Aplicação de tecnologias eletroquímicas (oxidação via radicais hidroxila, oxidação mediada via cloro ativo e eletrocoagulação) para o tratamento de efluentes reais ou sintéticos

In this work the degradation of real and synthetic wastewater was studied using electrochemical processes such as oxidation via hydroxyl radicals, mediated oxidation via active chlorine and electrocoagulation. The real effluent used was collected in the decanter tank of the Federal University of Rio Grande do Norte (ETE-UFRN) of Effluent Treatment Plant and the other a textile effluent dye Ácido Blue 113 (AB 113) was synthesized in the laboratory. In the electrochemical process, the effects of anode material, current density, the presence and concentration of chloride as well as the active chlorine species on site generated were evaluated. Electrodes of different compositions, Ti/Pt, Ti/Ru0,3Ti0,7O2, BDD, Pb/PbO2 and Ti/TiO2-nanotubes/PbO2 were used as anodes. These electrodes were subjected to electroanalytical analysis with the goal of checking how happen the anodic and cathodic processes across the concentrations of NaCl and supporting electrolyte used. The potential of oxygen evolution reaction were also checked. The effect of active chlorine species formed under the process efficiency was evaluated by removing the organic matter in the effluent-ETE UFRN. The wastewater treatment ETE-UFRN using Ti/Pt, DDB and Ti/Ru0,3Ti0,7O2 electrodes was evaluated, obtaining good performances. The electrochemical degradation of effluent-UFRN was able to promote the reduction of the concentration of TOC and COD in all tested anodes. However, Ti/Ru0,3Ti0,7O2 showed a considerable degradation due to active chlorine species generated on site. The results obtained from the electrochemical process in the presence of chloride were more satisfactory than those obtained in the absence. The addition of 0.021 M NaCl resulted in a faster removal of organic matter. Secondly, was prepared and characterized the electrode Ti/TiO2-nanotubes/PbO2 according to what the literature reports, however their preparation was to disk (10 cm diameter) with surface area and higher than that described by the same authors, aiming at application to textile effluent AB 113 dye. SEM images were taken to observe the growth of TiO2 nanotubes and confirm the electrodeposition of PbO2. Atomic Force Microscope was also used to confirm the formation of these nanotubes. Furthermore, was tested and found a high electrochemical stability of the electrode Ti/TiO2-nanotubes/PbO2 for applications such as long-term indicating a good electrocatalytic material. The electrochemical oxidation of AB 113 using Ti/Pt, Pb/PbO2 and Ti/TiO2-nanotubes/PbO2 and Al/Al (electrocoagulation) was also studied. However, the best color removal and COD decay were obtained when Ti/TiO2-nanotubes/PbO2 was used as the anode, removing up to 98% of color and 92,5% of COD decay. Analysis of GC/MS were performed in order to identify possible intermediates formed in the degradation of AB 113.

Síntese de carreadores de oxigênio à base de Ni e Co para estudo do processo de Chemical Looping usando CH4 como combustível

Increasing energy demand is being met largely by fossil fuel reserves, which emit CO2, SOx gases and various other pollutants. So does the search for fuels that emit fewer pollutants and have the same energy efficiency. In this context, hydrogen (H2) has been increasingly recognized as a potential carrier of energy for the near future. This is because the H2 can be obtained by different routes and has a wide application area , in addition to having clean burning, generating only H2O as a product of combustion , and higher energy density per unit mass . The Chemical Looping Reforming process (CLR) has been extensively investigated in recent years, it is possible to regenerate the catalyst by applying cycles of reduction and oxidation. This work has as main objective to develop catalysts based on nickel and cobalt to study the reactivity of reform with chemical recycling process. The catalysts were prepared by three different methods: combustion assisted by microwave, wet impregnation and co-precipitation. All catalysts synthesized have the same amount by weight of the active phases (60% w / w). The other 40 % m/m consists in La2O3 (8% w / w), Al2O3 (30% w / w) and MgO (2%). Oxygen carriers have been named as follows: N or C, nickel or cobalt, followed by the number 3 or 6, meaning 30 to 60% of active phase in the oxide form and C, CI or CP, which means self-combustion assisted by microwave, self-combustion assisted by microwave followed by wet impregnation and co-precipitation. The oxygen carriers were then characterized by the techniques of X-ray diffraction (XRD), surface area (BET), temperature programmed reduction (TPR) and scanning electron microscopy (SEM). The characterization results showed that the different synthesis methods have led to obtaining different morphologies and structures. Redox tests using CH4 as reducing agent and sintetic air as oxidant agent was done with N6C and C6C, N6CI and C6CI and N6CP and C6CP oxygen carriers. The tests revealed different behaviors, depending on active phase and on synthesis procedure. N6C oxygen carrier produced high levels of H2. The C6CI oxygen carrier produced CO2 and H2O without carbon deposits.

