeckungsgrad und die Auswirkungen der Wasserstoffbrückenbindung auf die Adsorption und das XPS-Spektrum. Niedrige und hohe Bedeckungsgrade von 0.25 bis 1 Monolage werden untersucht, um die Grundlage für die folgende Erhöhung der Wasserbedeckung, die normalerweise in Experimenten beobachtet wird, zu ermitteln. Das Einzeladsorptionsregime wurde erweitert, um eine echte Wasserdampfumgebung mittels der Gibbs-Energie zu berücksichtigen. Die Ensemblemethode wurde benutzt, um die durchschnittlichen Werte der energisch entarteten Adsorptionskonfigurationen zu interpretieren. Der Abstandsmatrixansatz wurde entwickelt, um die statistische Analyse zu ermöglichen. Die Methode reduziert mithilfe der Oberflächensymmetrie die Gesamtzahl der Adsorptionskonfigurationen, die zu berücksichtigen sind. Das XPS-Spektrum wird für verschiedene Wasserdampftemperaturen und Drücke simuliert. Es wird eine gute Übereinstimmung zwischen theoretischen und experimentellen Spektren erreicht und die geringen Unterschiede werden erklärt. Die Hauptmerkmale des XPS-Spektrums beim Anstieg von relativer Feuchtigkeit des Wasserdampfs werden beschrieben. Die Ähnlichkeiten und Unterschiede der Wasseradsorption auf Fe2O3 und Al2O3 werden betont und die wichtigsten Tendenzen werden abgeleitet. Auf Grund dieser Arbeit kann der Anfangsprozess der Fe2O3(0001)-Oberflächenbenetzung erklärt werden. / The present study is a comprehensive systematic theoretical investigation of the water adsorption on the Fe2O3(0001) surface. It covers a broad number of problems inherent to the initial stage of the water adsorption on the transition metal oxide surface: clean surface stability, the influence of surface oxygen defects, the role of the crystallographic and electronic structures on the adsorption configuration, elementary kinetics, the particular qualities of the low and high adsorption coverage regimes and the effect of the hydrogen bonding on adsorption and on the XPS spectra simulation. The low and high coverage regimes from 0.25 up to 1 monolayer water coverage were considered to form a basis for the following increase of water loading mainly observed in experiments. A single adsorption energy picture was expanded to take into account the water vapour environment through the Gibbs free energy. The statistical ensemble was employed to classify and interpret the averaged values of the adsorption configurations set rather than the ``invisible'' in experiment quantities intrinsic to the particular single adsorption configuration. In order to make the statistical analysis feasible an effective distance matrix scheme was developed. It helped to reduce the total number of structures to consider without loss of generality by virtue of the surface space symmetry. Based on the statistical contribution of each individual adsorption configuration, the O-1s XPS was simulated for the various water vapour environments. A good agreement between the simulated and experimental spectra was found. Wherever it was important, the similarities and differences between water adsorption on the Fe2O3, Al2O3 and Fe3O4 surfaces were stressed and the main tendencies were deduced. Based on the present study, the whole picture of the initial stage of the Fe2O3(0001) surface wetting process was established.
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Couplage AFM/Raman et spectroscopie Raman exaltée par effet de pointe de nanostructuresNajjar, Samar 23 September 2013 (has links) (PDF)
Pour mieux comprendre leurs propriétés, diverses nanostructures individuelles ont été étudiées à l'aide d'une technique couplant microscopie à force atomique et spectroscopie Raman confocale. Sous excitation lumineuse polarisée, la composition chimique, la structure et la présence de défauts a pu être précisée dans des nanobâtonnets d'oxydes métalliques (ZnO et α-Fe2O3). Sous irradiation laser résonnante, les spectres de nanotubes de carbone monoparoi enrobés de polymères ont révélé notamment l'absence de transfert de charge polymère-nanotube et un effet de désolvatation. Finalement, des feuillets de graphène oxydé et des ADNs double-brin peignés ont pu être préparés et caractérisés par spectroscopie Raman exaltée par effet de pointe en atteignant une résolution spatiale latérale voisine du rayon de courbure de l'apex de la pointe utilisée (12 nm), bien plus faible que la limite de diffraction, ce qui ouvre la voie à de nouveaux travaux spectroscopiques à l'échelle nanométrique.
