Tailoring Bimetallic Alloy Surface Properties by Kinetic Control of Self-Diffusion Processes at the Nanoscale

Achieving control of the nanoscale structure of binary alloys is of paramount importance for the design of novel materials with specific properties, leading to, for example, improved reaction rates and selectivity in catalysis, tailored magnetic behavior in electronics, and controlled growth of nanostructured materials such as graphene. By means of a combined experimental and theoretical approach, we show that the complex self-diffusion mechanisms determining these key properties can be mostly defined by kinetic rather than energetic effects. We explain how in the Ni-Cu system nanoscale control of self-diffusion and segregation processes close to the surface can be achieved by finely tuning the relative concentration of the alloy constituents. This allows tailoring the material functionality and provides a clear explanation of previously observed effects involved, for example, in the growth of graphene films and in the catalytic reduction of carbon dioxide.

Préparation et caractérisation de nanoparticules bimétalliques (Pt-Au) sur un substrat en diamant dopé au bore

Bahaa El Roustom

Using petrol as a main source of energy, during the 20th century, has caused considerable amounts of damage among which are atmospheric pollution and global warming. At the same time, many geologists and economists expect that the discovery rate of new petrol sources will not follow the market's demand causing a serious shortage of petrol in the near future. These alarming perspectives have motivated scientists around the world to develop new clean and renewable energy sources. It is in that objective that electrochemists intensified their research in order to develop the fuel cell technology. This latter consists in directly converting chemical energy into electricity. The main advantage of this technology over traditional energy production is that the fuel cell energy efficiency is Carnot cycle independent. The theoretical efficiency of such an energy source is nearly 90%. Direct Alcohol Fuel Cell (DAFC), fed by ethanol on one hand and by air (oxygen) in the other hand, is a very interesting option for such kind of energy production. Ethanol is a renewable energy source of vegetal origin whose CO2 production is consumed by plants during the cycle. Even though Pt has long been known to be a perfect catalyst for DAFC, it has some principal limitations, the most important ones being poisoning by intermediate products (OH on the cathodic side and CO on the anodic side) and a relatively high cost compared to other materials. These problems have pushed the experts in the field to focalize their research on the development of more suitable and better performing materials. Gold nanoparticles have shown a surprising catalytic activity, very different from the bulk, making them a preferential candidate to replace Pt. A system based on using two or more metals as catalysts (example Au-Pt) dispersed on an appropriate substrate seems to be also an interesting candidate to enhance the cell's efficiency. The substrate should be chemically inert, non-oxydable and should not present any interference with the electrochemical and electrocatalytic behaviour of the nanoparticles. In the first part, the employed substrate, which is boron doped diamond (BDD) is characterized. The substrate's main characteristics are its chemical inertness, its weak residual current and its resistance to corrosion. These characteristics contribute to making the substrate an ideal support for nanoparticles. In this work, the substrate is a diamond film, but for fuel cell applications diamond should be used as powder or dispersed particles. In chapters III and IV, we studied the effect of boron incorporation on the morphology and the behaviour of the diamond film. For this purpose, samples with different ratios of boron/carbon (B/C) in the vapour phase during preparation were characterized (B/C = 300, 1000, 2500 and 6000 ppm). Results showed that the grain size decreases with increasing boron content in the film. This is accompanied by a transition towards a quasi-metallic character. It was also found that graphitic impurities in the diamond film increase when the B/C ratio increases. We also established some graphitic impurities increase in the diamond film when the ratio of B/C increases. The identity of these impurities was established in chapter III as being surface redox couples (semi-quinone/semi-hydroquinone). Using cyclic voltametry we were able to observe a total elimination (B/C=300 ppm) or partial elimination (B/C=6000 ppm) of these surface redox couples. We also found in chapter IV that these surface redox couples are responsible of the electrochemical activity of the BDD electrode. BDD electrodes with different doping level B/C=300, 1000 and 6000 ppm) in the vapour phase are modified with IrO2 nanoparticles using the method of thermal decomposition. Our results showed that, at low potentials, the behaviour of the composite electrode IrO2/BDD with respect to the reaction of oxygen evolution is independent of the doping level. On the other hand, at high potentials, the weakly doped electrode (B/C=300 ppm) presents a supplementary overpotential due to the interface BDD-IrO2. An approach based on the double junction is developed in this work describing two distinct behaviours depending on the boron concentration in the diamond film. A new method for Au nanoparticles deposition on highly doped BDD electrodes (B/C= 2500 ppm) is presented in chapter VI. This method involves two steps: the first step consists on sputtering the equivalent of few nanolayers of Au on the diamond surface; the second step is a heat treatment in air at high temperatures. Several parameters that could influence the dispersion, the stability as well as the diameter of the Au nanoparticles are studied. In chapter VII, the behaviour of the composite electrode Au/BDD is studied in a solution containing redox couples in acid media. This electrode was simulated as an arrangement of active Au microelectrodes dispersed on a less active BDD substrate. The overall behaviour of the composite electrode (Au/BDD) has been related to the electrochemical rate constants on each material. In chapter VIII, another new synthesis method for a bimetallic system formed by Au and Pt nanoparticles dispersed on a BDD substrate is developed. This method consists in electrodepositing a small amount of Pt on a composite electrode Au/BDD. Our results showed that Pt was preferentially deposited on Au covering its whole surface. In fact, Au nanoparticles serve as germ of nucleation for Pt. In the following step, the bimetallic PtbAu/BDD is heated to 400°C in air to enhance the interaction between Au and Pt. The experiments showed that Au reappeared on the surface. The electrochemical behaviour of the bi-metallic electrode is characterized by a negative shift in the peak potential of reduction of Pt oxides. This is not the case of heterogeneous alloys obtained by the fusion of two metals at high temperatures. The composite electrode Au/BDD as well as the bi-metallic electrode Pt-Au/BDD are used for electrocatalytic applications. The studied reaction in chapter IX is the oxygen reduction reaction (ORR) in an acid medium. We found that the number of exchanged electrons increases with increasing the amount of Pt at the surface. Oxygen is reduced into H2O2 on the Au/BDD electrode and into H2O on the Pt-Au/BDD electrode. In chapter X we studied the reaction of oxidation of oxalic acid. The behaviour of both Au and Pt electrodes seemed very similar for this reaction. The bi-metallic electrode containing both Pt and Au on its surface has shown an intermediate behaviour between the behaviour of the two metals.

