On the stability of conventional and nano-structured carbon-based catalysts in the oxidative dehydrogenation of ethylbenzene under industrially relevant conditions

Relevant carbon-based materials, home-made carbon-silica hybrids, commercial activated carbon, and nanostructured multi-walled carbon nanotubes (MWCNT) were tested in the oxidative dehydrogenation of ethylbenzene (EB). Special attention was given to the reaction conditions, using a relatively concentrated EB feed (10 vol.% EB), and limited excess of O2 (O 2:EB = 0.6) in order to work at full oxygen conversion and consequently avoid O2 in the downstream processing and recycle streams. The temperature was varied between 425 and 475 °C, that is about 150-200 °C lower than that of the commercial steam dehydrogenation process. The stability was evaluated from runs of 60 h time on stream. Under the applied reactions conditions, all the carbon-based materials are apparently stable in the first 15 h time on stream. The effect of the gasification/burning was significantly visible only after this period where most of them fully decomposes. The carbon of the hybrids decomposes completely rendering the silica matrix and the activated carbon bed is fully consumed. Nano structured MWCNT is the most stable; the structure resists the demanding reaction conditions showing an EB conversion of ∼30% (but deactivating) with a steady selectivity of ∼80%. The catalyst stability under the ODH reaction conditions is predicted from the combustion apparent activation energies. © 2014 Elsevier Ltd. All rights reserved.

Micro/nano-structured superhydrophobic surfaces in the biomedical field: part I: basic concepts and biomimetic approaches.

Inspired by natural structures, great attention has been devoted to the study and development of surfaces with extreme wettable properties. The meticulous study of natural systems revealed that the micro/nano-topography of the surface is critical to obtaining unique wettability features, including superhydrophobicity. However, the surface chemistry also has an important role in such surface characteristics. As the interaction of biomaterials with the biological milieu occurs at the surface of the materials, it is expected that synthetic substrates with extreme and controllable wettability ranging from superhydrophilic to superhydrophobic regimes could bring about the possibility of new investigations of cellâ material interactions on nonconventional surfaces and the development of alternative devices with biomedical utility. This first part of the review will describe in detail how proteins and cells interact with micro/nano-structured surfaces exhibiting extreme wettabilities.

Adsorption and electropolymerization of toluidine blue on the nano structured octakis(hydridodimethylsiloxy)-octasilsesquioxane surface

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Development of newly conceived biomimetic nano-structured biomaterials as scaffolds for bone and osteochondral regeneration

The present research thesis was focused on the development of new biomaterials and devices for application in regenerative medicine, particularly in the repair/regeneration of bone and osteochondral regions affected by degenerative diseases such as Osteoarthritis and Osteoporosis or serious traumas. More specifically, the work was focused on the synthesis and physico-chemical-morphological characterization of: i) a new superparamagnetic apatite phase; ii) new biomimetic superparamagnetic bone and osteochondral scaffolds; iii) new bioactive bone cements for regenerative vertebroplasty. The new bio-devices were designed to exhibit high biomimicry with hard human tissues and with functionality promoting faster tissue repair and improved texturing. In particular, recent trends in tissue regeneration indicate magnetism as a new tool to stimulate cells towards tissue formation and organization; in this perspective a new superparamagnetic apatite was synthesized by doping apatite lattice with di-and trivalent iron ions during synthesis. This finding was the pin to synthesize newly conceived superparamagnetic bone and osteochondral scaffolds by reproducing in laboratory the biological processes yielding the formation of new bone, i.e. the self-assembly/organization of collagen fibrils and heterogeneous nucleation of nanosized, ionically substituted apatite mimicking the mineral part of bone. The new scaffolds can be magnetically switched on/off and function as workstations guiding fast tissue regeneration by minimally invasive and more efficient approaches. Moreover, in the view of specific treatments for patients affected by osteoporosis or traumas involving vertebrae weakening or fracture, the present work was also dedicated to the development of new self-setting injectable pastes based on strontium-substituted calcium phosphates, able to harden in vivo and transform into strontium-substituted hydroxyapatite. The addition of strontium may provide an anti-osteoporotic effect, aiding to restore the physiologic bone turnover. The ceramic-based paste was also added with bio-polymers, able to be progressively resorbed thus creating additional porosity in the cement body that favour cell colonization and osseointegration.

