Análise teórica da interação de CO, CO2 e NH3 com ZnO

This paper presents a study of the interaction of small molecules with ZnO surfaces by means of theoretical methods. The AM1 semi-empirical method was used for optimizing the geometric parameters of adsorbed molecules. The optimized AM1 structures were used in the calculations of the ab initio RHF method with the 3-21G* basis set. The interaction of CO, CO2 and NH3 molecules were studied with (ZnO)22 and (ZnO)60 cluster models. We have analyzed the interaction energy, SCF orbital energies, Mulliken charges and the density of states (DOS).

Cinética de redução do catalisador CuO/ZnO/Al2O3

The reduction kinetics of a CuO/ZnO/Al2O3 catalyst by hydrogen was investigated isothermally and by temperature programmed reduction (TPR). Two reducible Cu2+ species were detected; the first one was identified as CuO bulk and the other as Cu2+ strongly interacting with alumina, possibly in the form of copper aluminate. The activation energies for the reduction of these two species were 60 and 90 kJ mol-1, respectively, and the reaction order with respect to hydrogen was one. The isothermal reduction data showed that the isotropic growth model is the most appropriate to describe the reaction rate data for both Cu2+ species.

Nanocompósitos semicondutores ZnO/TiO2: testes fotocatalíticos

Titanium dioxide is an efficient photocatalist, being possible to improve its efficiency with better charge separation which occurs when it is coupled with other semiconductors. Nanometric particles of ZnO were used to impregnate TiO2 P25 in order to optimize its photocatalytic properties. ZnO/TiO2 composites were obtained at different proportions and were characterized by X-ray diffraction (XRD), micro-Raman and diffuse reflectance spectroscopies, measurement of surface area (BET) and scanning electron microscopy (SEM). Raman spectroscopy data revealed a change on the TiO2 surface due the presence of ZnO which was observed by an enlargement of TiO2 peaks and a change on the relation rate between anatase and rutile phases of the composites. The photodegradation of azo-dye Drimaren red revealed better efficiency for ZnO/TiO2 3% nanocomposite and for ZnO pure.

Propriedades eletrônicas, estruturais e constantes elásticas do ZnO

The electronic, structural properties and elastic constants of the wurtzite phase of zinc oxide, ZnO, was investigated using computer simulation at Density Functional Theory level, with B3LYP hybrid functional and Hartree-Fock methodology. The electronic properties as well the band energy was investigated through the analysis of the band structures and density of states (DOS), and the mechanical properties was studied through the calculus of the elastic constants C11, C33, C44, C12 e C13. The results are in good agreement with experimental data found in the literature and in accordance with results obtained by another theoretical methodology.

Fotoeletrodegradação do corante AO7 utilizando filmes de nanocompósitos de ZnO-TiO2

The Zn-TiO2nanocomposite films were prepared by electrodeposition, using an acidic zinc sulphate solution with TiO2 nanoparticles in suspension. The as-deposited samples have been heated in air at 450 ºC for 6 h. The XRD and SEM analyses pointed out to the metal matrix conversion from Zn to ZnO and a rich morphology of needles-shaped grains. These materials were used on the photoelectrochemical degradation of AO7, which was efficiently degraded, with 40% of color removal, after 2 h period at 1.0 V, under white light irradiation. The apparent first order rate constant of the photoelectrodegradation reaction was 4.12 x 10-3 min-1.

INFLUÊNCIA DO TRATAMENTO TÉRMICO NO NANOCOMPÓSITO FOTOCATALISADOR ZnO/TiO2

ZnO/TiO2 nanocomposites were prepared by impregnating zinc acetate dihydrate on the surface of titanium dioxide P25, followed by thermal treatment at 350, 600, 750, and 900 °C, in order to investigate the TiO2 phase and titanate formation and the role of the latter in the photocatalytic activity of the nanocomposite. In the nanocomposites, the anatase-to-rutile transition is favored due to the presence of Zn2+, and the conversion is nearly complete at 750 °C. The presence of zinc metatitanate in the sample heated at 600 °C had no significant effect on the nanocomposite photocatalytic activity.

Ba-DOPED ZnO MATERIALS: A DFT SIMULATION TO INVESTIGATE THE DOPING EFFECT ON FERROELECTRICITY

ZnO is a semiconductor material largely employed in the development of several electronic and optical devices due to its unique electronic, optical, piezo-, ferroelectric and structural properties. This study evaluates the properties of Ba-doped wurtzite-ZnO using quantum mechanical simulations based on the Density Functional Theory (DFT) allied to hybrid functional B3LYP. The Ba-doping caused increase in lattice parameters and slight distortions at the unit cell angle in a wurtzite structure. In addition, the doping process presented decrease in the band-gap (Eg) at low percentages suggesting band-gap engineering. For low doping amounts, the wavelength characteristic was observed in the visible range; whereas, for middle and high doping amounts, the wavelength belongs to the Ultraviolet range. The Ba atoms also influence the ferroelectric property, which is improved linearly with the doping amount, except for doping at 100% or wurtzite-BaO. The ferroelectric results indicate the ZnO:Ba is an strong option to replace perovskite materials in ferroelectric and flash-type memory devices.