EPFL2006

Submicro- and Nano-Structured Porous Materials for Production of High-Intensity Exotic Radioactive Ion Beams

Sandrina Fernandes

ISOLDE, the CERN Isotope Separator On-line DEvice is a unique source of low energy beams of radioactive isotopes - atomic nuclei that have too many or too few neutrons to be stable. The facility is like a small 'chemical factory', giving the possibility of changing one element to another, by selecting the atomic mass of the required isotope beam in the mass separator, rather as the 'alchemists' once imagined. It produces a total of more than 1000 different isotopes from helium to radium, with half-lives down to milliseconds, by impinging a 1.4 GeV proton beam from the Proton Synchrotron Booster (PSB) onto special targets, yielding a wide variety of atomic fragments. Different components then extract the nuclei and separate them according to mass. The post-accelerator REX (Radioactive beam EXperiment) at ISOLDE accelerates the radioactive beams up to 3 MeV/u for many experiments. A wide international user radioactive ion beam (RIB) community investigates fundamental aspects of nuclear physics, particle and atomic physics, solid-state physics, materials science, astrophysics, biophysics and medicine. However, there are still a number of radioactive isotopes which are not accessible for experimental physics, either because it has been impossible to produce the element of interest, too low yields (number of isotopes per second measured in the beam line) are obtained or due to the higher post-acceleration energies required for the user's experiments. The aim of this thesis was to synthesize oxide and carbide porous materials, to be used as thick targets to increase the intensity of exotic RIBs. This was done by the evaluation of their radioactive isotope release properties and of their stability under irradiation conditions at high temperatures. This thesis is focused on the study of the chemical and physical processes occurring in the target system where the isotopes are produced, before these enter the ion-source system, are mass-separated and are sent to the user beam lines. The products formed in nuclear reactions between a proton beam and the target must, at a first step, diffuse from the interior of the target out to the surface and evaporate from it. Minimum delay times for the diffusion process can be realized by achieving the shortest diffusion lengths of highly-permeable, low-density, open-structure targets and by operating at the highest possible temperature so that release times are minimized and commensurate with the half-life of the isotopes of interest. Whereas until now target materials with micro-scale structures have been synthesized and used for RIB production, new porous submicro- and nano-structured materials offer the advantage of having lower diffusion activation energy of atoms and thus larger diffusion coefficient than the corresponding bulk counterpart, thanks to the increase of surface to volume ratio of these materials. The potential of this phenomenon for isotope mass separation online (ISOL) targets and many other applications is an evident drop of temperature to maintain a fast diffusion process, and higher release efficiency for the production of intense exotic isotope beams. In Chapter 1 the ISOL technique and the RIB production issues are introduced, followed by a review of recent progresses on target materials to increase yield production in the principal existing and next-generation ISOL and In-Flight facilities worldwide. Chapter 2 gives the theoretical fundamentals of diffusion and effusion in solid materials, and addresses specifically diffusion, effusion and release properties of ISOL targets. The study presented in Chapter 3 consists in the evaluation of release properties in different polycrystalline silicon carbide samples. The diffusion coefficients for Be, Na, Mg and F isotopes were extracted from off-line release measurements done at ISOLDE. The full characterization of the release time structure inherent to the physical and chemical processes of the ISOL RIB production on a submicrometric SiC target material (target SiC #334) used at