Competing anisotropies in exchange biased nano-structured thin films

The magnetic anisotropies of a patterned, exchange biased Fe50Mn50/Ni80Fe20 system are studied using ferromagnetic resonance, supplemented by Brillouin light scattering experiments and Kerr magnetometry. The exchange biased bi-layer is partially etched into an antidot geometry so that the system approximates a Ni80 Fe20 layer in contact with antidot structured Fe50 Mn50 . Brillouin light scattering measurements of the spin wave frequency dependence on the wave vector reveal a magnonic band gap as expected for a periodic modulation of the magnetic properties. Analysis of the ferromagnetic resonance spectra reveals 8-fold and 4-fold contributions to the magnetic anisotropy. Additionally, the antidot patterning decreases the magnitude of the exchange bias and modifies strongly its angular dependence. Softening of all resonance modes is most pronounced for the applied magnetic field aligned within 10◦ of the antidot axis, in the direction of the bias. Given the degree to which one can tailor the ground state, the resulting asymmetry at low frequencies could make this an interesting candidate for applications such as selective/directional microwave filtering and multi-state magnetic logic.

Interface-mediated ferroelectric patterning and Mn valency in nano-structured PbTiO3/La0.7Sr0.3MnO3

We employed a multitechnique approach using piezo-force response microscopy and photoemission microscopy to investigate a self-organizing polarization domain pattern in PbTiO3/La0.7Sr0.3MnO3 (PTO/LSMO) nanostructures. The polarization is correlated with the nanostructure morphology as well as with the thickness and Mn valence of the LSMO template layer. On the LSMO dots, the PTO is upwards polarized, whereas outside the nanodots, the polarization appears both strain and interface roughness dependent. The results suggest that the electronic structure and strain of the PTO/LSMO interface contribute to determining the internal bias of the ferroelectric layer.

Active site engineering for heterogeneous catalysis using emerging nano-structured materials

The growing concern about the depletion of oil has spurred worldwide interest in finding alternative feedstocks for important petrochemical commodities and fuels. On the one hand, the enormous re-serves found (208 trillion cubic feet proven1), environmental sustainability and lower overall costs point to natural gas as the primary source for energy and chemicals in the near future.2 Nowadays the transformation of methane into useful chemicals and liquid fuels is only feasible via synthesis gas, a mixture of molecular hydrogen and carbon monoxide, that is further transformed to methanol or to hydrocarbons under moderate reaction conditions (150-350 °C and 10-100 bar).3 For a major cost reduction and in order to valorize small natural gas sources, either more efficient "syngas to products" catalysts should be produced or the manner in which methane is initially activated should be changed, ideally by developing catalysts able to directly oxidize methane to interesting products such as methanol. On the other hand, from the point of view of CO2 emissions, the use of the re-maining fossil resources will further contribute to global warming. In this scenario, the development of efficient routes for the transformation of CO2 into useful chemicals and fuels would represent a considerable step forward towards sustainability. Indeed, the environmental and economic incen-tives to develop processes for the conversion of CO2 into fuels and chemicals are great. However, for such conversions to become economically feasible, considerable research is necessary. In this lecture we will summarize our recent efforts into the design of new catalytic systems, based on MOFs and COFs, to address these challenges. Examples include the development of new Fe based FTS catalysts, electrocatalysts for the selective conversion of CO2 into syngas, the development of efficient catalysts for the utilization of formic acid as hydrogen storage vector and the development of new enzyme inspired systems for the direct transformation of methane to methanol under mild reaction conditions. References (1) http://www.clearonmoney.com/dw/doku.php?id=public:natural_gas_reserves. (2) Derouane, E. G.; Parmon, V.; Lemos, F.; Ribeiro, F. R. Sustainable Strategies for the Up-grading of Natural Gas: Fundamentals, Challenges, and Opportunities; Springer, 2005. (3) Rofer-DePoorter, C. K. Chemical Reviews. ACS Publications 1981, pp 447–474.

