The water treatment sludge (WTS) is a residue composed of organic and inorganic matter in a solid, liquid, and gaseous state that has a variable composition concerning its physical, chemical, and biological characteristics. The irregular disposal of WTS can promote harmful changes to the environment, such as reduction of dissolved oxygen and increase in the concentration of aluminum and other metals in the receiving watercourses. To propose a suitable purpose for this residue, this work evaluated the physical and mechanical properties of the concrete and corrosion resistance of the reinforcement in a cementitious composite using WTS in replacement to the natural sand. A conventional concrete and a conventional mortar were used as a reference and a 3% WTS-content concrete, and a 3% WTS-content mortar were prepared to evaluate the WTS influence in mechanical properties and corrosion resistance. By electrochemical measurements, it was observed that the resistance of the cementitious matrix was not altered by WTS addition. Regarding steel resistance, the WTS may promote a higher susceptibility to frame corrosion, which can be correlated to the lower pH than reference medium (REF). The concrete reinforcement characterization indicates that concretes with WTS can be used as reinforced concrete structure in urban areas.

Here we investigated the photoelectrodeposition of oxygen-evolving catalysts (OECs) based on oxy-hydroxides-phosphates of Co, Fe, or Ni (CoPi, FePi, and NiPi) on the WO3/BiVO4 heterojunction and their activity in water oxidation. The OECs were deposited by cycles of (i) open-circuit potential (OCP) and (ii) applying a potential positive enough to oxidize the metallic precursor on the WO3/BiVO4. The crystalline and optical properties of the photoanodes were not significantly affected by the OECs deposition. However, there was a remarkable increase in the photocurrent densities (jpc) to water oxidation, where the modification with FePi showed the best result, achieving 2.12 mA cm-2, which corresponds to 2.83 times higher than the heterojunction without the OECs. Furthermore, the OECs deposition changed the morphology of the heterojunction with the deposition of a thin film on its surface. In addition, during the FePi deposition, the BiVO4 layer seems to partially dissolve. Our study shows a facile methodology to boost the activity of photoanodes to the water oxidation by photoelectrodeposition of OECs.

There is a global concern with pollutants and organic contaminants and efficient and inexpensive methods are sought for the treatment of these toxic products. Generally, large volume reactors and the use of expensive equipment are required to monitor a photoreaction. The present work proposes the construction of a colorimetric equipment, which allows the online monitoring of photoreactions, using low-cost materials that allow the analysis from small aliquots. To show the applicability of the system, we studied the reduction reaction of 4-nitrophenol (4NP) with NaBH4. The impedimetric sensor enabled to construct the kinetic curve of the decrease in the chromophore band. It was possible to observe that the 4NP reduction reaction depends on: (i) chromophore concentration; (ii) stability of the reducing agent and; (iii) repulsion between the anions. The system developed here opens doors, as it can be used using a photocatalyst in the form of film, and it has also proved to be an inexpensive alternative for both research and teaching laboratories, as it allows the execution of chemical physics practices such as kinetic monitoring of reactions and mathematical adjustment of the curves.

Hydrogen is seen as a future energy carrier that will assist the global energy fuel demand. However, it is still necessary to study efficient and inexpensive catalysts that can be used on a large scale to make this technology practical. In this paper the electrodeposition of molybdenum disulfide (MoS2) film on titanium (Ti) substrate was performed by cyclic voltammetry and the film was evaluated for hydrogen evolution reaction (HER). The deposition optimized conditions was 25 cycles and 4 mmol L-1 (NH4)2[MoS4] in 0.1 mol L-1 NaClO4 solution. The film was characterized from X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and they showed an amorphous structure and high catalytic activity for HER. The Tafel slope was 85 mV dec-1 and overpotential at -10 mA cm-2 was -139 mV showing that Ti substrate compared with fluorine-tin doped oxide (FTO) substrate favored the HER and electroactivity of MoS2 films.

