Biblioteca Digital

Iron oxide nanoparticles, with size ranging from 50 to 100 nm, were synthesized by a solvothermal method. The amounts of iron(III) chloride precursor (from 2.5 to 10.0 mmol) and sodium hydroxide (between 10 and 30 mmol) were varied along with the synthesis temperature (180 or 200°C). Depending on the synthesis conditions, samples with magnetic properties consisting of magnetite (Fe3O4), or by a mixture of magnetite and maghemite (c-Fe2O3), and samples with no magnetism consisting of hematite (a-Fe2O3), were obtained. The catalytic activity of the materials was studied for the degradation of diphenhydramine using the photo-Fenton process. All materials performed well on the degradation of this emerging pollutant. The best compromise between catalytic activity and stability was obtained with pure magnetite nanoparticles prepared at 180°C from a 4:1 molar ratio between sodium hydroxide and iron(III) chloride. This cat- alyst was used in further studies at different pH (2.8–11.0), catalyst loads (up to 200 mg L-1) and hydrogen peroxide concentrations (1–50 mM). Complete degradation of diphenhydramine with 78% of mineralization was achieved at relatively low leaching of iron species from the catalyst to the aqueous solution (1.9 mg L-1). Acidic pH (2.8) is preferable to neutral or alkaline pH (i.e. 6.0...

Complex fac-[RuCl(3)(NO)(P-N)] (1) was synthesized from the reaction of [RuCl(3)(H(2)O)(2)(NO)] and the P-N ligand, o-[(N,N-dimethylamino)phenyl]diphenylphosphine) in refluxing methanol solution, while complex mer,trans-[RuCl(3)(NO)(P-N)] (2) was obtained by photochemical isomerization of (1) in dichloromethane solution. The third possible isomer mer, cis-[RuCl(3)(NO)(P-N)] (3) was never observed in direct synthesis as well as in photo-or thermal-isomerization reactions. When refluxing a methanol solution of complex (2) a thermally induced isomerization occurs and complex (1) is regenerated. The complexes were characterized by NMR ((31)P{(1)H}, (15)N{1H} and 1H), cyclic voltammetry, FTIR, UV-Vis, elemental analysis and X-ray diffraction structure determination. The (31)P{(1)H} NMR revealed the presence of singlet at 35.6 for (1) and 28.3 ppm for (2). The (1)H NMR spectrum for (1) presented two singlets for the methyl hydrogens at 3.81 and 3.13 ppm, while for (2) was observed only one singlet at 3.29 ppm. FTIR Ru-NO stretching in KBr pellets or CH(2)Cl(2) solution presented 1866 and 1872 cm(-1) for (1) and 1841 and 1860 cm(-1) for (2). Electrochemical analysis revealed a irreversible reduction attributed to Ru(II)-NO(+) -> Ru(II)-NO(0) at -0.81 V and -0.62 V...

This paper reports our initial research to obtain SrWO4 microcrystals by the injection of ions into a hot aqueous solution and their photocatalytic (PC) properties. These microcrystals were structurally characterized by X-ray diffraction (XRD), Rietveld refinements and Fourier transform (FT)-Raman spectroscopy. The shape and average size of these SrWO 4 microcrystals were observed by field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). In addition, we have investigated the PC activity of microcrystals for the degradation of rhodamine B (RhB) and rhodamine 6G (Rh6G) dyes. XRD patterns, Rietveld refinement data and FT-Raman spectroscopy confirmed that SrWO4 microcrystals have a scheelite-type tetragonal structure without deleterious phases. FT-Raman spectra exhibited 12 Raman-active modes in a range from 50 to 1000 cm-1. FE-SEM and TEM images suggested that the SrWO4 microcrystals (rice-like - 95%; star-, flower-, and urchin-like - 5%) were formed by means of primary/secondary nucleation events and self-assembly processes. Based on these FE-SEM/TEM images, a crystal growth mechanism was proposed and discussed in details in this work. Finally, a good PC activity was first discovered of the SrWO4 microcrystals for the degradation of RhB after 80 min and Rh6G after 50 min dyes under ultraviolet-light...