ISOLDE, was made. This last target development resulted in improvement of magnesium short-lived isotopes yields. This was the first demonstration of the successful use of a submicrometric porous material as an ISOL target material, which delivered unprecedented 8x104 21Mg ions per µC. In Chapter 4, the synthesis of porous submicro- and nano-structured alumina to be used as an ISOL target, was followed by materials characterization in terms of microstructure and related with selected isotope release properties. Whenever possible, the release mechanisms were explained or proposed. The approach is relevant for the study of microstructure effects in other solid porous oxide and carbide targets, for optimization of their release performance. Chapter 5 shows the results of the TARPIPE experiment, set up within the design study task of the foreseen ISOL-type European facility called EURISOL, to investigate proton irradiation damage on typical and novel ISOL target materials under continuous proton irradiation at high temperature (> 1273 K). Materials such as SiC, Al2O3, Y2O3, C and Ta in a variety of forms were irradiated at the 72 MeV proton irradiation station of injector 1 at PSI (Paul Scherrer Institute). The effects of radiation damage on these materials were evaluated from microstructure and chemical analyses before and after irradiation by visual inspection, gamma spectroscopy, scanning electronic microscopy and electron dispersive X-ray analysis on a case-by-case basis. The moderate structure evolution of the porous oxide and carbide samples tested confirms that these materials are good candidates for high-power solid targets to be used at the existing and next generation high-power ISOL facilities, such as TRIUMF (TRI-University Meson Facility) and EURISOL (EURopean Isotope Separator On-line). In Chapter 6, the development and testing of a composite high-power alumina target for neon isotope production associated to a cold FEBIAD ion-source exposed to unprecedented proton beam intensities is reported. A 0.5 GeV proton beam from TRIUMF was used up to 25 µA, a factor 10 with respect to the present oxide targets in operation. The yields obtained were compared to the ones delivered by using a 70 µA proton beam in SiC targets at this facility. The target performance in terms of diffusion properties was evaluated. A general conclusion and discussion are given in Chapter 7. The release studies obtained with irradiation and ion implantation techniques on prospective SiC and Al2O3 matrices resulted in the identification of alternative target matrices for fast radioisotope release; this was confirmed experimentally from Na and Mg elements release efficiency determined online for a SiC target. A high-power oxide/metal composite target made of micrometric structural length scale Al2O3 pellets and Nb foils was operated online at unprecedented beam power intensities. Composite targets made of Nb foils and submicro- and nano-structured porous Al2O3 are expected to further increase yields of exotic isotopes. This ISOL target concept can be applied in the future for many other refractory insulating ceramics by using gradient microstructures and/or different ceramic/metallic combinations. Special care has to be taken, in order to minimize the stress induced by a mismatch of the coefficient of thermal expansion in the different ceramic layers and/or the underlying metallic substrate. Micro- and nano-technology fabrication techniques can be used to tailor pore and grain size distribution in ceramic and metallic complex-shaped composite materials and to shape these in compacts, monoliths and fenestrated structures. A balance between large surface area and large macropore volume for optimum target radioisotope release performance must be achieved. The resulting target material must in addition be stable at high temperatures, have good thermo-mechanical resistance and high thermal conductivity under irradiation for long irradiation time. The understanding of isotope release mechanisms in different solid materials, including the porous and dense fast-ion conductors will contribute to the production of exotic RIB at unprecedented high-intensity.

