Pyrolysis and auto-gasification of black liquor in presence of ZnO: An integrated process for Zn/ZnO nanostructure production and bioenergy generation

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Reduction of the photocatalytic activity of ZnO nanoparticles for UV protection applications

The detrimental effects of UV radiation are having a significant impact on our life and environment. The development of effective UV shielding agents is therefore of great importance to our society. ZnO nanoparticles are considered to be one of the most effective UV blocking agents. However, the development of ZnO-based UV shielding products is currently hindered due to the adverse effects of the inherent photocatalytic activity exhibited by ZnO. This paper reports our recent study on the possibility of reducing the photoactivity of ZnO nanoparticles via surface modification and impurity doping. It was found that the photoactivity was drastically reduced by SiO2-coatings that were applied to ZnO quantum dots using the Stöber method and a microemulsion technique. The effect of transition metal doping on the photoactivity was also studied using mechanochemical processing and a co-precipitation method. Cobalt doping reduced the photoactivity, while manganese doping led to mixed results, possibly due to the difference in the location of dopant ions derived from the difference in the synthesis methods.

Reduction of the photocatalytic activity of ZnO by impurity doping

 The thesis systematically presents several methods to synthesize the photocatalytic activity reduced ZnO by impurity doping and coating which is suitable for many commercial and medical applications in sun-screening area. The author has published one book chapter and many high quality journal papers.

Bio-hydrogen production based on catalytic reforming of volatiles generated by cellulose pyrolysis: an integrated process for ZnO reduction and zinc nanostructures fabrication

The paper presents a process of cellulose thermal degradation with bio-hydrogen generation and zinc nanostructures synthesis. Production of zinc nanowires and zinc nanoflowers was performed by a novel processes based on cellulose pyrolysis, volatiles reforming and direct reduction of ZnO. The bio-hydrogen generated in situ promoted the ZnO reduction with Zn nanostructures formation by vapor–solid (VS) route. The cellulose and cellulose/ZnO samples were characterized by thermal analyses (TG/DTG/DTA) and the gases evolved were analyzed by FTIR spectroscopy (TG/FTIR). The hydrogen was detected by TPR (Temperature Programmed Reaction) tests. The results showed that in the presence of ZnO the cellulose thermal degradation produced larger amounts of H2 when compared to pure cellulose. The process was also carried out in a tubular furnace with N2 atmosphere, at temperatures up to 900 °C, and different heating rates. The nanostructures growth was catalyst-free, without pressure reduction, at temperatures lower than those required in the carbothermal reduction of ZnO with fossil carbon. The nanostructures were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). The optical properties were investigated by photoluminescence (PL). One mechanism was presented in an attempt to explain the synthesis of zinc nanostructures that are crystalline, were obtained without significant re-oxidation and whose morphologies are dependent on the heating rates of the process. This route presents a potential use as an industrial process taking into account the simple operational conditions, the low costs of cellulose and the importance of bio-hydrogen and nanostructured zinc.

Gold coating of silica and zinc oxide nanoparticles by the surface reduction of gold(I) chloride