In spite of selenide semiconductors having a wide application area, TlCu2 Se2 (TCSe) is poorly studied and its synthesis by non-vacuum or thermic methodology in film form is non-existent. Generally, the main problems of applying these TCSe compounds are related to complicated single phase growth, and the great time consuming and non-scalable fabrication method. In this work, the facile, fast, scalable and new electrochemical deposition of this material was proposed as a workaround for these main problems and obtaining single phase thin film. Thus, the electrodeposited Tlx Cu3 - x Se2 films were characterized by scanning electron microscopy, X-ray diffraction (with Rietveld refinement) and energy dispersive X-ray spectroscopy. They showed interesting variation of composition (x =1.1, 1.2, and 1.25) and morphology as function of the electrodeposition potential, electrolytic bath temperature and thermal treatment.

Um novo sensor baseado em nanotubos de carbono de paredes múltiplas modificado com bastões de SnO2 foi desenvolvido para a determinação eletroquímica de levofloxacino. A morfologia, a estrutura, e o comportamento eletroquímico do eletrodo compósito foram caracterizados por microscopia eletrônica de varredura, energia dispersiva de raios X e voltametria cíclica, respectivamente. Voltametria de pulso diferencial em solução tampão fosfato pH 6,0 permitiu a aplicação de um método para determinar níveis de levofloxacino em um intervalo de 1,0-9,9 µmol L-1, com limite de detecção calculado em 0,2 µmol L-1 (72,0 mg L-1).

A new sensor based on multi-walled carbon nanotubes modified with SnO2 rods for the electrochemical determination of levofloxacin has been investigated. The morphology, the structure, and the electrochemical performance of the composite electrode were characterised by scanning electron microscopy, energy dispersive X-ray spectroscopy, and cyclic voltammetry, respectively. Differential pulse voltammetry in phosphate buffer solution at pH 6.0, allowed the application of a method to determine levofloxacin levels in a range of 1.0-9.9 µmol L-1, with a limit of detection calculated at 0.2 µmol L-1 (72.0 mg L-1).

Nesse trabalho foram obtidos eletrodepósitos de filmes finos de ZnTe sobre substrato de Pt, usando pulsos potenciotásticos. A influência do número de pulsos, tempo de deposição para cada elemento (Zn ou Te) e a ordem de deposição das camadas (Zn/Te ou Te/Zn) na morfologia, propriedades ópticas e na foto-corrente foi avaliada. Os dados de microanálise mostraram que a razão Zn/Te variou entre 0,12 e 0,30 sendo que o filme não era estequiométrico. Entretanto, o valor de energia da banda proibida obtido, em todas as condições experimentais utilizadas neste trabalho, foi de 2,28 eV, indicando a formação do filme de ZnTe. As amsotras com maior porcentagem de Zn apresentaram maior fotocorrente, a qual foi da ordem de 2,64 µA cm-2 e uma morfologia do tipo dendrítica.

In this work, the ZnTe thin films were electrodeposited using potentiostatic steps, on Pt substrate. The effect of steps number, the deposition time for each element (Zn or Te) and layer order (Zn/Te or Te/Zn) in the morphology, composition, band gap energy and photocurrent was evaluated. Microanalysis data showed that the ratio Zn/Te ranged from 0.12 and 0.30 and the film was not stoichiometric. However, the band-gap value obtained from in all experimental conditions used in this work was 2.28 eV, indicating film growth of ZnTe. The samples with higher Zn showed higher photocurrent, which was of the order of 2.64 µA cm-2 and dendritic morphology.

Medidas de transientes de corrente e microscopia eletrônica de varredura foram utilizados para caracterizar o processo de eletrocristalização e morfologia de ligas de estanho-zinco eletrodepositadas sobre Pt, na ausência e na presença de ácido tartárico. O modelo de Scharifker e Hills foi utilizado para analisar os transientes de corrente e revelou que o processo de eletrocristalização da liga Sn-Zn na presença de tartarato, sob as condições estudadas, é governado por nucleação progressiva tridimensional controlada por difusão. Na ausência do complexante, os resultados indicaram que o processo de nucleação varia de instantâneo para progressivo à medida que o potencial de deposição torna-se mais negativo, ou seja, pela incorporação de zinco ao depósito. Os resultados de microscopia mostraram depósitos com duas camadas com morfologias diferentes e que a mesma sofre influência do potencial de deposição.