Active Surface Deformation Technology for Management of Marine Biofouling

Biofouling, the accumulation of biomolecules, cells, organisms and their deposits on submerged and implanted surfaces, is a ubiquitous problem across various human endeavors including maritime operations, medicine, food industries and biotechnology. Since several decades, there have been substantial research efforts towards developing various types of antifouling and fouling release approaches to control bioaccumulation on man-made surfaces. In this work we hypothesized, investigated and developed dynamic change of the surface area and topology of elastomers as a general approach for biofouling management. Further, we combined dynamic surface deformation of elastomers with other existing antifouling and fouling-release approaches to develop multifunctional, pro-active biofouling control strategies.

This research work was focused on developing fundamental, new and environment-friendly approaches for biofouling management with emphasis on marine model systems and applications, but which also provided fundamental insights into the control of infectious biofilms on biomedical devices. We used different methods (mechanical stretching, electrical-actuation and pneumatic-actuation) to generate dynamic deformation of elastomer surfaces. Our initial studies showed that dynamic surface deformation methods are effective in detaching laboratory grown bacterial biofilms and barnacles. Further systematic studies revealed that a threshold critical surface strain is required to debond a biofilm from the surface, and this critical strain is dependent on the biofilm mechanical properties including adhesion energy, thickness and modulus. To test the dynamic surface deformation approach in natural environment, we conducted field studies (at Beaufort, NC) in natural seawater using pneumatic-actuation of silicone elastomer. The field studies also confirmed that a critical substrate strain is needed to detach natural biofilm accumulated in seawater. Additionally, the results from the field studies suggested that substrate modulus also affect the critical strain needed to debond biofilms. To sum up, both the laboratory and the field studies proved that dynamic surface deformation approach can effectively detach various biofilms and barnacles, and therefore offers a non-toxic and environmental friendly approach for biofouling management.

Deformable elastomer systems used in our studies are easy to fabricate and can be used as complementary approach for existing commercial strategies for biofouling control. To this end, we aimed towards developed proactive multifunctional surfaces and proposed two different approaches: (i) modification of elastomers with antifouling polymers to produce multifunctional, and (ii) incorporation of silicone-oil additives into the elastomer to enhance fouling-release performance.

In approach (i), we modified poly(vinylmethylsiloxane) elastomer surfaces with zwitterionic polymers using thiol-ene click chemistry and controlled free radical polymerization. These surfaces exhibited both fouling resistance and triggered fouling-release functionalities. The zwitterionic polymers exhibited fouling resistance over short-term (∼hours) exposure to bacteria and barnacle cyprids. The biofilms that eventually accumulated over prolonged-exposure (∼days) were easily detached by applying mechanical strain to the elastomer substrate. In approach (ii), we incorporated silicone-oil additives in deformable elastomer and studied synergistic effect of silicone-oils and surface strain on barnacle detachment. We hypothesized that incorporation of silicone-oil additive reduces the amount of surface strain needed to detach barnacles. Our experimental results supported the above hypothesis and suggested that surface-action of silicone-oils plays a major role in decreasing the strain needed to detach barnacles. Further, we also examined the effect of change in substrate modulus and showed that stiffer substrates require lower amount of strain to detach barnacles.

In summary, this study shows that (1) dynamic surface deformation can be used as an effective, environmental friendly approach for biofouling control (2) stretchable elastomer surfaces modified with anti-fouling polymers provides a pro-active, dual-mode approach for biofouling control, and (3) incorporation of silicone-oils additives into stretchable elastomers improves the fouling-release performance of dynamic surface deformation technology. Dynamic surface deformation by itself and as a supplementary approach can be utilized biofouling management in biomedical, industrial and marine applications.

Experimental data from column and batch samples

The presented thesis was written in the frame of a project called 'seepage water prognosis'. It was funded by the Federal Ministry for Education and Science (BMBF). 41 German institutions among them research institutes of universities, public authorities and engineering companies were financed for three years respectively. The aim was to work out the scientific basis that is needed to carry out a seepage water prognosis (Oberacker und Eberle, 2002). According to the Federal German Soil Protection Act (Federal Bulletin, 1998) a seepage water prognosis is required in order to avoid future soil impacts from the application of recycling products. The participants focused on the development of either methods to determine the source strength of the materials investigated, which is defined as the total mass flow caused by natural leaching or on models to predict the contaminants transport through the underlying soil. Annual meetings of all participants as well as separate meetings of the two subprojects were held. The department of Geosciences in Bremen participated with two subprojects. The aim of the subproject that resulted in this thesis was the development of easily applicable, valid, and generally accepted laboratory methods for the determination of the source strength. In the scope of the second subproject my colleague Veith Becker developed a computer model for the transport prognosis with the source strength as the main input parameter.

