Developing new non-noble metal electrocatalysts for oxygen reduction reaction (ORR) is an essential challenge in electrochemical device research. Among these, we highlight the metal Schiff-base complexes, which can be used as modified carbon paste electrodes (CPE). Herein, we present a facile one-pot method for preparing a new family of cobalt(II) complexes with Schiffbase ligands obtained from glycine and para-substituted aldehydes. Complexes were characterized by different techniques, and the effects of para-substituents on the electronic properties of the complexes were confirmed by ultraviolet-visible spectroscopy and cyclic voltammetry (CV). The CV was also used to evaluate the ORR behavior of metal complex-modified CPE in an alkaline medium. The three complex-modified CPE were found to be highly effective for ORR, and the electron-withdrawing character of para-substituent affects the electrochemical reactivity. Density functional theory (DFT) calculations were used to complement the study and correlate the electrochemical activity, the redox potentials, and the Hammett parameter (σp) with the singly occupied molecular orbital (SOMO) energy of the complexes. DFT data were also able to shed light on the likely ORR mechanism. In summary, electronic tuning of the ligand affects the electronic properties of the metal center and allows for systematic oxygen reduction-catalytic control. nonnoble non noble (ORR research these Schiff base CPE. . (CPE) Herein onepot one pot cobaltII cobalt II cobalt(II parasubstituted para substituted aldehydes techniques parasubstituents substituents ultravioletvisible ultraviolet visible CV. (CV) complexmodified complex medium electronwithdrawing electron withdrawing parasubstituent substituent reactivity (DFT activity potentials σp (σp SOMO (SOMO mechanism summary reductioncatalytic catalytic control (CPE (CV

Lithium manganese oxide, LiMn2O4, was synthesized in two temperature stages, where the first consisted by an ecofriendly solution combustion method at 300 °C. Finally, the as-burned powders were thermal treated at 500 and 700 °C. The structural and morphological changes were evaluated by the Rietveld method and density functional theory (DFT) calculations. The Rietveld refinement indicates obtaining the spinel cubic phase LiMn2O4 and a small amount of Mn2O3. The analyses by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show a porous microstructure composed of nano-sized crystallites for the sample treated at 500 °C. In cyclic voltammetry, it was possible to observe that the reduction-oxidation reaction is reversible due to the shape of voltammograms and the anodic and cathodic peaks of Mn ions. The theoretical calculations considered the experimental crystallographic parameters. The unit cell volume change was evaluated according to distinct amounts of lithium ions in the structure. The removal of the Li+ cations from the oxides promotes a volume contraction. Therefore, it was possible to evaluate the participation of the Mn3+ ions in the frontier region between the valence and conduction bands. The density of states (DOS) calculation shows a predominant contribution of the O 2p and Mn 3d orbitals in the frontier orbitals.

A bauxita do Pará é constituída pelas seguintes camadas: nodular (BN), nodular cristalizada (BNC), cristalizada (BC), cristalizada - amorfa (BCBA) e amorfa (BA). Deste perfil geológico, somente a camada BC é lavrada, beneficiada, transportada através de mineroduto e purificada no processo Bayer. As camadas BCBA e BA possuem um elevado teor de SiO2 reativa (6-7%), o que inviabiliza sua utilização no processo. Uma proposta para dobrar as reservas de bauxita, de acordo com o parâmetro comercial, depende de um estudo de caracterização e de beneficiamento que permita identificar as principais dificuldades da utilização da camada BCBA na obtenção de alumina. Assim, este trabalho consistiu na caracterização da bauxita BCBA e no estudo reológico, com o objetivo de verificar a viabilidade desta bauxita para a produção de alumina e do seu transporte por meio de mineroduto. A caracterização da bauxita BCBA utilizou as técnicas de FRX, DRX, IV, MEV, distribuição do tamanho de partículas por meio de peneiramento, potencial zeta, a análise química pelas técnicas de absorção atômica e titulação potenciométrica. Para estudar a influência da concentração de sólidos, distribuição do tamanho de partículas obtida por diferentes tempos de moagem, temperatura e pH na viscosidade, realizou-se um planejamento de experimento 2(4-1), com ponto central. A bauxita BCBA é essencialmente gibbsítica e encontra-se associada aos minerais caulinita e hematita. Após as etapas de britagem, moagem e peneiramento, verificou-se que esta bauxita contém um teor de 41,7% de Al2O3 disponível e 7,1% de SiO2 reativa. A DRX e o IV indicaram a caulinita como a fase responsável pelo alto teor de sílica reativa desta bauxita. A avaliação estatística das variáveis de preparo da polpa indicou que a concentração de sólidos é a variável de maior influência na viscosidade, seguida pela influência da distribuição de tamanho de partículas e do pH.

