Desenvolvimento de materiais nanoestruturados à base de SiO2-Nb2O5 preparados por uma nova rota sol-gel com aplicações em fotônica

Este trabalho concentra-se na preparação e caracterizações estrutural e espectroscópica de materiais nanoestruturados à base de SiO2-Nb2O5 dopados e codopados com íons Er3+, Yb3+ e Eu3+ na forma de pós e guias de onda planares. Os nanocompósitos foram preparados através de uma nova rota sol-gel utilizando óxido de nióbio como precursor em substituição ao alcóxido de nióbio. A correlação estrutura propriedades luminescentes foi estudada por difração de raios X, microscopia eletrônica de transmissão, espectroscopia vibracional de absorção no infravermelho, espectroscopia vibracional de espalhamento Raman, análise térmica, reflectância difusa e especular, espectroscopia de fotoluminescência e acoplamento M-line. Inicialmente foi avaliado a influência da concentração de nióbio nas propriedades estruturais e luminescentes de nanocompósitos (100-x)Si-xNb dopados e codopados com íons Er3+, Yb3+ e Eu3+ tratados termicamente a 900 °C por 3h. A cristalização do Nb2O5 foi dependente da concentração de Nb na matriz, com a distribuição dos íons lantanídeos preferencialmente no Nb2O5, afetando as propriedades luminescentes. Para os nanocompósitos codopados com íons Er3+ e Yb3+ foram obtidos valores de largura de banda a meia altura (FWHM) da ordem de 70 nm na região de 1550 nm e tempos de vida de até 5,2 ms. A emissão na região do visível, decorrente de processos de conversão ascendente, revelou-se dependente da concentração de nióbio. Foi verificada emissão preferencial na região do verde para menores concentrações de Nb. Enquanto que, para as maiores concentrações, processos de relaxação cruzada levaram a um aumento relativo na intensidade de emissão na região do vermelho. A eficiência quântica de emissão dos nanocompósitos (100-x)Si-xNb dopados com Eu3+ variou com o comprimento de onda de excitação, refletindo os diferentes sítios de simetria ocupados por este íons nesta estrutura complexa. A influência da temperatura de tratamento térmico no processo de cristalização do Nb2O5 em nanocompósitos 70Si:30Nb codopados com íons Er3+ e Yb3+ foi avaliada. Material amorfo foi obtido a 700 °C enquanto que a 900 e 1100 °C foram identificas as fases ortorrômbica (fase T) e monoclínica (fase M) do Nb2O5. Intensa emissão na região de 1550 nm com valores de FWHM de 52 e 67 nm e tempos de vida de 5,6 e 5,4 ms foram verificados a 700 e 900 °C sob excitação em 977 nm, respectivamente. Por fim, foram obtidos guias de onda planares com excelentes propriedades ópticas e com grande potencial de aplicação em dispositivos de amplificação óptica. Especificamente, materiais fotônicos com banda larga de emissão na região do infravermelho foram preparados, indicando fortemente a potencialidade para a aplicação em telecomunicações envolvendo não somente a banda C como também as bandas L e S em materiais contendo somente íons Er3+ como centros emissores.

Estudo das propriedades inibidoras de corrosão das imidazolinas oleica e quaternária e seu encapsulamento em partículas inertes.