Experimental data on photophysiology and growth rates of the invasive foraminifera Amphistegina lobifera showing high thermal tolerance from the Eastern Mediterranean and the Gulf of Aqaba

Invasive species allow an investigation of trait retention and adaptations after exposure to new habitats. Recent work on corals from the Gulf of Aqaba (GoA) shows that tolerance to high temperature persists thousands of years after invasion, without any apparent adaptive advantage. Here we test whether thermal tolerance retention also occurs in another symbiont-bearing calcifying organism. To this end, we investigate the thermal tolerance of the benthic foraminifera Amphistegina lobifera from the GoA (29° 30.14167 N 34° 55.085 E) and compare it to a recent "Lessepsian invader population" from the Eastern Mediterranean (EaM) (32° 37.386 N, 34°55.169 E). We first established that the studied populations are genetically homogenous but distinct from a population in Australia, and that they contain a similar consortium of diatom symbionts, confirming their recent common descent. Thereafter, we exposed specimens from GoA and EaM to elevated temperatures for three weeks and monitored survivorship, growth rates and photophysiology. Both populations exhibited a similar pattern of temperature tolerance. A consistent reduction of photosynthetic dark yields was observed at 34°C and reduced growth was observed at 32°C. The apparent tolerance to sustained exposure to high temperature cannot have a direct adaptive importance, as peak summer temperatures in both locations remain <32°C. Instead, it seems that in the studied foraminifera tolerance to high temperature is a conservative trait and the EaM population retained this trait since its recent invasion. Such pre-adaptation to higher temperatures confers A. lobifera a clear adaptive advantage in shallow and episodically high temperature environments in the Mediterranean under further warming.

Seawater carbonate chemistry and biological processed during experiments with corals Porites sp. & Stylophora pistillata, 2010

Uptake of anthropogenic CO2 by the oceans is altering seawater chemistry with potentially serious consequences for coral reef ecosystems due to the reduction of seawater pH and aragonite saturation state (omega arag). The objectives of this long-term study were to investigate the viability of two ecologically important reef-building coral species, massive Porites sp. and Stylophora pistilata, exposed to high pCO2(or low pH) conditions and to observe possible changes in physiologically related parameters as well as skeletal isotopic composition. Fragments of Porites sp. and S. pistilata were kept for 6-14 months under controlled aquarium conditions characterized by normal and elevated pCO2 conditions, corresponding to pHTvalues of 8.09, 7.49, and 7.19, respectively. In contrast with shorter, and therefore more transient experiments, the long experimental timescale achieved in this study ensures complete equilibration and steady state with the experimental environment and guarantees that the data provide insights into viable and stably growing corals. During the experiments, all coral fragments survived and added new skeleton, even at seawater omega arag <1, implying that the coral skeleton is formed by mechanisms under strong biological control. Measurements of boron (B), carbon (C) and oxygen (O) isotopic composition of skeleton, C isotopic composition of coral tissue and symbiont zooxanthellae, along with physiological data (such as skeletal growth, tissue biomass, zooxanthellae cell density and chlorophyll concentration) allow for a direct comparison with corals living under normal conditions and sampled simultaneously. Skeletal growth and zooxanthellae density were found to decrease, whereas coral tissue biomass (measured as protein concentration) and zooxanthellae chlorophyll concentrations increased under high pCO2 (low pH) conditions. Both species showed similar trends of delta11B depletion and delta18O enrichment under reduced pH, whereas the delta13C results imply species-specific metabolic response to high pCO2 conditions. The skeletal delta11B values plot above seawater delta11B vs. pH borate fractionation curves calculated using either the theoretically derived deltaB value of 1.0194 (Kakihana et al., Bull. Chem. Soc. Jpn. 50(1977), 158) or the empirical deltaB value of 1.0272 (Klochko et al., EPSL 248 (2006), 261). However, the effective deltaB must be greater than 1.0200 in order to yield calculated coral skeletal delta11B values for pH conditions where omega arag >1. The delta11B vs. pH offset from the literature seawater delta11B vs. pH fractionation curves suggests a change in the ratio of skeletal material laid down during dark and light calcification and/or an internal pH regulation, presumably controlled by ion-transport enzymes. Finally, seawater pH significantly influences skeletal delta13C and delta18O. This must be taken into consideration when reconstructing paleo-environmental conditions from coral skeleton