OBTAINING ZnO IMMOBILIZED OVER DIFFERENT SUBSTRATES BY HYDROTHERMAL TREATMENT FOR PHOTOCATALYSIS APPLICATION

The aim of this work is to systematically explore the effect of the synthesis conditions of ZnO structures, immobilized on different substrates by hydrothermal treatment, in its photocatalytic activity. A circumscribed central composite design of experiments was used to analyze the effects of reagents stoichiometry, reaction time and temperature, covering a wide range of these variables. The substrates used were etched glass, copper and zinc foils. The photocatalytic activity of the as-obtained ZnO samples was evaluated through photocatalytic degradation of rhodamine B (RhB) in aqueous solution under UV irradiation. Zinc foils presented the best immobilized film quality and the maximum dye removal was 80% in one hour of UV exposure.

Estudo da corrosão de cadinhos de SnO2-ZnO, na fusão de vidros contendo metais pesados

Neste trabalho foi estudada resistência de cadinhos de SnO2 dopados com 1%mol de ZnO frente a corrosão na fusão de vidro contendo metais pesados. Os cadinhos foram obtidos através do processo de colagem de barbotina, e a sinterização foi realizada até a temperatura de 1400ºC por 4 horas. Os vidros foram fundidos uma única vez por 1 hora, sendo que o vidro de composição 50B2O3-50PbO à 700 ºC, o de composição 60B2O3-40BaO à 1150 ºC e o de composição 66,67B2O3-33,33PbO à 700 ºC, sendo resfriados no interior dos cadinhos. Estes cadinhos foram então preparados e analisados por MEV-EDS.

Synthesis, structural and morphological characterization of CeO2-ZnO nanosized powder systems from Pechini's method

This work reports on the investigation of nanosized CeO2-ZnO systems prepared by Pechini's method. The structural and morphological characterization of CeO2-ZnO systems as well as the characterization of CeO2 and ZnO separately, showed that the employed method result in powders with spheroidal particles whose size are in the range 30 - 200 nm, which is appropriate to provide homogeneous suspensions. The ZnO present in the prepared mixed oxides seems to increase particle size distribution and to influence the arrangement of the particles after powder dispersion.

Influência de adições sucessivas de zinco, na forma de esterco suíno ou de óxido, no rendimento de matéria seca de milho

Em Santa Catarina, significativa porção dos dejetos das produções confinadas de suínos ainda está sendo jogada nos rios e córregos. Ao invés de poluentes, esses materiais poderiam ser utilizados como fertilizantes do solo, mas o uso contínuo de grandes quantidades pode ocasionar fitotoxidez de alguns nutrientes bem como poluir as águas superficiais e subterrâneas. O presente trabalho objetivou avaliar o rendimento de matéria seca de milho, decorrente da adição de quantidades crescentes e cumulativas de Zn ao solo, aplicadas na forma de ZnO ou de dejetos de suínos (alimentados com ração enriquecida com zinco). Foram realizados três cultivos sucessivos com 30 dias cada, em casa de vegetação, em vasos com 5,0 kg (base seca) de um Latossolo, que continha 590 g kg-1 de argila e pH 5,9. As doses de Zn utilizadas equivaleram a 0; 6,25; 12,5; 25 e 50 mg kg-1 de solo e foram aplicadas antes de cada cultivo. Determinaram-se a matéria seca da parte aérea, o Zn no solo, extraído com HCl 0,1 mol L-1, e a concentração e o acúmulo de Zn no tecido vegetal. A concentração de Zn no solo e nas plantas, assim como a quantidade de Zn absorvido, aumentou com o aumento da dose e com as reaplicações desse nutriente, tendo sido o teor de Zn no solo maior nos tratamentos com esterco suíno do que com ZnO. O rendimento de matéria seca não foi afetado pela aplicação de nenhuma das fontes de Zn, em qualquer cultivo. A adição cumulativa de até 150 mg kg-1 de Zn de solo elevou o teor de Zn no solo e na planta para valores superiores a 160 e 250 mg kg-1, respectivamente, e mesmo assim não ocasionou toxidez desse nutriente ao milho em seu estádio inicial de crescimento, mostrando que a amplitude entre suficiência e toxidez de Zn é ampla nesse solo.