Functional nanostructured catalysts based on the niobates to the dry methane reforming and ethylene homologation reactions

Catalytic activity and selectivity of niobate-based nanostructured materials were investigated. Dry methane reforming (DMR) and ethylene homologation reaction (EHR) were selected as test reactions. KSr 2Nb5O15, Sr2NaNb5O 15 and NaSr2(NiNb4)O15 δ niobate powders were prepared by the high energy ball milling method and calcined in a reductor atmosphere. N2 adsorption isotherms, X-ray diffraction and infrared spectroscopy characterization was performed. Hydrogen pretreated niobates showed from low to moderate catalytic initial activity in DMR's test, nevertheless the materials were deactivated rapidly and the kinetic parameters associated to deactivation were estimated. Otherwise, non-treated catalysts showed a high initial activity in EHR's test and KSr2Nb 5O15 catalyst requires 24 h to the total deactivation with a high selectivity to form propylene. A reaction mechanism to the propylene formation is discussed. © 2012 Elsevier Ltd. All rights reserved.

Weld joint characteristics by nano-materials addition

The need for industries to remain competitive in the welding business, has created necessity to develop innovative processes that can exceed customer’s demand. Significant development in improving weld efficiency, during the past decades, still have their drawbacks, specifically in the weld strength properties. The recent innovative technologies have created smallest possible solid material known as nanomaterial and their introduction in welding production has improved the weld strength properties and to overcome unstable microstructures in the weld. This study utilizes a qualitative research method, to elaborate the methods of introducing nanomaterial to the weldments and the characteristic of the welds produced by different welding processes. The study mainly focuses on changes in the microstructural formation and strength properties on the welded joint and also discusses those factors influencing such improvements, due to the addition of nanomaterials. The effect of nanomaterial addition in welding process modifies the physics of joining region, thereby, resulting in significant improvement in the strength properties, with stable microstructure in the weld. The addition of nanomaterials in the welding processes are, through coating on base metal, addition in filler metal and utilizing nanostructured base metal. However, due to its insignificant size, the addition of nanomaterials directly to the weld, would poses complications. The factors having major influence on the joint integrity are dispersion of nanomaterials, characteristics of the nanomaterials, quantity of nanomaterials and selection of nanomaterials. The addition of nanomaterials does not affect the fundamental properties and characteristics of base metals and the filler metal. However, in some cases, the addition of nanomaterials lead to the deterioration of the joint properties by unstable microstructural formations. Still research are ongoing to achieve high joint integrity, in various materials through different welding processes and also on other factors that influence the joint strength.

Effect of silver nano particles on the fluorescence quantum yield of Rhodamine 6G determined using dual beam thermal lens method

Nano structured noble metals have very important applications in diverse fields as photovoltaics, catalysis, electronic and magnetic devices, etc. Here, we report the application of dual beam thermal lens technique for the determination of the effect of silver sol on the absolute fluorescence quantum yield (FQY) of the laser dye rhodamine 6G. A 532 nm radiation from a diode pumped solid state laser was used as the excitation source. It has been observed that the presence of silver sol decreases the fluorescence quantum efficiency. This is expected to have a very important consequence in enhancing Raman scattering which is an important spectrochemical tool that provides information on molecular structures. We have also observed that the presence of silver sol can enhance the thermal lens signal which makes the detection of the signal easier at any concentration.

Síntese, caracterização e aplicação de LaSBA-15 e como catalisador para obtenção de biodiesel de soja via rota etílica

Biodiesel is an alternative fuel, renewable, biodegradable and nontoxic. The transesterification of vegetable oils or animal fat with alcohol is most common form of production of this fuel. The procedure for production of biodiesel occurs most commonly through the transesterification reaction in which catalysts are used to accelerate and increase their income and may be basic, acid or enzyme. The use of homogeneous catalysis requires specific conditions and purification steps of the reaction products (alkyl ester and glycerol) and removal of the catalyst at the end of the reaction. As an alternative to improve the yield of the transesterification reaction, minimize the cost of production is that many studies are being conducted with the application of heterogeneous catalysis. The use of nano-structured materials as catalysts in the production of biodiesel is a biofuel alternative for a similar to mineral diesel. Although slower, can esterify transesterified triglycerides and free fatty acids and suffer little influence of water, which may be present in the raw material. This study aimed at the synthesis, characterization and application of nano-structured materials as catalysts in the transesterification reaction of soybean oil to produce biodiesel by ethylic route. The type material containing SBA-15 mesoporous lanthanum embedded within rightly Si / La = 50 was used catalyst. Solid samples were characterized by X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, nitrogen adsorption and desorption. For the transesterification process, we used a molar ratio of 20:1 alcohol and oil with 0.250 g of catalyst at 60°C and times of 6 hours of reaction. It was determined the content of ethyl esters by H-NMR analysis and gas chromatography. It was found that the variable of conversion obtained was 80%, showing a good catalytic activity LaSBA-15 in the transesterification of vegetable oils via ethylic route