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Surface- and tip-enhanced Raman spectroscopy reveals spin-waves in iron oxide nanoparticlesRodriguez, Raul D., Sheremet, Evgeniya, Deckert-Gaudig, Tanja, Chaneac, Corinne, Hietschold, Michael, Deckert, Volker, Zahn, Dietrich R. T. 03 June 2015 (has links)
Nanomaterials have the remarkable characteristic of displaying physical properties different from their bulk counterparts. An additional degree of complexity and functionality arises when oxide nanoparticles interact with metallic nanostructures. In this context the Raman spectra due to plasmonic enhancement of iron oxide nanocrystals are here reported showing the activation of spin-waves. Iron oxide nanoparticles on gold and silver tips are found to display a band around 1584 cm−1 attributed to a spin-wave magnon mode. This magnon mode is not observed for nanoparticles deposited on silicon (111) or on glass substrates. Metal–nanoparticle interaction and the strongly localized electromagnetic field contribute to the appearance of this mode. The localized excitation that generates this mode is confirmed by tip-enhanced Raman spectroscopy (TERS). The appearance of the spin-waves only when the TERS tip is in close proximity to a nanocrystal edge suggests that the coupling of a localized plasmon with spin-waves arises due to broken symmetry at the nanoparticle border and the additional electric field confinement. Beyond phonon confinement effects previously reported in similar systems, this work offers significant insights on the plasmon-assisted generation and detection of spin-waves optically induced. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.
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High Capacity Porous Electrode Materials of Li-ion BatteriesPenki, Tirupathi Rao January 2014 (has links) (PDF)
Lithium-ion battery is attractive for various applications because of its high energy density. The performance of Li-ion battery is influenced by several properties of the electrode materials such as particle size, surface area, ionic and electronic conductivity, etc. Porosity is another important property of the electrode material, which influences the performance. Pores can allow the electrolyte to creep inside the particles and also facilitate volume expansion/contraction arising from intercalation/deintercalation of Li+ ions. Additionally, the rate capability and cycle-life can be enhanced. The following porous electrode materials are investigated.
Poorly crystalline porous -MnO2 is synthesized by hydrothermal route from a neutral aqueous solution of KMnO4 at 180 oC and the reaction time of 24 h. On heating, there is a decrease in BET surface area and also a change in morphology from nanopetals to clusters of nanorods. As prepared MnO2 delivers a high discharge specific capacity of 275 mAh g-1 at a specific current of 40 mA g-1 (C/5 rate). Lithium rich manganese oxide (Li2MnO3) is prepared by reverse microemulsion method employing Pluronic acid (P123) as a soft template. It has a well crystalline structure with a broadly distributed mesoporosity but low surface area. However, the sample gains surface area with narrowly distributed mesoporosity and also electrochemical activity after treating in 4 M H2SO4. A discharge capacity of about 160 mAh g-1 is obtained at a discharge current of 30 mA g-1. When the acid-treated sample is heated at 300 °C, the resulting porous sample with a large surface area and dual porosity provides a discharge capacity of 240 mAh g-1 at a discharge current density of 30 mA g-1. Solid solutions of Li2MnO3 and LiMO2 (M=Mn, Ni, Co, Fe and their composites) are more attractive positive electrode materials because of its high capacity >200 mAh g-1.The solid solutions are prepared by microemulsion and polymer template route, which results in porous products. All the solid solution samples exhibit high discharge capacities with high rate capability.
Porous flower-like α-Fe2O3 nanostructures is synthesized by ethylene glycol mediated iron alkoxide as an intermediate and heated at different temperatures from 300 to 700 oC. The α-Fe2O3 samples possess porosity with high surface area and deliver discharge capacity values of 1063, 1168, 1183, 1152 and 968 mAh g-1 at a specific current of 50 mA g-1 when prepared at 300, 400, 500, 600 and 700 oC, respectively. Partially exfoliated and reduced graphene oxide (PE-RGO) is prepared by thermal exfoliation of graphite oxide (GO) under normal air atmosphere at 200-500 oC. Discharge capacity values of 771, 832, 1074 and 823 mAh g -1 are obtained with current density of 30 mA g-1 at 1st cycle for PE-RGO samples prepared at 200, 300, 400 and 500 oC, respectively. The electrochemical performance improves on increasing of exfoliation temperature, which is attributed to an increase in surface area. The high rate capability is attributed to porous nature of the material. Results of these studies are presented and discussed in the thesis.
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