Polymers as carriers for rhizobial inoculant formulations

The aim of this work was to evaluate the efficiency of carboxymethyl cellulose (CMC) and starch blends as carrier materials of rhizobial inoculants regarding their capacity to maintain viable cells and promote cowpea (Vigna unguiculata) nodulation. The experimental design adopted was completely randomized, with three replicates. Forty different compositions of carboxymethyl cellulose (CMC) with starch, compatibilized or not with different proportions of MgO or ZnO, were evaluated regarding their ability of maintaining rhizobial viable cells during the storage period of one month at room temperature, in an initial screening. Thereafter, selected inoculant carrier blends were evaluated regarding their ability to maintain viable rhizobial cells for a period of 165 days, and their performance as inoculant carriers was compared to a peat-based inoculant carrier under greenhouse conditions. Rhizobial cells were better maintained in blends containing 50-60% CMC. Compatibilizing agents did not increase survival of rhizobial cells for 30 days of storage. The cowpea nodulation of polymer blends was statistically the same of peat-based inoculants. CMC/starch polymer blends are efficient carriers to rhizobial inoculants for up to 165 days of storage, when compatibilized with MgO (1%).

Modos de aplicação de calcário e de micronutrientes em pomar de laranjeira 'Natal' e análise comparativa de custos

De acordo com o Agrianual (2005), a produção citrícola brasileira é de 17,7 milhões de toneladas ano-1,ocupando aproximadamente 1 milhão de hectares no território brasileiro e, deste total, 810 mil hectares localizam-se no Estado de São Paulo. A maioria dos solos brasileiros, inclusive aqueles onde foram instalados os pomares cítricos, apresenta reação ácida. Esta é, sem dúvida, a principal condição desfavorável dos solos e um dos fatores limitantes da produção em solos tropicais. O presente trabalho teve por objetivo estudar o efeito de diferentes modos de aplicação de calcário e de micronutrientes e analisar, de forma comparativa, os custos destes tratamentos em um pomar de laranjeira. O experimento foi desenvolvido na Fazenda Morumbi, município de Estrela D'Oeste-SP, num Argissolo Vermelho-Amarelo. A variedade de laranjeira utilizada foi a 'Natal', enxertada em limão Cravo, com 6 anos de idade e espaçamento 5 x 8 m. O delineamento experimental foi em parcelas subdivididas, com 3 repetições, com 5 tratamentos principais (sem calcário; a necessidade total de calcário (NC) incorporado; NC sem incorporação; ¹/2 NC no primeiro ano + ¹/2 NC no segundo ano e ¹/3 NC no primeiro ano, + ¹/3 NC no segundo ano, + ¹/3 NC no terceiro ano) e dois tratamentos secundários [micronutrientes via solo (FTE-BR 12: 11,5 % de ZnO e B2O3; 1% CuO; 5,4% de Fe2O3; 5,5% de MnO2; 0,2% de MoO3) e micronutrientes via foliar (sulfato de zinco a 0,5% e ácido bórico a 0,08%)], distribuídos em blocos casualizados. Não houve efeito significativo dos modos de aplicação da calagem e de micronutrientes sobre as variáveis avaliadas (produção, sólidos solúveis totais, acidez total titulável). Para massa média do fruto, o efeito significativo aconteceu apenas no primeiro ano, com a calagem em dose única e sem incorporação, e micronutrientes via solo. Concluiu-se que não houve efeito significativo dos modos de aplicação do calcário e dos micronutrientes para produção e massa média dos frutos da laranjeira 'Natal', e a receita líquida foi positiva em todos os tratamentos, sendo que o tratamento 5 [¹/3 da necessidade total de calcário (NC) no 1º ano + ¹/3 da NC no 2º ano, + ¹/3 da NC no 3º ano] apresentou o melhor valor acumulado (U$ 3.721,85 ha-1).

Synthesis, characterization and thermal behaviour of solid-state compounds of benzoates with some bivalent transition metal ions

Solid-state MBz compounds, where M stands for bivalent Mn, Fe, Co, Ni, Cu and Zn and Bz is benzoate, have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), infrared spectroscopy and complexometry were used to characterize and to study the thermal behaviour of these compounds. The procedure used in the preparation of the compounds via reaction of basic carbonates with benzoic acid is not efficient in eliminating excess acid. However the TG-DTA curves permitted to verify that the binary compounds can be obtained by thermosynthesis, because the benzoic acid can be eliminated before the thermal decomposition of these compounds. The results led to information about the composition, dehydration, thermal stability, thermal decomposition and structure of the isolated compounds. On heating, these compounds decompose in two (Mn, Co, Ni, Zn) or three (Fe, Cu) steps with formation of the respective oxide (Mn3O4, Fe2O3, Co3O4, NiO, CuO and ZnO) as final residue. The theoretical and experimental spectroscopic studies suggest a covalent bidentate bond between ligand and metallic center.

Kinetic measurements during transient film growth on zinc

The electrochemical behaviour of zinc has been extensively studied in alkaline and acid media, but only a few studies have been reported in neutral solutions, particularly in deaerated media. Zinc passivation in neutral medium and the effect of the ClO4- ion on the nucleation and growth of the passive layer is studied in this paper by a transient technique at different electrolyte concentrations and applied potentials. ZnO growth rate was shown to decrease with increasing electrolyte concentration. Moreover, passive layer growth occurred followed by pitting nucleation and growth. Film growth and pit nucleation are explained by means of the Macdonald and Engell-Stolica models.