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Metal-organic frameworks (MOFs) are hybrid materials that are being explored as active electrode materials in energy storage devices, such as rechargeable batteries and supercapacitors (SCs), due to their high surface area, controllable chemical composition, and periodic ordering. However, the facile and controlled synthesis of a pure MOF phase without impurities or without going through a complicated purification process (that also reduces the yield) are challenges that must be resolved for their potential industrial applications. Moreover, various oxide formations of the Ni during Ni-MOF synthesis also represent an issue that affects the purity and performance. To resolve these issues, we report the controlled synthesis of nickel-based metal-organic frameworks (NiMOFs) by optimizing different growth parameters during hydrothermal synthesis and by utilizing nickel chloride as metal salt and H2bdt as the organic ligand, in a ratio of 1:1 at 150 °C. Furthermore, the synthesis was optimized by introducing a magnetic stirring stage, and the reaction temperature varied across 100, 150, and 200 °C to achieve the optimized growth of the NiMOFs crystal. The rarely used H2bdt ligand for Ni-MOF synthesis and the introduction of the ultrasonication stage before putting it in the furnace led to the formation of a pure phase without impurities and oxide formation. The synthesized materials were further characterized by powder X-ray diffraction (XRD) technique, scanning electron microscopy (SEM), and UV-vis spectroscopy. The SEM images exhibited the formation of nano NiMOFs having a rectangular prism shape. The average size was 126.25 nm, 176.0 nm, and 268.4 nm for the samples (1:1)s synthesized at 100 °C, 150 °C, and 200 °C, respectively. The electrochemical performances were examined in a three-electrode configuration, in a wide potential window from -0.4 V to 0.55 V, and an electrolyte concentration of 2M KOH was maintained for each measurement. The charge-discharge galvanostatic measurement results in specific capacitances of 606.62 F/g, 307.33 F/g, and 287.42 F/g at a current density of 1 A/g for the synthesized materials at 100 °C, 150 °C, and 200 °C, respectively.

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The design and manufacture of highly efficient nanocatalysts for the oxygen reduction reaction (ORR) is key to achieve the massive use of proton exchange membrane fuel cells. Up to date, Pt nanocatalysts are widely used for the ORR, but they have various disadvantages such as high cost, limited activity and partial stability. Therefore, different strategies have been implemented to eliminate or reduce the use of Pt in the nanocatalysts for the ORR. Among these, Pt-free metal nanocatalysts have received considerable relevance due to their good catalytic activity and slightly lower cost with respect to Pt. Consequently, nowadays, there are outstanding advances in the design of novel Pt-free metal nanocatalysts for the ORR. In this direction, combining experimental findings and theoretical insights is a low-cost methodology-in terms of both computational cost and laboratory resources-for the design of Pt-free metal nanocatalysts for the ORR in acid media. Therefore, coupled experimental and theoretical investigations are revised and discussed in detail in this review article.

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This paper reports a theoretical and experimental investigation on the recombinant protein rotavirus VP6 as a bioelectrochemical interface. Our motivation arises from the highly active zones of VP6 which can interact with biological structures and metals, as well as its useful features such as self-assembly, polymorphism, and active surface charge. A molecular simulation study was performed to analyze the charge transfer properties of theVP6 trimer under an applied electric field. The electrostatic properties were evaluated via the nonlinear second-order Poisson-Boltzmann equation, using finite element methods based on parameter discretization and calculation of solute/solvent interaction forces, which account for mean-field screening effects. The electrochemical study validated the theoretical predictions for VP6 in their different assemblies (trimers and nanotubes) when they are used as electrodes in 10 mM K3[Fe(CN)6], 1 M KCl. Applying a potential sweep promotes charge transfer, facilitates redox activity of the ferricyanide ion. Furthermore, protein assemblies decreased electrode electrical resistance and enabled gold particle electrodeposition on the protein VP6. These results suggest that VP6 is a promising conductive biomaterial that promotes charge transfer of redox probes and could be used as a new scaffold to create bio-electrochemical interfaces.

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The morphology, microstructure, chemistry, electronic properties, and electrochemical behavior of a boron-doped nanocrystalline diamond (BDD) thin film grown on quartz were evaluated. Diamond optically transparent electrodes (OTEs) are useful for transmission spectroelectrochemical measurements, offering excellent stability during anodic and cathodic polarization and exposure to a variety of chemical environments. We report on the characterization of a BDD OTE by atomic force microscopy, optical spectroscopy, Raman spectroscopic mapping, alternating-current Hall effect measurements, X-ray photoelectron spectroscopy, and electrochemical methods. The results reported herein provide the first comprehensive study of the relationship between the physical and chemical structure and electronic properties of a diamond OTE and the electrode's electrochemical activity.