Entre os inibidores de corrosão clássicos que já são utilizados na indústria do petróleo, foram estudadas a imidazolina oleica e a quaternária através de técnicas eletroquímicas, gravimétrica e analíticas, para avaliar a eficiência de inibição e como esses inibidores atuam em meio ácido. O meio agressivo foi uma solução de NaCl 3,5% em massa acidificada com ácido clorídrico até atingir um pH=2 com o objetivo de simular o ambiente de extração petrolífera. O substrato empregado foi o aço carbono 1020. As técnicas eletroquímicas utilizadas foram: monitoramento do potencial de circuito aberto, medidas de resistência de polarização linear, espectroscopia de impedância eletroquímica (EIE ) e curvas de polarização. Os valores das componentes real e imaginária de impedância indicam uma resistência maior aos processos de transferência de carga com o aumento da concentração dos inibidores e os Diagramas de Bode de ângulo de fase, revelaram a presença de uma camada de inibidor adsorvida sobre o metal com uma constante de tempo em altas frequências observada para a imidazolina oleica e quaternária. Para a imidazolina quaternária, verificou-se que só para tempos maiores de imersão é que o filme se adsorve de forma eficiente demonstrando uma cinética mais lenta de adsorção. Nos ensaios gravimétricos, os resultados de taxa de corrosão em m/ano foram decrescentes com o tempo após período de imersão de 30 dias, para ambas as imidazolinas. O uso das técnicas analíticas foi necessário a fim de se compreender melhor o comportamento das imidazolinas sobre o aço no meio estudado. Os resultados da análise de íons férricos em solução, por emissão atômica, foram obtidos durante várias amostragens durante o período do ensaio de perda de massa, e foi possível verificar um processo de inibição da corrosão até doze dias de imersão do metal, depois disto ocorre um disparo na quantidade de ferro liberado em solução, sugerindo que pode estar ocorrendo uma degradação do inibidor após 12 dias de imersão. Para esclarecer esse ponto, análises por espectroscopia Raman dos produtos de fundo formados durante os ensaios de perda de massa indicaramm que a degradação pode realmente estar ocorrendo. Foi confirmado, também por espectroscopia Raman sobre a superfície do aço após imersão prévia em solução contendo a imidazolina oleica, que há uma película adsorvida que protege o metal do meio agressivo. Técnica de microscopia eletrônica de varredura foi utilizada para caracterizar os corpos de prova na ausência e presença do inibidor, depois dos ensaios eletroquímicos e foi possível caracterizar, através dessa técnica a maior eficiência inibidora do filme de imidazolina quaternária. Dois tipos de nanoconatiners foram avaliados para o encapsulamento das duas imidazolinas estudadas: nanocontainers a base do argilomineral haloiista e sílica mesoporosa tipo SBA 15. Resultados de impedância eletroquímica mostraram a liberação dos inibidores de corrosão encapsulados com o tempo de imersão. Análise na região do infravermelho por sonda de fibra ótica foi utilizada para comprovar química e qualitativamente a liberação do inibidor a partir dos nanorreservatórios, no meio agressivo.

Mechanistic Importance of Redox Potentials and Conformational Flexibility in Electron-Transferring Flavoproteins

The mitochondrial matrix flavoproteins electron transfer flavoprotein (ETF) and electron transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO) are responsible for linking fatty acid β-oxidation with the main mitochondrial respiratory chain. Electrons derived from flavoprotein dehydrogenases are transferred sequentially through ETF and ETF-QO to ubiquinone and then into the respiratory chain via complex III. In this study, the effects of changes in ETF-QO redox potentials on its activity and the conformational flexibility of ETF were investigated. ETF-QO contains one [4Fe-4S]2+,1+ and one flavin adenine dinucleotide (FAD). In the porcine protein, threonine 367 is hydrogen bonded to N1 and O2 of the flavin ring of the FAD. The analogous site in Rhodobacter sphaeroides ETF-QO is asparagine 338. Mutations N338T and N338A were introduced into the R. sphaeroides protein by site-directed mutagenesis to determine the impact of hydrogen bonding at this site on redox potentials and activity. FAD redox potentials were measured by potentiometric titration probed by electron paramagnetic resonance (EPR) spectroscopy. The N338T and N338A mutations lowered the midpoint potentials, which resulted in a decrease in the quinone reductase activity and negligible impact on disproportionation of ETF1e- catalyzed by ETF-QO. These observations indicate that the FAD is involved in electron transfer to ubiquinone, but not in electron transfer from ETF to ETF-QO. Therefore it is proposed that the iron-sulfur cluster is the immediate acceptor from ETF. It has been proposed that the αII domain of ETF is mobile, allowing promiscuous interactions with structurally different partners. Double electron-electron resonance (DEER) was used to measure the distance between spin labels at various sites and an enzymatically reduced FAD cofactor in Paracoccus denitrificans ETF. Two or three interspin distance distributions were observed for spin-labels in the αI (A43C) and βIII (A111C) domains, but only one is observed for a label in the βII (A210C) domain. This suggests that the αII domain adopts several stable conformations which may correspond to a closed/inactive conformation and an open/active conformation. An additional mutation, E162A, was introduced to increase the mobility of the αII domain. The E162A mutation doubled the activity compared to wild-type and caused the distance distributions to become wider. The DEER method has the potential to characterize conformational changes in ETF that occur when it interacts with various redox partners.