Much has been talking about the advantages of polymeric nanocomposites, but little is known about the influence of nanoparticles on the stability of these materials. In this sense, we studied the influence of both oxides of zirconium and titanium, known to have photocatalytic properties, as well as the influence of synthetic clay Laponite on the photodegradation of styrene-butadiene rubber (SBR). SBR nanocomposites were prepared by the colloidal route by mixing commercial polymer lattices and nanometric anatase TiO2, monoclinic ZrO2 or exfoliated Laponite clays colloidal suspensions. To better understand the degradation mechanisms that occur in these nanocomposites, the efficiency of different photocatalysts under ultraviolet radiation was monitored by FT-IR and UV-vis spectroscopies and by differential scanning calorimetric. It was observed that TiO2 and ZrO2 nanoparticles undoubtedly acted as catalysts during the photodegradation process with different efficiencies and rates. However, when compared to pure SBR samples, the polymer degradation mechanism was unaffected. Unlike studies with nanocomposites montmorillonite, exfoliated laponite clay effectively acts as a photostabilizer of polymer UV photodegradation. Copyright © 2012 Wiley Periodicals...

Dissertação de mestrado integrado em Engenharia Civil; Os avanços nanotecnológicos atingem inúmeras áreas da ciência, mas no âmbito da sustentabilidade dos materiais de construção os progressos embora importantes são escassos e acima de tudo objeto de reduzida divulgação. O presente artigo sintetiza uma avaliação do estado da arte relativa a alguns dos contributos da nanotecnologia para a sustentabilidade dos materiais de construção. No mesmo, se aborda a compreensão dos compostos gerados durante a hidratação do cimento Portland, o aumento da resistência e da durabilidade de argamassas e betões pela adição de nanopartículas e nanotubos e de que forma a adição de nanopartículas pode contribuir para a autolimpeza, a purificação do ar e a capacidade bactericida em materiais construtivos por via do efeito fotocatalítico. A presente dissertação de mestrado aborda ainda os últimos desenvolvimentos da nanotecnologia com vista à eficiência energética, nomeadamente pela produção de isolamentos térmicos de elevado desempenho, janelas com baixa condutibilidade térmica, vidros com transmitância variável e materiais de mudança de fase mais eficientes. Os contributos da nanotecnologia para a ecoeficiência dos materiais de construção são muito amplos...

Nanostructured semi-conductor materials based on titanium dioxide, with effective photo-catalytic properties under UV illumination, were synthesized using sol-gel technology and characterized by X-Ray diffraction and scanning electron microscopy, with the objective of studying the photo-catalytic hydrogen production from water. The need to decrease the electron-hole recombination rate was accounted for by metal doping and the addition of ethanol as a hole trap. Aqueous suspensions of the semiconductor powders, with noble metal loadings (Pt) of 1.5 wt% were used and the effect of solution pH and temperature (20-70ºC) on hydrogen production were studied, for a selected catalyst concentration. Hydrogen production rates were found to be linear with solution temperature with values larger than published literature data.

The photo-catalytic production of hydrogen by means of irradiation of a suspension of semiconductor oxides presents attractive features over other methods with higher cost such as water electrolysis. In this work, photocatalytic hydrogen production from water is studied, using ethanol as sacrificial agent. New nanostructured multifunctionalised semiconductor materials based on titanium dioxide, with effective photo-catalytic properties under UV illumination were synthesized using sol-gel technology and characterised by X-Ray diffraction and scanning electron microscopy. Aqueous suspensions of the semiconductor powders were used and the effect of solution pH and temperature (20-70ºC) as well as the effect of concentration of ethanol on hydrogen production were studied, for fixed concentrations of the catalyst. Comparison is made with doped Degussa-P25 TiO2 titanium dioxide. The need to decrease the electron-hole recombination rate was accounted for by metal doping [1] with the ethanol molecule acting as a hole trap. An increase in the hydrogen production rate was found as a result of the percentage of metal on doped titania and optimisation of experimental conditions with rate values being superior to recently published literature data [2]. Particle size...