Current transients measurements and scanning electron microscopy were used to characterize the electrocrystallization process and morphology of tin-zinc alloys electrodeposited on Pt, in the absence and in the presence of tartaric acid. The model of Scharifker and Hills was used to analyze the current transients and it revealed that Sn-Zn electrocrystallization process in the presence of tartrate, under the studied conditions, is governed by three-dimensional progressive nucleation controlled by diffusion. In the absence of the complexant, the results indicated that nucleation process changes from instantaneous to progressive when the deposition potential becomes more negative, or when the incorporation of zinc occured to the deposit. The microscopic results showed deposits with two layers with different morphologies and is also influenced by deposition potential.

Neste trabalho estudou-se a eletrodeposição de ligas de Fe-Mo e Ni-Mo sobre eletrodos de Pt em meio de citrato de sódio em pH 4,0. O comportamento das ligas foi avaliado por voltametria ciclica em diferentes razões dos íon metálicos. Os depósitos foram caracterizados por MEV, EDX e difração de raios-X. Nos voltamogramas cíclicos os picos de dissolução só aparecem para soluções com maior concentração de íons Fe ou Ni. Análises de MEV mostraram morfologias diferentes para as duas ligas estudadas sendo que as de Ni-Mo são mais uniformes e espessas. O conteúdo de Mo e O nas ligas Ni-Mo é maior do que na de Fe-Mo. A deposição das ligas de Ni-Mo é do tipo anômala.

This paper reports on a study of the electrodeposition of Ni-Mo and Fe-Mo alloys on Pt electrodes in a sodium citrate solution at pH 4.0. The alloys were subjected to cyclic voltammetry at different ion concentration ratios to identify their behavior. The electrodeposited coatings were analyzed by SEM, EDX and XRD. The results of the cyclic voltammetry tests indicated the presence of dissolution peaks only with high Ni or Fe ion concentrations. The SEM analysis revealed that the two alloys had dissimilar morphologies and the Ni-Mo alloys were homogeneous and thick. The Mo and O contents were higher in the Ni-Mo than in the Fe-Mo alloys. Anomalous deposition was found to occur in the co-deposition of Ni and Mo.

A deposição em regime de subtensão de Zn sobre Pt policristalina foi estudada em três diferentes soluções ácidas para diferentes concentrações de Zn2+. As cargas voltamétricas e a inibição, promovida pelo recobrimento máximo da superfície com Zn ads, na adsorção e na reação de desprendimento de hidrogênio foram usados para se postular modelos de adsorção. A co-adsorção dos ânions HSO4-, ClO4- e F-, tanto sobre o substrato de Pt como sobre os ad-átomos, exercem um papel muito importante na natureza da camada adsorvida. Sobre Pt, a carga máxima de redissolução do Zn ads encontrada foi aproximadamente 210 miC cm-2, exceto para o meio de fluoreto com Zn2+ 10-3 mol L-1, onde se encontrou um valor de aproximadamente 350 miC cm-2. Uma pequena inibição na reação de desprendimento de hidrogênio foi observada em ácido sulfúrico e perclórico, mas uma intensa inibição foi constatada em meio de ácido fluorídrico. Estes resultados foram associados com a interação dos volumosos oxi-ânions tanto com os ad-átomos como com o substrato. Finalmente, experimentos de coleção com o eletrodo rotatório de disco-anel foram feitos em meio de HF e os resultados confirmaram a carga máxima obtida dos voltamogramas. Os experimentos feitos com o eletrodo rotatório confirmaram que os picos voltamétricos analisados são relacionados com a deposição em subtensão do Zn.