Estudo dos espectros vibracionais de poliacetilenos substituídos

Neste trabalho foram sintetizados a poli-2-etinilpiridina (P2EP), poli-4etinilpiridina (P4EP), o iodeto de poli(2-N-t-butilpiridiniumilacetileno) (P2EPtBu) e a poli-β-etinilnaftaleno (Pβ:EN), os quais são poliacetilenos substituídos. Estes polímeros, juntamente com o cloreto de poli(2-piridínio-2-piridilacetileno) (P2EPH), foram caracterizados por espectroscopia vibracional no infravermelho e Raman. Estes polímeros apresentaram variação na posição das bandas Raman com a energia da radiação excitante - chamada dispersão Raman ou fotosseletividade - da ordem de 10 cm-1, bem inferior ao apresentado pelo poliacetileno (cerca de 60 cm-1). Este deslocamento foi interpretado utilizando-se dois dos modelos existentes para descrever este fenômeno: o Modelo de Modo de Amplitude (AMM) e o Modelo de Coordenada de Conjugação Efetiva (ECCM), os quais fornecem informações sobre a estrutura polimérica e sobre seus níveis eletrônicos. Utilizando-se o AMM foi possível obter informações sobre os níveis eletrônicos excitados de mesma simetria que o estado eletrônico fundamental. Por outro lado, o ECCM, com a ajuda de cálculos DFT, mostrou diferenças na extensão da conjugação e no grau de dimerização entre o P2EP na forma cis e trans e indicou que este polímero apresentava, predominantemente, a estrutura cis, fato este confirmado pelos espectros no infravermelho. A dopagem com I2 provocou efeitos diferentes na estrutura dos polímeros. Os espectros no infravermelho dos polímeros dopados indicaram que o P2EP e o P2EPH apresentaram aumento na quantidade de segmentos cis enquanto o P2EPtBu apresentou diminuição na quantidade desses segmentos. Os espectros Raman dos polímeros dopados confirmaram os dados dos espectros no infravermelho. Esta diferença foi interpretada como sendo devida à diferença no volume do substituinte, pois grupos volumosos favorecem o isômero trans-cisóide onde a distância entre os substituintes é maior. A dopagem também levou a um aumento na condutividade dos polímeros, porém os valores de condutividade obtidos foram bem inferiores que os apresentados pelo poliacetileno dopado (10-5 a 10-7 contra 102 S cm-1, tipicamente).

Preparation, characterisation and testing of CuO/Ce0.8Zr0.2O2 catalysts for NO oxidation to NO2 and mild temperature diesel soot combustion