1. The hydrolysis of a variety of galactosides and other glycosides by α-galactosidases I and II of Vicia faba was studied. 2. The effect of temperature on kinetic parameters was also examined. 3. Both enzymes are inhibited by excess of substrate (p-nitrophenyl α-d-galactoside); with enzyme I this is competitive and is caused by the galactosyl moiety. 4. Enzyme I is inhibited by oligosaccharides possessing terminal non-reducing galactose residues and to a smaller extent by l-arabinose and d-fucose. 5. The effect of pH on Km and Vmax. values suggests that carboxyl and imidazole groups are involved in the catalytic activity of enzyme I. 6. Photo-oxidation experiments with enzyme I also suggest that an imidazole group is present at the active site.

We report photo-catalytic H2 production by hydrogenase (H2ase)-quantum dot (QD) hybrid assemblies. Quenching of the CdTe exciton emission is observed, consistent with electron transfer from quantum dot to H2ase. GC analysis shows light driven H2 production in the presence of a sacrificial electron donor with an efficiency of 4%, which is likely a lower limit to these hybrid systems. FTIR was employed for direct observation of active site reduction in unprecedented detail for photo-driven H2ase catalysis with sensitivity towards both H2ase and sacrificial electron donor. Photosensitization with Ru(bpy)32+ shows distinct FTIR photo- reduction properties generating all states along the steady-state catalytic cycle with minimal H2 production indicating slow, sequential one electron reduction steps. Comparing H2ase activity and FTIR results of both systems shows that QDs bind more efficiently for electron transfer and the final enzyme state is different for the two sensitizers. The possible origins of these differences and their implications for the enzymatic mechanism are discussed.

We evaluate a theoretical model in which Ru is substituting for Ti at the (100) surface of anatase TiO2. Charge transfer from the photo-excited TiO2 substrate to the catalytic site triggers the photo-catalytic event (such as water oxidation or reduction half-reaction). We perform ab-initio computational modeling of the charge transfer dynamics on the interface of TiO2 nanorod and catalytic site. A slab of TiO2 represents a fragment of TiO2 nanorod in the anatase phase. Titanium to ruthenium replacement is performed in a way to match the symmetry of TiO2 substrate. One molecular layer of adsorbed water is taken into consideration to mimic the experimental conditions. It is found that these adsorbed water molecules saturate dangling surface bonds and drastically affect the electronic properties of systems investigated. The modeling is performed by reduced density matrix method in the basis of Kohn-Sham orbitals. A nano-catalyst modeled through replacement defect contributes energy levels near the bottom of the conduction band of TiO2 nano-structure. An exciton in the nano-rod is dissipating due to interaction with lattice vibrations, treated through non-adiabatic coupling. The electron relaxes to conduction band edge and then to the Ru cite with faster rate than hole relaxes to the Ru cite. These results are of the importance for an optimal design of nano-materials for photo-catalytic water splitting and solar energy harvesting.

Nanostructured composites based on titanium dioxide have been studied in order to improve optical and photo-catalytic properties, as well as their performance in gas sensors. In this work, titanium and tin dioxides were simultaneously synthesized by the polyol method resulting in TiO2 platelet coated with SnO2 nanoparticles as was observed by scanning electron microscopy. The thermal analysis showed that the combined synthesis promotes more easily the crystallization of the TiO2 rutile phase. The composite obtained after heat treatment at 500 degrees C showed to be formed of almost only rutile phases of both oxides. The optical properties analyzed by UV-Vis spectroscopy showed that the combined oxides have higher absorbance, which reinforces a model found in the literature based on the flow of photo-generated electrons to the conduction band of SnO2 delaying the recombination of charges.