The underpotential deposition of Zn on polycrystalline Pt was studied in three different acid solutions for different Zn2+ concentrations. The voltammetric charges and the inhibition promoted by the maximum coverage of Zn ads in the hydrogen adsorption and evolution reactions were used to postulate adsorption models. It was shown that the co-adsorption of anions HSO4-, ClO4- and F-, either on the substrate or on the ad-atoms, exerts a marked influence in the ad-layer nature. On Pt, the maximum values found for the redissolution charge were around 210 muC cm-2, except for 10-3 mol L-1 Zn2+ in fluoride medium where a value of 350 muC cm-2 was obtained. A negligible inhibition of the hydrogen evolution reaction was recorded in sulfuric and perchloric acid solutions while a strong inhibition was found for fluoride medium. These results were related to the interaction of the large oxy-anions either with the substrate or the ad-atoms. Collection experiments were performed with the rotating ring-disk electrode system (RRDE) and the results confirmed the large charge value obtained in the HF electrolyte. The experiments performed with the RDDE also demonstrated that the voltammetric peaks analyzed here are associated with UPD Zn.

A eletrodeposição de Fe, Co e ligas de Fe-Co foi investigada a partir de soluções de cloreto em pH 2.0. As ligas Fe-Co foram depositadas a partir de soluções com razão molar de 1:10, 1:1 e 10:1. O processo de eletrocristalização dos metais foi estudado através de saltos potenciostáticos. O modelo de Scharifker e Hills foi utilizado para analisar os transientes de corrente. Os resultados experimentais obtidos para Co e ligas de Fe-Co, depositadas a partir da solução de 1:10 ajustaram-se ao de um mecanismo de nucleação progressiva. No caso de Fe puro e ligas de Fe-Co, depositadas a partir das soluções 1:1 e 10:1, o processo de nucleação ocorreu pelo mecanismo de nucleação instantânea. A densidade do número de núcleos calculados variou de 2.6 a 19.1 x 10³ cm-2 para Fe e a taxa de formação de núcleos para Co de 0.10 a 15.8 x 10(6) cm-2 s-1.

The electrodeposition of Fe, Co and Fe-Co alloys onto Pt has been investigated from chloride solutions at pH 2.0. The Fe-Co alloys were deposited from solutions with molar ratio of 1:10, 1:1 and 10:1. Electrocrystallization of metals was studied by potentiostatic steps. The Scharifker and Hills model was used to analyze current transients. A progressive nucleation mechanism was found to fit the experimental results for both Co and Fe-Co alloys deposited from 1:10 solution. In the case of pure Fe and Fe-Co alloy, deposited from 1:1 and 10:1 solutions, the nucleation process occurred by the instantaneous mechanism. The nuclei number densities and rate of nucleation were calculated and their values were 2.6 to 19.1 x 10³ cm-2 for Fe and 0.10 to 15.8 x 10(6) cm-2 s-1 for Co deposition.

This work reviews recent studies of underpotential deposition (UPD) of several metals on Pt and Au substrates performed in the Grupo de Materiais Eletroquímicos e Métodos Eletroanalíticos (IQSC -- USP, São Carlos). The UPD Cu, Cd and Pb on Pt were analysed in terms of their influence in the oxygen evolution reaction. Partial blockage of surface active sites, promoted by Pb ad-atoms, resulted in a change from water to hydrogen peroxide as the final product. The Ag UPD on Pt and Au substrates was also discussed in this work. A detailed model of charge calculation for Ag monolayer was developed and confirmed by the rotating ring-disk data. The partial charge transfer in UPD studies was analysed in the Cd/Pt and Cd/Au systems and a value of 0.5 was found for the adsorption electrovalence of Cd ad-ions. The Sn/Pt UPD systems were studied from the point of view of the valences of metallic ions in solution. The deposition from Sn(IV) generates a full monolayer with a maximum occupation of approximately 40% of the surface active sites (340 µC cm-2) plus 105 µC cm-2 of Hads (half monolayer). Changing the metallic ion for Sn(II), it was possible to deposit a full monolayer (210 µC cm-2) without any detectable Hads. Finally, the effect of anions was discussed in the Zn/Pt and Zn/Au systems. Here, the hydrogen evolution reaction (her) and the hydrogen adsorption/desorption were used in order to investigate the maximum coverage of the surface with Zn ad-atoms. The full monolayer, characterised by the complete absence of Hads, was achieved only in 0.5 M HF solutions.