CuO/ceria-zirconia catalysts have been prepared, deeply characterised (N2 adsorption–desorption isotherms at −196 °C, XRD, Raman spectroscopy, XPS, TEM and H2-TPR) and tested for NO oxidation to NO2 in TPR conditions, and for soot combustion at mild temperature (400 °C) in a NOx/O2 stream. The behaviour has been compared to that of a reference Pt/alumina commercial catalyst. The ceria-zirconia support was prepared by the co-precipitation method, and different amounts of copper (0.5, 1, 2, 4 and 6 wt%) were loaded by incipient wetness impregnation. The results revealed that copper is well-dispersed onto the ceria-zirconia support for the catalysts with low copper loading and CuO particles were only identified by XRD in samples with 4 and 6% of copper. A very low loading of copper increases significantly the activity for the NO oxidation to NO2 with regard to the ceria-zirconia support and an optimum was found for a 4% CuO/ceria-zirconia composition, showing a very high activity (54% at 348 °C). The soot combustion rate at 400 °C obtained with the 2% CuO/ceria-zirconia catalyst is slightly lower to that of 1% Pt/alumina in terms of mass of catalyst but higher in terms of price of catalyst.

Electrocatalytic Performance of SiO2-SWCNT Nanocomposites Prepared by Electroassisted Deposition

Composite materials made of porous SiO2 matrices filled with single-walled carbon nanotubes (SWCNTs) were deposited on electrodes by an electroassisted deposition method. The synthesized materials were characterized by several techniques, showing that porous silica prevents the aggregation of SWCNT on the electrodes, as could be observed by transmission electron microscopy and Raman spectroscopy. Different redox probes were employed to test their electrochemical sensing properties. The silica layer allows the permeation of the redox probes to the electrode surface and improves the electrochemical reversibility indicating an electrocatalytic effect by the incorporation of dispersed SWCNT into the silica films.

Production of nanoTiC–graphite composites using Ti-doped self-sintering carbon mesophase powder

This work reports the synthesis of nanoTiC–graphite composites using mesophase pitch containing titanium as TiC or TiO2 nanoparticles. NanoTiC–graphite composites have been prepared using Ti-doped self-sintering mesophase powders as starting materials without using any binders or a metal carbide-carbon mixing stage. The effect of manufacture variables on the graphite compacts properties was studied. Graphites were characterised using XRD and Raman spectroscopy, SEM and TEM, as well as by their mechanical, electrical and thermal properties. The presence of TiC promotes graphitisation producing materials with larger crystal sizes. The kind of titanium source and mesophase content of the starting pitch affects to the final properties. Mesophase pitch with higher amount of mesophase content produces graphites with higher degree of graphitisation. The incorporation of TiC nanoparticles to the graphites composites improved thermal conductivity more than four times, and mechanical properties are not significantly modified by the presence of TiC.

Clay-supported graphene materials: application to hydrogen storage

The present work refers to clay–graphene nanomaterials prepared by a green way using caramel from sucrose and two types of natural clays (montmorillonite and sepiolite) as precursors, with the aim of evaluating their potential use in hydrogen storage. The impregnation of the clay substrates by caramel in aqueous media, followed by a thermal treatment in the absence of oxygen of these clay–caramel intermediates gives rise to graphene-like materials, which remain strongly bound to the silicate support. The nature of the resulting materials was characterized by different techniques such as XRD, Raman spectroscopy and TEM, as well as by adsorption isotherms of N2, CO2 and H2O. These carbon–clay nanocomposites can act as adsorbents for hydrogen storage, achieving, at 298 K and 20 MPa, over 0.1 wt% of hydrogen adsorption excess related to the total mass of the system, and a maximum value close to 0.4 wt% of hydrogen specifically related to the carbon mass. The very high isosteric heat for hydrogen sorption determined from adsorption isotherms at different temperatures (14.5 kJ mol−1) fits well with the theoretical values available for hydrogen storage on materials that show a strong stabilization of the H2 molecule upon adsorption.