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The present work reports on the synthesis of a redox-tagged peptide with self-assembling capability aiming applications in electrochemically active capacitive surfaces (associated with the presence of the redox centers) generally useful in electroanalytical applications. Peptide containing ferrocene (fc) molecular (redox) group (Ac-Cys-Ile-Ile-Lys(fc)-Ile-Ile-COOH) was thus synthesized by solid phase peptide synthesis (SPPS). To obtain the electrochemically active capacitive interface, the side chain of the cysteine was covalently bound to the gold electrode (sulfur group) and the side chain of Lys was used to attach the ferrocene in the peptide chain. After obtaining the purified redox-tagged peptide, the self-assembly and redox capability was characterized by cyclic voltammetry (CV) and electrochemical impedance-based capacitance spectroscopy techniques. The obtained results confirmed that the redox-tagged peptide was successfully attached by forming an electroactive self-assembled monolayer onto gold electrode. The design of redox active self-assembly ferrocene-tagged peptide is predictably useful in the development of biosensor devices precisely to detect, in a label-free platform, those biomarkers of clinical relevance. © 2016 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 106: 357-367, 2016.

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Este trabalho avaliou o comportamento eletroquímico do metal de base (MB) de uma liga a base de níquel-cromo em relação a juntas soldadas desta liga obtidas pelos processos de brasagem (BRA) e Tungsten Inert Gas (TIG), imersos em saliva artificial com pH 2,5 e 5,5. Foram também realizados ensaios de microdureza e caracterização microestrutural, por meio de microscopia óptica e eletrônica de varredura e análise química semi-quantitativa por EDS, nos grupos MB, TIG, BRA e no cordão de solda a laser (LAS). O MB apresentou uma matriz rica em níquel e cromo, distribuída em um arranjo dendrítico típico, apresentando inclusões metálicas de silício e titânio, além de porosidades. As soldas TIG e LAS revelaram uma microestrutura mais refinada que o MB, mostrando, entretanto, uma mesma composição química e distribuição de seus elementos. A solda BRA apresentou diferenças marcantes em sua microestrutura, composição química e distribuição de seus elementos em relação ao MB. Os dados de microdureza Vickers (HV), potencial de corrosão (Ecorr) e densidade de corrente de corrosão (jcorr) foram analisados com ANOVA e teste de Tukey (p<0,05). Para determinação da influência do pH quanto a resistência à corrosão dos grupos MB, TIG e BRA, empregou-se o teste t de Student (p<0,05). O MB apresentou menor média de microdureza (256,13 ± 9,39 HV), seguido pelos grupos TIG (271,53 ± 8,07 HV), LAS (303,73 ± 13,93 HV) e BRA (551,99 ± 37,73 HV). Em pH 2,5 as médias do Ecorr (mV) para o MB, TIG e BRA foram, respectivamente, -67,9 ± 8,43, -52,78 ± 16,74, e -284,33 ± 19,04; e em pH 5,5, médias de -54,03 ± 21,15, -62,08 ± 20,16 e -278,8 ± 28,96. Os valores médios de jcorr (µA.cm-2) para o MB, TIG e BRA em pH 2,5 foram, respectivamente, 2,49 ± 0,95, 5,584 ± 1,64 e 27,45 ± 4,9; e em pH 5,5, médias de 1,929 ± 0,83, 4,267 ± 1,51 e 54,2 ± 11,96. Os grupos MB e TIG apresentaram boa resistência à corrosão, com maior módulo de impedância em relação ao grupo BRA. As diferenças no pH da ...

This study evaluated and compared the electrochemical behavior of the base metal (BM) of a nickel-chromium dental alloy with welded joints obtained by brazing processes (BRA) and Tungsten Inert Gas (TIG), when immersed in artificial saliva at pH 2.5 and 5.5. Microhardness, microstructural characterization by means of optical microscopy, scanning electron microscopy (SEM) and semi-quantitative chemical analysis by Energy Dispersive Spectroscopy (EDS), were performed in the groups BM, TIG, BRA and in joints weld by laser (LAS). The BM showed a matrix rich in nickel and chromium, distributed in a typical dendritic arrangement, with inclusions of silicon and titanium, and porosities. LAS and TIG welds reveled a microstructure more refined than the BM, however, the same chemical composition and distribution of its elements. BRA showed marked differences in their microstructure, chemical composition and distribution of the elements in relation to BM. Vickers microhardness (HV), corrosion potential (Ecorr) and corrosion current density (jcorr) were statistically analyzed with ANOVA and Tukey test (p <0.05). In order to determine the influence of pH and corrosion resistance in groups BM, TIG and BRA, Student t test, with significance level of 95% was used. BM had the lowest average microhardness (HV 256.13 ± 9.39), followed by groups TIG (271.53 ± 8.07 HV), LAS (303.73 ± 13.93 HV) and BRA (551, HV 99 ± 37.73). At pH 2.5 the average Ecorr (mV) for the MB and TIG were respectively -67.9 ± 8.43 and -52.78 ± 16.74, and at pH 5.5, averaging -54, 03 ± 21.15 and -62.08 ± 20.16. LAS group showed averages of Ecorr (mV) at pH 2.5 and 5.5, respectively, -284.33 ± 19.04 and 28.96 ± -278.8. The average values of jcorr (ìA.cm-2) to BM and TIG at pH 2.5 were respectively 2.49 ± 0.95 and 5.584 ± 1.64, and at pH 5.5, 1.929 ± 0.83 and 4.267 ± 1.51. Average jcorr for LAS group (ìA.cm-2) at pH 2.5 and 5.5 were respectively 27.45 ± 4.9 and 11.96 ± 54.2. BM and TIG ...

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