Conventional techniques to form selective surface energy regions on rigid inorganic substrates are not suitable for polymer interfaces due to sensitive and soft limitation of intrinsic polymer properties. Therefore, there is a strong demand for finding a novel and compatible method for polymeric surface energy modification. Here, by employing the confined photo-catalytic oxidation method, we successfully demonstrate full polymer filed-effect transistors fabricated through four-step spin-coating process on a flexible polymer substrate. The approach shows negligible etching effect on polymeric film. Even more, the insulating property of polymeric dielectric is not affected by the method, which is vital for polymer electronics. Finally, the self-aligned full polymer field-effect transistors on the flexible polymeric substrate are fabricated, showing good electrical properties and mechanical flexibility under bending tests.

Understanding of the dynamic process of laser-induced ultrafast electron tunneling is still very limited. It has been thought that the photo-catalytic reaction of adsorbents on the surface is either dependent on the number of resultant electron-hole pairs where excess energy is lost to the lattice through coupling with phonon modes, or dependent on irradiation photon wavelength. We used UV (355 nm) laser pulses to excite electrons from the valence band to the conduction band of titanium dioxide (TiO2), zinc oxide (ZnO) and bismuth cobalt zinc oxide (Bi2O3)0.07(CoO)0.03(ZnO)0.9 semiconductor nanoparticles with different photo catalytic properties. Photoelectrons are extracted, accelerated in a static electric field and eventually captured by charge deficient atoms of adsorbed organic molecules. A time-of-flight mass spectrometer was used to detect negative molecules and fragment ions generated by un-paired electron directed bond cleavages. We show that the probability of electron tunneling is determined by the strength of the static electric field and intrinsic electron mobility of semiconductors. Photo-catalytic dissociation or polymerization reactions of adsorbents are highly dependent on the kinetic energy of tunneling electrons as well as the strength of laser influx. By using this approach...

Mesoporous silica, specifically SBA-15, acid-treated multi-walled carbon nanotubes and a hybrid nanocomposite of SBA-15 coated onto the sidewalls acid-treated multi-walled carbon nanotubes (CNTs) were prepared and used as supports for anatase TiO2. Sol-gel methods were adapted for the synthesis of selected supports and for coating the materials with selected wt% loading of titania. Physical and chemical properties of the supports and catalyst composite materials were investigated by powder X-ray diffraction (XRD), Raman spectroscopy, thermogravimetric analysis, scanning electron microscope (SEM), high-resolution transmission electron microscope (HRTEM), UV-vis diffuse reflectance spectroscopy and fluorescence spectroscopy. The photo-activity of the catalyst composites were evaluated on the decolorisation of methylene blue as a model pollutant. Coating CNTs with SBA-15 improved the thermal stability and textural properties of the nanotubes. All supported titania composites had high surface areas (207–301 m2/g), altered band gap energies and reduced TiO2 crystallite sizes. The TiO2/SBA-CNT composite showed enhanced photo-catalytic properties and activity than the TiO2/SBA-15 and TiO2/CNT composites. In addition, an interesting observation was noted with the TiO2/SBA-15 nanocomposites...

Recently it has been reported that palladium nanocubes (PdNC) are capable of generating singlet oxygen without photo-excitation simply via chemisorption of molecular oxygen on its surface. Such a trait would make PdNC a highly versatile catalyst suitable in organic synthesis and a Reactive Oxygen Species (ROS) inducing cancer treatment reagent. Here we thoroughly investigated the catalytic activity of PdNC with respect to their ability to produce singlet oxygen and to oxidize 3,5,3′,5′-tetramethyl-benzidine (TMB), as well as, analyzed the cytotoxic properties of PdNC on HeLa cells. Our findings showed no evidence of singlet oxygen production by PdNC. The nanocubes’ activity is not necessarily linked to activation of oxygen. The oxidation of substrate on PdNC can be a first step followed by PdNC regeneration with oxygen or other oxidant. The catalytic activity of PdNC towards oxidation of TMB is very high and shows direct two-electrons oxidation when the surface of PdNC is clean and the ratio of TMB/PdNC is not very high. Sequential one electron oxidation is observed when the pristine quality of PdNC surface is compromised by serum or uncontrolled impurities and/or the ratio of TMB/PdNC is high. Clean PdNC in serum-free media efficiently induce apoptosis of HeLa cells. It is the primary route of cell death and is associated with hyperpolarization of mitochondria...