The possibility of a surface inner sphere electron transfer mechanism leading to the coating of gold via the surface reduction of gold(I) chloride on metal and semi-metal oxide nanoparticles was investigated. Silica and zinc oxide nanoparticles are known to have very different surface chemistry, potentially leading to a new class of gold coated nanoparticles. Monodisperse silica nanoparticles were synthesised by the well known Stöber protocol in conjunction with sonication. The nanoparticle size was regulated solely by varying the amount of ammonia solution added. The presence of surface hydroxyl groups was investigated by liquid proton NMR. The resultant nanoparticle size was directly measured by the use of TEM. The synthesised silica nanoparticles were dispersed in acetonitrile (MeCN) and added to a bis acetonitrile gold(I) co-ordination complex [Au(MeCN)2]+ in MeCN. The silica hydroxyl groups were deprotonated in the presence of MeCN generating a formal negative charge on the siloxy groups. This allowed the [Au(MeCN)2]+ complex to undergo ligand exchange with the silica nanoparticles, which formed a surface co-ordination complex with reduction to gold(0), that proceeded by a surface inner sphere electron transfer mechanism. The residual [Au(MeCN)2]+ complex was allowed to react with water, disproportionating into gold(0) and gold(III) respectively, with gold(0) being added to the reduced gold already bound on the silica surface. The so-formed metallic gold seed surface was found to be suitable for the conventional reduction of gold(III) to gold(0) by ascorbic acid. This process generated a thin and uniform gold coating on the silica nanoparticles. This process was modified to include uniformly gold coated composite zinc oxide nanoparticles (Au@ZnO NPs) using surface co-ordination chemistry. AuCl dissolved in acetonitrile (MeCN) supplied chloride ions which were adsorbed onto ZnO NPs. The co-ordinated gold(I) was reduced on the ZnO surface to gold(0) by the inner sphere electron transfer mechanism. Addition of water disproportionated the remaining gold(I) to gold(0) and gold(III). Gold(0) bonded to gold(0) on the NP surface with gold(III) was reduced to gold(0) by ascorbic acid (ASC), which completed the gold coating process. This gold coating process of Au@ZnO NPs was modified to incorporate iodide instead of chloride. ZnO NPs were synthesised by the use of sodium oxide, zinc iodide and potassium iodide in refluxing basic ethanol with iodide controlling the presence of chemisorbed oxygen. These ZnO NPs were treated by the addition of gold(I) chloride dissolved in acetonitrile leaving chloride anions co-ordinated on the ZnO NP surface. This allowed acetonitrile ligands in the added [Au(MeCN)2]+ complex to surface exchange with adsorbed chloride from the dissolved AuCl on the ZnO NP surface. Gold(I) was then reduced by the surface inner sphere electron transfer mechanism. The presence of the reduced gold on the ZnO NPs allowed adsorption of iodide to generate a uniform deposition of gold onto the ZnO NP surface without the use of additional reducing agents or heat.

Optical, Field-Emission, and Antimicrobial Properties of ZnO Nanostructured Films Deposited at Room Temperature by Activated Reactive Evaporation

ZnO nanostructures were deposited on flexible polymer sheet and cotton fabrics at room temperature by activated reactive evaporation. Room-temperature photoluminescence spectrum of ZnO nanostructured film exhibited a week intrinsic UV emission and a strong broad yellow-orange visible emission. TEM and HRTEM studies show that the grown nanostructures are crystalline in nature and their growth direction was indentified to be along [002]. ZnO nanostructures grown on the copper-coated flexible polymer sheets exhibited stable field-emissio characteristics with a threshold voltage of 2.74 V/mu m (250 mu A) and a very large field enhancement factor (beta) of 23,213. Cotton fabric coated with ZnO nanostructures show an excellent antimicrobial activity against Staphylococcus aureus bacteria (Gram positive), and similar to 73% reduction in the bacterial population is achieved compared to uncoated fabrics after 4 h in viability. Using a shadow mask technique, we also selectively deposited the nanostructures at room temperature on polymer substrates.

Structural, EPR, photo and thermoluminescence properties of ZnO:Fe nanoparticles

Zn(1-x)Fe(x)O(1+0.5x) (x = 0.5-5 mol%) nanoparticles were synthesized by a low temperature solution combustion route. The structural characterization of these nanoparticles by PXRD, SEM and TEM confirmed the phase purity of the samples and indicated a reduction in the particle size with increase in Fe content. A small increase in micro strain in the Fe doped nanocrystals is observed from W-H plots. EPR spectrum exhibits an intense resonance signal with effective g values at g approximate to 2.0 with a sextet hyperfine structure (hfs) besides a weak signal at g approximate to 4.13. The signal at g approximate to 2.0 with a sextet hyperfine structure might be due to manganese impurity where as the resonance signal at g approximate to 4.13 is due to iron. The optical band gap E-g was found to decrease with increase of Fe content. Raman spectra exhibit two non-polar optical phonon (E-2) modes at low and high frequencies at 100 and 435 cm(-1) in Fe doped samples. These modes broaden and disappear with increase of Fe do pant concentration. TL measurements of gamma-irradiated (1-5 kGy) samples show a main glow peak at 368 degrees C at a warming rate of 6.7 degrees Cs-1. The thermal activation parameters were estimated from Glow peak shape method. The average activation energy was found to be in the range 0.34-2.81 eV. (C) 2012 Elsevier B.V. All rights reserved.

Stabilization of the high-temperature and high-pressure cubic phase of ZnO by temperature-controlled milling

The reversible transition of wurtzite to rock salt phase under pressure is well reported in literature. The cubic phase is unstable under ambient conditions both in the bulk and in nanoparticles. This paper reports defect-induced stabilization of cubic ZnO phase in sub 20 nm ZnO particles and explores their optical properties. The size reduction was achieved by ball milling in a specially designed mill which allows a control of the milling temperature. The process of synthesis involved both variation of milling temperature (including low temperature similar to 150 K) and impact pressure. We show that these have profound influence in the introduction of defects and stabilization of the cubic phase. A molecular dynamics simulation is presented to explain the observed results. The measured optical properties have further supported the observations of defect-induced stabilization of cubic ZnO and reduction in particle size.