Electrochemistry of carbon based engineered structures

The main aims of my PhD research work have been the investigation of the redox, photophysical and electronic properties of carbon nanotubes (CNT) and their possible uses as functional substrates for the (electro)catalytic production of oxygen and as molecular connectors for Quantum-dot Molecular Automata. While for CNT many and diverse applications in electronics, in sensors and biosensors field, as a structural reinforcing in composite materials have long been proposed, the study of their properties as individual species has been for long a challenging task. CNT are in fact virtually insoluble in any solvent and, for years, most of the studies has been carried out on bulk samples (bundles). In Chapter 2 an appropriate description of carbon nanotubes is reported, about their production methods and the functionalization strategies for their solubilization. In Chapter 3 an extensive voltammetric and vis-NIR spectroelectrochemical investigation of true solutions of unfunctionalized individual single wall CNT (SWNT) is reported that permitted to determine for the first time the standard electrochemical potentials of reduction and oxidation as a function of the tube diameter of a large number of semiconducting SWNTs. We also established the Fermi energy and the exciton binding energy for individual tubes in solution and, from the linear correlation found between the potentials and the optical transition energies, one to calculate the redox potentials of SWNTs that are insufficiently abundant or absent in the samples. In Chapter 4 we report on very efficient and stable nano-structured, oxygen-evolving anodes (OEA) that were obtained by the assembly of an oxygen evolving polyoxometalate cluster, (a totally inorganic ruthenium catalyst) with a conducting bed of multiwalled carbon nanotubes (MWCNT). Here, MWCNT were effectively used as carrier of the polyoxometallate for the electrocatalytic production of oxygen and turned out to greatly increase both the efficiency and stability of the device avoiding the release of the catalysts. Our bioinspired electrode addresses the major challenge of artificial photosynthesis, i.e. efficient water oxidation, taking us closer to when we might power the planet with carbon-free fuels. In Chapter 5 a study on surface-active chiral bis-ferrocenes conveniently designed in order to act as prototypical units for molecular computing devices is reported. Preliminary electrochemical studies in liquid environment demonstrated the capability of such molecules to enter three indistinguishable oxidation states. Side chains introduction allowed to organize them in the form of self-assembled monolayers (SAM) onto a surface and to study the molecular and redox properties on solid substrates. Electrochemical studies on SAMs of these molecules confirmed their attitude to undergo fast (Nernstian) electron transfer processes generating, in the positive potential region, either the full oxidized Fc+-Fc+ or the partly oxidized Fc+-Fc species. Finally, in Chapter 6 we report on a preliminary electrochemical study of graphene solutions prepared according to an original procedure recently described in the literature. Graphene is the newly-born of carbon nanomaterials and is certainly bound to be among the most promising materials for the next nanoelectronic generation.

Quantitative depth profiling of Ce 3+ in Pt/CeO 2 by in situ high-energy XPS in a hydrogen atmosphere

The redox property of ceria is a key factor in the catalytic activity of ceria-based catalysts. The oxidation state of well-defined ceria nanocubes in gas environments was analysed in situ by a novel combination of near-ambient pressure X-ray Photoelectron Spectroscopy (XPS) and high-energy XPS at a synchrotron X-ray source. In situ high-energy XPS is a promising new tool to determine the electronic structure of matter under defined conditions. The aim was to quantitatively determine the degree of cerium reduction in a nano-structured ceria-supported platinum catalyst as a function of the gas environment. To obtain a non-destructive depth profile at near-ambient pressure, in situ high-energy XPS analysis was performed by varying the kinetic energy of photoelectrons from 1 to 5 keV, and, thus, the probing depth. In ceria nanocubes doped with platinum, oxygen vacancies formed only in the uppermost layers of ceria in an atmosphere of 1 mbar hydrogen and 403 K. For pristine ceria nanocubes, no change in the cerium oxidation state in various hydrogen or oxygen atmospheres was observed as a function of probing depth. In the absence of platinum, hydrogen does not dissociate and, thus, does not lead to reduction of ceria.