Probing the Electrocatalytic Oxygen Reduction Reaction Reactivity of Immobilized Multicopper Oxidase CueO

The bioelectrocatalytic (oxygen reduction reaction, ORR) properties of the multicopper oxidase CueO immobilized on gold electrodes were investigated. Macroscopic electrochemical techniques were combined with in situ scanning tunneling microscopy (STM) and surface-enhanced Raman spectroscopy at the ensemble and at the single-molecule level. Self-assembled monolayer of mercaptopropionic acid, cysteamine, and p-aminothiophenol were chosen as redox mediators. The highest ORR activity was observed for the protein attached to amino-terminated adlayers. In situ STM experiments revealed that the presence of oxygen causes distinct structure and electronic changes in the metallic centers of the enzyme, which determine the rate of intramolecular electron transfer and, consequently, affect the rate of electron tunneling through the protein. Complementary Raman spectroscopy experiments provided access for monitoring structural changes in the redox state of the type 1 copper center of the immobilized enzyme during the CueO-catalyzed oxygen reduction cycle. These results unequivocally demonstrate the existence of a direct electronic communication between the electrode substrate and the type 1 copper center.

Preferential oxidation of CO in excess of H2 on Pt/CeO2–Nb2O5 catalysts

A series of CeO2–Nb2O5 mixed oxides with different Nb content, as well as the pure oxides, have been synthesized by co-precipitation with excess urea. These materials have been used as supports for platinum catalysts, with [Pt(NH3)4](NO3)2 as precursor. Both supports and catalysts have been characterized by several techniques: N2 physisorption at 77 K, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, UV–vis spectroscopy, scanning electron microscopy, transmission electron microscopy, temperature-programmed reduction and temperature-programmed desorption (CO and H2), and their catalytic behaviour has been determined in the PROX reaction, both with an ideal gas mixture (CO, O2 and H2) and in simulated reformate gas containing CO2 and H2O. Raman spectroscopy analysis has shown the likely substitution of some Ce4+ cations by Nb5+ to some extent in supports with low niobium contents. Moreover, the presence of Nb in the supports hinders their ability to adsorb CO and to oxidize it to CO2. However, an improvement of the catalytic activity for CO oxidation is obtained by adding Nb to the support, although the Pt/Nb2O5 catalyst shows very low activity. The best results are found with the Pt/0.7CeO2–0.3Nb2O5 catalyst, which shows a high CO conversion (85%) and a high yield (around 0.6) after a reduction treatment at 523 K. The effect of the presence of CO2 and H2O in the feed has also been determined.

Catalytic performance of CuO/Ce0.8Zr0.2O2 loaded onto SiC-DPF in NOx-assisted combustion of diesel soot

This work presents a comparative study between the catalytic performance of the 2% CuO/ceria-zirconia powder catalyst and the same catalyst supported on silicon carbide DPF (Diesel Particulate Filter) towards NO oxidation reaction and soot combustion reaction. The ceria-zirconia catalyst was prepared by the co-precipitation method and 2 wt% copper was incorporated by the incipient wetness impregnation method. The catalyst was incorporated onto the ceramic support using a simple and organic solvent-free procedure by a simply dipping the DPF into an aqueous solution of the catalyst. The powder catalyst has been characterized using N2 adsorption at −196 °C, XRD and Raman Spectroscopy; whereas the catalytic coating morphology has been evaluated by SEM and the mechanical stability by an adherence test. Both catalyst configurations were tested for NO oxidation to NO2 and for soot combustion under NOx/O2. The results revealed that incorporation of the very active copper/ceria-zirconia catalyst onto SiC-DPF has been successfully achieved by a simple coating procedure. Furthermore, the catalytic coating has shown suitable mechanical, chemical and thermal stability. A satisfactory catalytic performance of the catalytic-coated filter was reached towards the NO oxidation reaction. Moreover, it was proved that the catalytic coating is stable and the corresponding coated DPF can be reused for several cycles of NO oxidation without a significant decrease in its activity. Finally, it was verified that the loose-contact mode is a good choice to simulate the catalytic performance of this active phase in a real diesel particulate filter.

