Significantly enhancement of sunlight photocatalytic performance of ZnO by doping with transition metal oxides

In this study we report, the synthesis of ZnO and its doping with Transition Metal Oxides -TMO-, such as Cr2O3, MnO2, FeO, CoO, NiO, Cu2O and CuO. Various characterization techniques were employed to investigate the structural properties. The X-ray diffraction (XRD) data and Rietveld refinement confirmed the presence of TMO phases and that the ZnO structure was not affected by the doping with TMO which was corroborated using transmission Electron microscopy (TEM). Surface areas were low due to blockage of adsorption sites by particle aggregation. TMO doping concentration in the range of 3.7–5.1% was important to calculate the catalytic activity. The UV–Visible spectra showed the variation in the band gap of TMO/ZnO ranging from 3.45 to 2.46 eV. The surface catalyzed decomposition of H2O2 was used as the model reaction to examine the photocatalytic activity following the oxygen production and the systems were compared to bulk ZnO and commercial TiO2-degussa (Aeroxyde-P25). The results indicate that the introduction of TMO species increase significantly the photocatalytic activity. The sunlight photocatalytic performance in ZnO-doped was greater than bulk-ZnO and in the case of MnO2, CoO, Cu2O and CuO surpasses TiO2 (P25-Degussa). This report opens up a new pathway to the design of high-performance materials used in photocatalytic degradation under visible light irradiation

Characterization of copper microelectrodes, following a homemade lithography, technique, and gold electroless deposition

We report the fabrication and characterization of copper microelectrodes obtained by a homemade lithography technique and after gold electroless deposition. For the fabrication, planes consisting of arrays of electrodes (black in color) with bow tie shape were designed and printed on a transparent paper (Canson ltd.). Using an embroidery frame with a silk fabric, a photographic emulsion was spread on the silk and simultaneously pressing the Canson paper on it. The system was introduced into a closed box and exposed with a UV light. The designed electrode templates prevented direct exposition of the UV light over copper films and indelible ink was spread over it. After the ink was dried, the copper film is immersed into ferric acid to attack the uncovered copper parts (where there is no ink). In this way, we obtained copper electrodes with initial gap separation of ~142μm and subsequently, they followed electroless deposition of gold to make the copper electrodes to contact. For the characterization, electrical measurements were performed. They present ohmic resistance values in the order of 106 Ω produced by surface scattering of the electrons within the gold microwire and enhanced by oxidation of the copper electrodes

Hyperfine Magnetic Properties Alloys Zr (FexCr1-x)2 Hydrides.

Investigamos as propriedades magnéticas e as interações hiperfinas das ligas \'ZR\'\'(\'FE IND. x\'\'CR IND. 1-x\') IND. 2\' (0.3 < x < 0.7) e seus hidretos, através de medidas de magnetização em campos até 9 T, suscetibilidade AC e espectroscopia Mossbauer. A difração de raios X confirmou a estrutura de fase de Laves hexagonal Cl4 para todas as amostras. Os espectros Mossbauer das ligas à temperatura ambiente apresentaram dois dubletos quadrupolares, que podiam ser atribuídos de duas maneiras aos sítios cristalográficos 2a e 6h do Fe. Esta ambigüidade foi resolvida por um cálculo de cargas pontuais, com as posições atômicas determinadas por refinamento Rietveld. Medidas magnéticas e de Mössbauer a baixas temperaturas indicaram que todas as ligas da faixa de concentrações estudada apresentaram comportamento de vidros de spin, sem ordem magnética de longo alcance. As temperaturas de congelamento de spins observadas puderam ser descritas em seu conjunto pela equação de Vogel-Fulcher. A concentração crítica de Fe para a formação de momentos magnéticos foi determinada. O efeito da absorção de hidrogênio foi investigado: a) com o teor máximo de H em todas as ligas, b) com teores intermediários na liga \'ZR\'\'(\'FE IND. 0.5\'\'CR IND. 0.5\') IND. 2\'. Nesta última, os espectros Mössbauer mostraram a coexistência de uma fase pobre e uma fase rica em H. O desdobramento quadrupolar do Fe no sítio 6h apresentou variação com a temperatura, atribuída a efeitos de difusão de hidrogênio. O principal efeito do hidrogênio sobre o magnetismo das ligas foi um incremento notável dos momentos magnéticos, porém sem aparecimento de ordem ferromagnética; ao contrário, observou-se um pequeno abaixamento das temperaturas de congelamento de spins.We have investigated the magnetic properties and hyperfine interactions in the \'ZR\'\'(\'FE IND. x\'\'CR IND. 1-x\') IND. 2\' (0.3 < x < 0.7) alloys and their hydrides, by means of magnetization measurements in fields up to 9 T, AC susceptibility and Mõssbauer spectroscopy. X-ray diffraction confirmed the Laves phase Cl4 hexagonal structure for all samples. The room temperature Mõssbauer spectra of all samples showed two quadrupolar doublets, which could be assigned in two ways to the Fe crystallographic sites 2a and 6h. This ambiguity was solved by a point-charge calculation using atomic positions determined by Rietveld refinement. Magnetic and Mõssbauer measurements at low temperatures indicated that all investigated samples showed spin-glass behavior, without long-range magnetic order. The set of observed spin freezing temperatures could be described with the Vogel-Fulcher equation. The critical Fe concentration for magnetic moment formation has been determined. The effect of hydrogen absorption was investigated: a) with the maximum H content for all alloys, b) with intermediate H contents for the \'ZR\'\'(\'FE IND. 0.5\'\'CR IND. 0.5\') IND. 2\' alloy. Mõssbauer spectra for the latter samples showed the coexistence of a H-poor and a H-rich phase. The Fe quadrupole splitting at the 6h site exhibited a temperature dependence which was attributed to hydrogen diffusion effects. The main effect of hydrogen on the magnetism was a significant increase in magnetic moments, yet without ferromagnetic ordering; a slight lowering of spin freezing temperatures was actually observed