Collection of vegetation and soil surface cover in the Jena Experiment (time series since 2002)

This collection contains measurements of vegetation and soil surface cover measured on the plots of the different sub-experiments at the field site of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. The following series of datasets are contained in this collection: 1. Measurements of vegetation cover, i.e. the proportion of soil surface area that is covered by different categories of plants per estimated plot area. Data was collected on the plant community level (sown plant community, weed plant community, dead plant material, and bare ground) and on the level of individual plant species in case of the species that have been sown into the plots to create the gradient of plant diversity.

An effective three-dimensional ordered mesoporous CuCo2O4 as electrocatalyst for Li-O2 batteries

Three-dimensional ordered mesoporous (3DOM) CuCo₂O₄ materials have been synthesized via a hard template and used as bifunctional electrocatalysts for rechargeable Li-O₂ batteries. The characterization of the catalyst by X-ray diffractometry and transmission electron microscopy confirms the formation of a single-phase, 3-dimensional, ordered mesoporous CuCo₂O₄ structure. The as-prepared CuCo₂O₄ nanoparticles possess a high specific surface area of 97.1 m² g^{- 1} and a spinel crystalline structure. Cyclic voltammetry demonstrates that mesoporous CuCo₂O₄ catalyst enhances the kinetics for either oxygen reduction reaction (ORR) or oxygen evolution reaction (OER). The Li-O₂ battery utilizing 3DOM CuCo₂O₄ shows a higher specific capacity of 7456 mAh g^{- 1} than that with pure Ketjen black (KB). Moreover, the CuCo₂O₄-based electrode enables much enhanced cyclability with a 610 mV smaller discharge-recharge voltage gap than that of the carbon-only cathode at a current rate of 100 mA g^{- 1}. Such excellent catalytic performance of CuCo₂O₄ could be associated with its larger surface area and 3D ordered mesoporous structure. The excellent electrochemical performances coupled with its facile and cost-effective way will render the 3D mesoporous CuCo₂O₄ nanostructures as attractive electrode materials for promising application in Li-O₂ batteries.

Produzione di alcol furfurilico da furfurale in fase gas con catalizzatori a base di CaO

The hydrogenation of biomass-derived molecules is a key reaction in upgrading these compounds into chemicals and fuels. The use of catalytic transfer hydrogenation, employing alcohols as hydrogen sources, offers an alternative approach to this process, avoiding the use of H2 under high pressure and precious metal catalysts. In this work, the gas-phase conversion of biomass-derived furfural into furfuryl alcohol and 2-methylfuran was studied, using methanol as the H-transfer agent and CaO-based catalysts. The results obtained with this catalyst were compared with those obtained by using MgO, which due to its basic properties and to its high surface area, at present appears to be among the best basic catalysts used for the conversion of biomass-derived molecules. Pure CaO, despite having a very low surface area, compared to MgO catalyst (5 m2/g vs. 172 m2/g), was shown to reduce furfural into its corresponding unsaturated alcohol at 350°C, thus allowing selective H-transfer from methanol to the substrate. These results highlight the potential application of the H-transfer reaction over CaO based catalysts as an efficient process for the selective reduction of biomass-derived molecules.

How to design the surface of peptide-loaded nanoparticles for efficient oral bioavailability?

International audience

Desenvolvimento de uma célula a combustível de glicerol direto em meio alcalino

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2015.

Desenvolvimento de uma célula a combustível de glicerol direto em meio alcalino

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2015.

Evolution of strength and physical properties of ultramafic and carbonate rocks under hydrothermal conditions