Superior performance of gold supported on doped CeO2 catalysts for the preferential CO oxidation (PROX)

Herein, the preferential oxidation of CO in excess hydrogen (PROX reaction) was studied over Au catalysts supported on ceria and Y or Nb doped ceria. Both supports and catalysts have been extensively characterized by a number of advanced techniques; XRD, N2-adsortion, Raman spectroscopy, XPS, and H2-TPR. The catalytic results showed that when an ideal mixture of H2 and CO is used for the PROX reaction the gold supported on pure ceria behaves better than the others samples. However, when a typical reformate gas composition containing CO2 and H2O is used, the gold supported on Nb doped sample behaves better than gold supported in pure ceria. It is suggested that niobium hampers the strong adsorption of CO2 and H2O in the active sites, thus improving the catalytic performance in real reformate gas.

Promoter effect of sodium in graphene-supported Ni and Ni–CeO2 catalyst for the low-temperature WGS reaction

The low temperature water–gas shift (WGS) reaction has been studied over Ni–CeO2/Graphene and Ni/Graphene. The catalysts were prepared with 5 wt.% Ni and 20 wt.% CeO2 loadings, by deposition-precipitation employing sodium hydroxide and urea as precipitating agents. The materials were characterized by TEM, powder X-ray diffraction, Raman spectroscopy, H2-temperature-programmed reduction and X-ray photoelectron spectroscopy (XPS). The characterization and the reaction results indicated that the interaction between the active species and the support is higher than with activated carbon, and this hinders the reducibility of ceria and thus the catalytic performance. On the other hand, the presence of residual sodium in samples prepared by precipitation with NaOH facilitated the reduction of ceria. The catalytic activity was highly improved in the presence of sodium, what can be explained on the basis of an associative reaction mechanism which is favored over Ni-O-Na entities.

The effect of carbon nanofillers on the performance of electromechanical polyaniline-based composite actuators

Different types of crystalline carbon nanomaterials were used to reinforce polyaniline for use in electromechanical bilayer bending actuators. The objective is to analyze how the different graphitic structures of the nanocarbons affect and improve the in situ polymerized polyaniline composites and their subsequent actuator behavior. The nanocarbons investigated were multiwalled carbon nanotubes, nitrogen-doped carbon nanotubes, helical-ribbon carbon nanofibers and graphene oxide, each one presenting different shape and structural characteristics. Films of nanocarbon-PAni composite were tested in a liquid electrolyte cell system. Experimental design was used to select the type of nanocarbon filler and composite loadings, and yielded a good balance of electromechanical properties. Raman spectroscopy suggests good interaction between PAni and the nanocarbon fillers. Electron microscopy showed that graphene oxide dispersed the best, followed by multiwall carbon nanotubes, while nitrogen-doped nanotube composites showed dispersion problems and thus poor performance. Multiwall carbon nanotube composite actuators showed the best performance based on the combination of bending angle, bending velocity and maximum working cycles, while graphene oxide attained similarly good performance due to its best dispersion. This parallel testing of a broad set of nanocarbon fillers on PAni-composite actuators is unprecedented to the best of our knowledge and shows that the type and properties of the carbon nanomaterial are critical to the performance of electromechanical devices with other conditions remaining equal.

Vitrinite reflectance of ODP Leg 139 samples (Table 1)

Isolated kerogens from four sites in the Middle Valley hydrothermal region of the Juan de Fuca Ridge (Ocean Drilling Project (ODP) Leg 139) were analysed by electron paramagnetic resonance (EPR) spectroscopy. Measurements of peak width, spin density and power saturation for site 857 kerogens, which increased regularly in maturity downhole, show correlation with vitrinite reflectance values from 0.61 to 2.5%, indicating the start of the oil window at depths from 200 to 400 m. Spin density increases to 1.56 * 10**17 spins per gram and peak width decreases to 3.45 G (gauss) with increasing depth. The tendency to power saturate also decreases with increasing maturity and increasing vitrinite reflectance within the oil window. These trends are consistent with a model in which exchange processes are occurring and cause changes in the EPR behavior of samples from this site. Sediments from other Middle Valley sites, 855, 856 and 858 contain large quantities of pyrite with Mn2+ impurities which interact with the carbon radical to distort the EPR measurements.