Experimental evidence of the spin-glass transition in the diluted magnetic semiconductor Zn(1-x)Mn(x)In(2)Se(4)

This work reports on magnetic measurements of the quasi-two-dimensional (quasi-2D) system Zn(1-x)Mn(x)In(2)Se(4), with 0.01 <= x <= 1.00. For x > 0.67, the quasi-2D system seems to develop a spin-glass behaviour. Evidence of a true phase transition phenomenon is provided by the steep increase of the nonlinear susceptibility chi(nl) when approaching T(C) from above. The static scaling of chi(nl) data yields critical exponents delta = 4.0 +/- 0.2, phi = 4.37 +/- 0.17 and TC = 3.4 +/- 0.1 K for the sample with x = 1.00 and similar values for the sample with x = 0.87. These critical exponents are in good agreement with values reported for other spin-glass systems with short-range interactions

Growth and formation mechanism of shape-selective preparation of ZnO structures : correlation of structural, vibrational and optical properties

A shape-selective preparation method was used to obtain highly crystalline rod-, needle-, nut-, and doughnut-like ZnO morphologies with distinct particle sizes and surface areas. We study the nucleation and growth mechanism of those structures and the influence of physical–chemical parameters, such as the solvent and the pH of the solution, on the morphology, as well as the structural and optical properties. A clear correlation between the growth rate along the c-axis and surface defects was established. Our results suggest that the needle- and rod-like morphologies are formed due to the crystal growth orientation along the c-axis and the occurrence of crystalline defects, such as oxygen vacancies and interstitial Zn2+ located at the surface, whereas nuts and doughnuts are formed due to growth along all crystalline planes except those related to growth along the c-axis. Based on the experimental results, growth mechanisms for the formation of ZnO structures were proposed. We believe this synthetic route will be of guidance to prepare several materials whose shapes will depend on the desired applications

Core-shell Au/Fe3O4 nanocomposite synthesized by thermal decomposition method : structural, optical, and magnetic properties

Core-shell structure Au@Fe3O4 nanoparticles was synthesized via a thermal decomposition method, evidencing through interplanar atomic distances of ~ 0.23 nm and ~ 0.48 nm finding in the center and the shell of the particles, matching to the (1 1 1) Au and (1 1 1) magnetite planes, respectively. The nanocomposite has an average diameter of the core of ~ 10.5 nm and a thickness of the shell of ~1.85 nm, accessed by TEM. X-ray diffraction carried out on the sample shows the crystal structure of fcc Au and fcc Fe3O4 without a spurious crystalline phase. Besides, Rietveld refinement displays an outer diameter of ~ 8.1 and ~ 12.3 for the core and shell, respectively, the latter using the Scherrer constant of 0.9 and 1.43, respectively. The UV–vis characterization result shows a surface plasmon resonance spectra of Au@Fe3O4 nanoparticles at ~ 540 nm, which advise a successful core–shell coupling of Au and the Fe3O4. Finally, the magnetic response displays a system with a superparamagnetic state at room temperature and with a distribution of blocking temperatures associated with the enhanced surface contribution related to the hollow magnetite structure's inner and outer surface. From the mean TB, the effective magnetic anisotropy J/m3 was obtained, which is in agreement with the expected for the magnetite phase

PEGylation of SPIONs by polycondensation reactions: A new strategy to improve colloidal stability in biological media

In this study, we report on a new route of PEGylation of superparamagnetic iron oxide nanoparticles (SPIONs) by polycondensation reaction with carboxylate groups. Structural and magnetic characterizations were performed by X-ray diffractometry (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and vibrating sample magnetometry (VSM). The XRD confirmed the spinel structure with a crystallite average diameter in the range of 3.5-4.1 nm in good agreement with the average diameter obtained by TEM (4.60-4.97 nm). The TGA data indicate the presence of PEG attached onto the SPIONs' surface. The SPIONs were superparamagnetic at room temperature with saturation magnetization (M S) from 36.7 to 54.1 emu/g. The colloidal stability of citrate- and PEG-coated SPIONs was evaluated by means of dynamic light scattering measurements as a function of pH, ionic strength, and nature of dispersion media (phosphate buffer and cell culture media). Our findings demonstrated that the PEG polymer chain length plays a key role in the coagulation behavior of the Mag-PEG suspensions. The excellent colloidal stability under the extreme conditions we evaluated, such as high ionic strength, pH near the isoelectric point, and cell culture media, revealed that suspensions comprising PEG-coated SPION, with PEG of molecular weight 600 and above, present steric stabilization attributed to the polymer chains attached onto the surface of SPIONs. © 2013 Springer Science+Business Media Dordrecht