Interaction of rocks with fluids can significantly change mineral assemblage and structure. This so-called hydrothermal alteration is ubiquitous in the Earth’s crust. Though the behavior of hydrothermally altered rocks can have planet-scale consequences, such as facilitating oceanic spreading along slow ridge segments and recycling volatiles into the mantle at subduction zones, the mechanisms involved in the hydrothermal alteration are often microscopic. Fluid-rock interactions take place where the fluid and rock meet. Fluid distribution, flux rate and reactive surface area control the efficiency and extent of hydrothermal alteration. Fluid-rock interactions, such as dissolution, precipitation and fluid mediated fracture and frictional sliding lead to changes in porosity and pore structure that feed back into the hydraulic and mechanical behavior of the bulk rock. Examining the nature of this highly coupled system involves coordinating observations of the mineralogy and structure of naturally altered rocks and laboratory investigation of the fine scale mechanisms of transformation under controlled conditions. In this study, I focus on fluid-rock interactions involving two common lithologies, carbonates and ultramafics, in order to elucidate the coupling between mechanical, hydraulic and chemical processes in these rocks. I perform constant strain-rate triaxial deformation and constant-stress creep tests on several suites of samples while monitoring the evolution of sample strain, permeability and physical properties. Subsequent microstructures are analyzed using optical and scanning electron microscopy. This work yields laboratory-based constraints on the extent and mechanisms of water weakening in carbonates and carbonation reactions in ultramafic rocks. I find that inundation with pore fluid thereby reducing permeability. This effect is sensitive to pore fluid saturation with respect to calcium carbonate. Fluid inundation weakens dunites as well. The addition of carbon dioxide to pore fluid enhances compaction and partial recovery of strength compared to pure water samples. Enhanced compaction in CO2-rich fluid samples is not accompanied by enhanced permeability reduction. Analysis of sample microstructures indicates that precipitation of carbonates along fracture surfaces is responsible for the partial restrengthening and channelized dissolution of olivine is responsible for permeability maintenance.

Obtenção e caracterização de nanopartículas de argilominerais

Natural nanoclays are of great interest particularly for the production of polymer-based nanocomposites. In this work, kaolinite clays from two natural deposits in the State of the Rio Grande do Norte and Paraiba were purified with thermal treatment and chemical treatments, and characterized. Front to the gotten data, had been proposals methodologies for elimination or reduction of coarse particle texts, oxide of iron and organic substance. These methodologies had consisted of the combination of operations with thermal treatments, carried through in electric oven, and acid chemical attacks with and hydrogen peroxide. The Analyzers Thermogravimetric was used to examine the thermal stability of the nanoclays. The analysis indicated weight losses at temperatures under 110 ºC and over the temperature range of 350 to 550 ºC. Based on the thermal analysis data, the samples were submitted to a thermal treatment at 500 °C, for 8 h, to remove organic components. The X-ray diffraction patterns indicated that thermal treatment under 500 °C affect the basic structure of kaolinite. The BET surface area measurements ranged from 32 to 38 m2/g for clay samples with thermal treatment and from 36 to 53 m2/g for chemically treated samples. Thus, although the thermal treatment increased the surface area, through the removal of organic components, the effect was not significant and chemical treatment is more efficient, not affect the basic structure of kaolinite, to improve particle dispersion. SEM analysis confirms that the clay is agglomerated forming micron-size particles

Obtenção de óxidos a base de níquel e cobalto para reação de oxidação parcial do metano

Nickel-based catalysts supported on alumina have been widely used in various reactions to obtain synthesis gas or hydrogen. Usually, higher conversion levels are obtained by these catalysts, however, the deactivation by coke formation and sintering of metal particles are still problems to be solved. Several approaches have been employed in order to minimize these problems, among which stands out in recent years the use of additives such as oxides of alkali metals and rare earths. Similarly, the use of methodologies for the synthesis faster, easier, applicable on an industrial scale and to allow control of the microstructural characteristics of these catalysts, can together provide the solution to this problem. In this work, oxides with spinel type structure AB2O4, where A represents divalent cation and B represents trivalent cations are an important class of ceramic materials investigated worldwide in different fields of applications. The nickel cobaltite (NiCo2O4) was oxides of spinel type which has attracted considerable interest due to its applicability in several areas, such as chemical sensors, flat panel displays, optical limiters, electrode materials, pigments, electrocatalysis, electronic ceramics, among others. The catalyst precursor NiCo2O4 was prepared by a new chemical synthesis route using gelatine as directing agent. The polymer resin obtained was calcined at 350°C. The samples were calcined at different temperatures (550, 750 and 950°C) and characterized by X ray diffraction, measurements of specific surface area, temperature programmed reduction and scanning electron microscopy. The materials heat treated at 550 and 750°C were tested in the partial oxidation of methane. The set of techniques revealed, for solid preparations, the presence of the phase of spinel-type structure with the NiCo2O4 NixCo1-xO solid solution. This solid solution was identified by Rietveld refinement at all temperatures of heat treatment. The catalyst precursors calcined at 550 and 750°C showed conversion levels around 25 and 75%, respectively. The reason H2/CO was around 2 to the precursor treated at 750°C, proposed reason for the reaction of partial oxidation of methane, one can conclude that this material can be shown to produce synthesis gas suitable for use in the synthesis Fischer-Tropsch process