The aim of the present work is spectroscopic and thermodynamic study of DNA catalytic properties in the following processes: a) redox; b) formation of inter-strand cross-links; c) performing of photo-dynamic effects; d) nanoscale resonance radiationless electron excitation energy transfer. The most attention is paid to the latter, as truly nanoscale method in its origin. The nanoscale method of laser induced fluorescence resonance energy transfer (FRET) to donor (acridine orange) - acceptor (ethidium bromide) intercalator pair for quantitative and qualitative study of stability quality DNA double helix in solution in real time is offered. FRET method allows to estimate the concentration of double helix areas with high quality stability applicable for intercalation in DNA after it was subjected to stress effect. It gives the opportunity to compare various types of DNAs with 1) different origin; 2) various damage degrees; 3) being in various functional state. Alternative model and mechanisms of photodynamic effect on DNA in solutions are proposed. They are based on photoenergy degradation in solutions. The energy activates electrolytic dissociation of water molecules on H3O+ and OH- and acts as a catalyst for hydrolyse reactions of phosphordiester and glycoside linkages.; Comment: 51 pages...

We present here results of our first principles studies of the sulfur doping effects on the electronic and geometric structures of graphitic carbon nitride (g-C3N4). Using the Ab initio thermodynamics approach combined with some kinetic analysis, we reveal the favorable S-doping configurations By analyzing the valence charge densities of the doped and un-doped systems, we find that sulfur partially donates its px- and py- electrons to the system with some back donation to the S pz-states. To obtain accurate description of the excited electronic states, we calculate the electronic structure of the systems using the GW method. The band gap width calculated for g-C3N4 is found to be equal to 2.7 eV that is in agreement with experiment. We find the S doping to cause a significant narrowing the gap. Furthermore, the electronic states just above the gap become occupied upon doping that makes the material a conductor. Analysis of the projected local densities of states provides insight into the mechanism underlying such dramatic changes in the electronic structure of g-C3N4 upon the S doping. Based on our results, we propose a possible explanation for the S doping effect on the photo-catalytic properties of g-C3N4 observed in the experiments.

Agricultural lands under food and bio-energy crops, managed grass and permanent crops including agro-forestry, occupy about 40-50% of the Earth's land surface^1^. In 2005, agriculture accounted for an estimated emission of 5.1 to 6.1 GtCO2-eq/yr (10-12% of total global anthropogenic emissions of greenhouse gases (GHGs))^1^. However, measures to mitigate GHGs emission from agricultural soils are limited to improved cropland practices such as crop rotation, nutrient management, tillage/residue management, agroforestry, and return to natural vegetation^2^. These practices are not only far from substantially reducing GHGs emissions from soils or permanentlystabilizing soil organic matter^1-4^, but are also predicted to hardly match more than amaximum of 25% of the GHGs reductions required by the Kyoto Protocol within 2050^5^.Despite the knowledge that GHGs release from soil largely derives from biochemicaltransformations of plant litter and soil organic matter (SOM)^6-8^, no new and much wished biotechnological measures are adopted so far to augment mitigation^1^. Here we propose an innovative approach to mitigate GHGs emissions from soils based on the insitu photo-polymerization of SOM under biomimetic catalysis. Three Mediterranean soils of different physical and chemical properties were added with a synthetic watersolubleiron-porphyrin...

In this paper a set of TiO2 and Fe/TiO2 delaminated clays, prepared by different synthesis procedures, was characterized by electron paramagnetic resonance (EPR) spectroscopy. EPR analyses revealed an important shift of the central g-value as consequence of Fe3+ insertion (substitution) in the TiO2 structure by a sensitive and direct method of iron incorporation. A series of additional g-values, symmetrically distributed around the central absorption line, was attributed to some electron trapping sites (defects) remained in the TiO2 framework. The spectroscopic characterizations carried out in this work contribute to understand the photo-catalytic properties previously observed for these solids.