Numerical simulation of the growth of ZnO nanostructures in a tube furnace by physical vapour deposition

Zinc oxide is a versatile II-VI naturally n-type semiconductor that exhibits piezoelectric properties. By controlling the growth kinetics during a simple carbothermal reduction process a wide range of 1D nanostructures such as nanowires, nanobelts, and nanotetrapods have been synthesized. The driving force: for the nanostructure growth is the Zn vapour supersaturation and supply rate which, if known, can be used to predict and explain the type of crystal structure that results. A model which attempts to determine the Zn vapour concentration as a function of position in the growth furnace is described. A numerical simulation package, COMSOL, was used to simultaneously model the effects of fluid flow, diffusion and heat transfer in a tube furnace made specifically for ZnO nanostructure growth. Parameters such as the temperature, pressure, and flow rate are used as inputs to the model to show the effect that each one has on the Zn concentration profile. An experimental parametric study of ZnO nanostructure growth was also conducted and compared to the model predictions for the Zn concentration in the tube. © 2008 Materials Research Society.

Structural and optical properties of ZnO films on SrTiO3 substrates by MOCVD

ZnO films have been fabricated on (0 0 1), (0 1 1) and (1 1 1) SrTiO3 (STO) substrates by metal-organic chemical vapour deposition (MOCVD). It is interesting that the ZnO films on (0 0 1) and (0 1 1) STO substrates show polar and semipolar orientations, which are different from previous reports, while the same growing direction of polar ZnO with previous results is found on (1 1 1) STO. For the atomic arrangements, two orthogonal domains and a single domain are observed on (0 0 1) and (1 1 1) STO, respectively. Photoluminescence spectra show that every sample has a sharp near-band-edge emission peak at about 3.28 eV without any deep-level emission band between 1.5 and 2.8 eV, implying a high optical quality. A violet emission around 3.0 eV is observed only in ZnO films on (0 0 1) and (0 1 1) STO substrates grown at 600 degrees C, which is discussed briefly. Additionally, the semipolar ZnO does not weaken the emission efficiency along with the reduction in the polarization effect compared with polar ZnO. These results show that high-quality polar and semipolar ZnO films can be grown on STO substrates by MOCVD.

Nanostructure and properties of ZnO films produced by the pyrosol process

Indium doped ZnO films were deposited by the pyrosol process on glass substrates at different temperatures from solutions containing In/Zn molar ratios up to 10%. The nanostructure of the films was investigated using grazing-incidence small angle X-ray scattering (GISAXS). The mass density was determined by X-ray reflectivity and the composition by X-ray photoelectron spectroscopy. The GISAXS measurements revealed an anisotropic pattern for films deposited at 573 and 623 K and a isotropic one for those deposited at higher temperatures. The anisotropic patterns indicate the presence of elongated nanopores with their long axes perpendicular to the film surface. In contrast, the isotropic nature of GISAXS patterns of films grown at high temperatures (673 and 723 K) suggests the presence of spherical voids. The pore size distribution function determined from the isotropic patterns indicates a multimodal size distribution. on the other hand, the measured mass density of the doped films with isotropic nanotexture is higher than that of the anisotropic films while the electric resistivity is significantly lower. This is in agreement with the detected strong reduction of the void density and specific surface area at approximately constant pore size.

A new interpretation for the degradation phenomenon of ZnO varistors

The electrical degradation phenomena of zinc oxide-based varistors were studied using a high-energy current pulse and a.c. polarization at different temperatures. Activation energy measurements during the degradation process showed that these phenomena are associated with diffusion and that the diffusion-controlling species are slower than Zn., For degradation promoted by current pulses of 8×20 μs, the Schottky potential barrier deformation was measured. A decrease in height and width of the potential barrier due to the reduction of surface states density, N s, without a significant change in donor density, N d, was observed. To explain these results, a modification of the unstable components model is proposed for the potential barrier in which the degradation is due to oxi-reduction reactions between atomic defects. These reactions promote the elimination of zinc vacancies and/or adsorbed oxygen on the grain boundaries. © 1992 Chapman & Hall.