Bauxite from Pará is constituted by the following layers: nodular (BN), nodular crystallized (BNC), crystallized (BC), crystallized - amorphous (BCBA) and amorphous (BA). From this geological profile only the BC layer is mined, dressed, transported through pipelines and purified in the Bayer process. The BCBA and BA layers have a high content of reactive SiO2 (6-7%) which makes its use unfeasible to the process. A proposal to double bauxite reserves, in accordance with the commercial parameter, depends on a study of characterization and beneficiation to identify the main difficulties for BCBA utilization in the Bayer process. Thus, the goals of this work were the characterization of BCBA bauxite as well as the rheological study to verify the feasibility of this bauxite for alumina production and its transport through pipeline. The characterization of BCBA bauxite used the following techniques: XRF, XRD, IR, SEM/EDS, particle size distribution through wet screening, zeta potential as well as chemical analysis by atomic absorption and potentiometric titration. To study the influence of solids concentration, particle size distribution produced by different grinding times, temperature and pH on the viscosity of bauxite pulp, a matrix experiment 24-1 around mean values was performed. The BCBA bauxite is essentially gibbsitic and is associated with kaolinite and hematite. After the steps of crushing, grinding, and screening this bauxite contains 41.7% of available Al2O3 and 7.1% of reactive SiO2. The XRD and IR identified kaolinite as the phase responsible for the high level of reactive silica in this bauxite. The statistical evaluation of the variables of the pulp preparation indicated that the solid concentration is the most influential variable on viscosity, followed by the influence of particle size and pH.

Os óxidos mistos SiO2/MxOy obtidos pelo processo sol-gel, designados de compósitos, normalmente aliam as propriedades mecânicas e químicas da sílica gel com as propriedades químicas do óxido metálico (MxOy), apresentando propriedades tais como: elevado grau de dispersão e homogeneidade das partículas do óxido metálico na matriz de sílica, assim como elevada resistência mecânica e química. O objetivo deste trabalho foi o de preparar e caracterizar materiais do sistema SiO2/Mn xOy, obtidos pelo processo sol-gel, utilizando diferentes concentrações dos precursores de Mn (II), acetato ou nitrato. A técnica de fluorescência de raios X (FRX) mostrou que a concentração do óxido metálico nos materiais é dependente do precursor utilizado e da sua concentração no meio reacional, variando de 9,4% até 20,9% em massa. A maior concentração de óxido de manganês foi obtida quando se utilizou como precursor o (CH3CO2)2Mn.4H2O. Os espectros de infravermelho indicam que a rede de SiO2 é pouco perturbada pelo aumento da quantidade de óxido de manganês, sugerindo que o Mn xOy está disperso na superfície da matriz de sílica. Os difratogramas de raiosX (DRX) mostram que os materiais apresentam baixa cristalinidade. No entanto, observa-se uma mudança no DRX em 2θ = 35,7º quando o material é aquecido a 400 0C, provavelmente devido à formação de cristalitos de Mn3O4. O método de síntese proposto para os materiais SiO2/Mn xOy é reprodutível. A aplicação destes materiais como eletrodos para a redução de O2 foi avaliada e observou-se que a atividade eletrocatalítica desses materiais pode ser aumentada através do seu aquecimento a 400 0C.

The mixed oxides SiO2/MxOy obtained by the sol-gel process, designated as composites, usually combine both mechanical and chemical properties of silica gel with the chemical properties of metal oxide (MxOy), showing properties such as: high degree of dispersion and homogeneity of metal oxide particles in the silica matrix, as well as high mechanical and chemical resistance. The goal of this work was to prepare and characterize materials in the system SiO2/Mn xOy obtained by the sol-gel process, using different concentrations of Mn (II) precursors (acetate or nitrate). The technique of X-ray fluorescence showed that the concentration of metal oxide in the materials is dependent on the precursor used and its concentration, ranging from 9.4% up to 20.9% by mass. The highest concentration of manganese oxide was obtained when (CH3CO2)2Mn.4H2O was used as precursor. The infrared spectra indicate that the network of SiO2 is not disturbed by the increase in the quantity of manganese oxide, suggesting that the Mn xOy is dispersed on the surface of the silica matrix. The X-ray diffraction showed the low crystallinity of these materials. However, there is a change in the XRD on 2θ = 35.7(0) when the material is heated to 400 0C, probably due to the formation of Mn3O4 crystallites. The proposed synthesis method for materials SiO2/Mn xOy is reproducible. Application of these materials as electrodes for the reduction of O2 was evaluated and it was found that the electrocatalytic activity of these materials can be increased by heating them at 400 0C.

The mineral waste studied was host rock from a chromite mine located in Andorinha/Bahia, extracted and stockpiled in yards without specific application. Host rock was submitted to chemical analysis, XRD, SEM-EDS, IR and TGA and classified according to ABNT standards for solid waste classification. Analyses confirmed that this host rock, classified as ultrabasic, consists mainly of dolomite, calcite and diopside. Hazard assessment results showed this host rock should be classified as class II B - inert waste, important for its potential application in agriculture as a soil acidity correction agent.

Density Functional Theory (DFT) calculations on the interactions of small atoms (H, C, O, and S) on first-row transition metal clusters were performed. The results show that the adsorption site may vary between the metal surface and the edge of the cluster. The adsorption energies, adatom-nearest neighbor and adatom-metal plane distances were also determined. Finally, the authors present a discussion about the performance of these metals as anodes on solid oxide fuel cells. The results obtained agree with empirical data, indicating that the theoretical model used is adequate

In this paper the current status of fuel cells is described with particular emphasis on high (T > 800 ºC) and intermediate (T < 800 ºC) temperature solid oxide fuel cells. Also the importance of the fuel cell technology is shown. Reviewed are the fundamental features, the basic principles, types of fuel cell, fabrication methods, cell configurations and the development of components (cathodes, anodes, electrolytes, interconnect) and materials.

O uso de cromatografia sob pressão ("flash chromatography") utilizando-se coluna de gel de sílica impregnada com hidróxido de potássio levou ao fracionamento dos constituintes químicos de Copaifera cearensis Huber ex Ducke. A fração ácida, após esterificação com diazometano, foi analisada por cromatografia gasosa de alta resolução acoplada à espectrometria de massas ou à espectrometria no infravermelho, possibilitando a identificação de onze diterpenos ácidos. Fracionamentos adicionais da fração ácida por cromatografia líquida de alta eficiência em fase reversa levaram ao isolamento de diversos ácidos diterpênicos e de um sesquiterpênico que foram identificados através de seus dados espectroscópicos. A análise da sílica impregnada com hidróxido de potássio mostrou que, além da deposição do hidróxido na superfície da sílica, ocorreu troca iônica com formação de resíduos Si-OK.

Various acid diterpenes of Copaifera cearensis Huber ex Ducke were isolated from the crude extract by flash Silica Gel/Potassium Hydroxide Chromatography. The main components were identified by GC-MS analyses. Further fractionation by reversed phase (RP) semi-preparative HPLC allowed isolation and identification of minor components and provided additional spectral data of those compounds. It was possible to detect the presence of eleven acid diterpenes in addition to a sesquiterpene acid. In addition to potassium hydroxide deposition on the silica surface, the presence of Si-OK residues, resulting from a cation exchange process, was established.