EPFL2010

Toxicity study of nanostructures

Lenke Horváth

The great achievement of nanotechnology is the controlled synthesis of a large variety of nanometer-size materials like needle-formed nanotubes, nanowires and two-dimensional graphene flakes. Due to their unique physico-chemical properties, these nanostructures are considered to be of great benefit for many applications in engineering, electronics, alternative energies and nanomedicine. Since the expectations for the improvement of our everyday life through engineered nanomaterials are high, there is rapid expansion of their manufacturing, which makes it likely that intentional and unintentional human and environmental exposure will increase in the near future. Consequently, the concern grows, related to their possible health hazards, as some of them strongly resemble asbestos. Motivated by this issue, we have investigated the in vitro acute cellular toxicity associated with four model nanomaterials: carbon nanotubes, boron nitride nanotubes, titanium dioxide nanofilaments and graphene oxide. This study focused on the toxic effect these nanomaterials had on cell types found in the respiratory system, where exposure to these materials is most prominent. These are lung epithelial cells, macrophages, and fibroblasts, but also other cell types like kidney cells were tested. The cytotoxicity was assessed by using MTT, DNA and FMCA assays, which measure different endpoints such as metabolic activity, cell proliferation and viable cell number. The cell death was determined by the Annexin V assay. We employed various microscopic techniques: light microscopy to reveal the morphological alterations associated with the nanomaterial toxicity at the cellular level; scanning electron microscopy to study the cell-nanomaterial interactions on the surface of the cell membrane; transmission electron microscopy to examine the uptake and subsequent localization of the nanomaterials within the cytosol and cell organelles. In addition, the generation of intracellular reactive oxygen species induced by graphene oxide was detected by the DCF assay. Last but not least, the pro-inflammatory potential and the biochemical perturbations in cells exposed to boron nitride nanotubes were investigated by Western blot and Synchrotron Infrared Microspectroscopy (SIRMS), respectively. All these techniques point to the adverse effects of the investigated nanostructures: i) The toxic effect of carbon nanotubes and carbon nanoparticles showed a time- and dose-dependent impairment in the metabolic activity of the cells characteristic for each cell type. Moreover, distinct morphological alterations typical for cell death were particularly apparent in macrophages. ii) The toxic potential of boron nitride nanotubes exhibited more pronounced adverse effects than carbon nanotubes. This was demonstrated by cell viability assays combined with cytopathological and biochemical analyses, showing induction of serious morphological changes, particularly in macrophages and fibroblasts, and biochemical processes characteristic for cell death. A higher acute toxicity was determined for boron nitride nanotubes when compared to crocidolite asbestos and their pro-inflammatory potential was demonstrated by the secretion of mature IL-1β cytokine in macrophages. iii) Titanium dioxide nanofilaments were also shown to impair the metabolic activity of the studied cells and induce morphological changes pointing to cell insult. iv) Graphene oxide exhibited a mild cytotoxic action in comparison to carbon nanotubes on epithelial cells and macrophages. The interaction of the nanomaterial with the cell surface generated reactive oxygen species during the initial phase of the exposure and transmission electron microscopy showed that graphene oxide flakes are taken up via the endocytic pathway. In summary, our findings highlight important physico-chemical parameters, which are important in relation to the toxic effect of nanomaterials. These are: i) the chemical composition; ii) the surface modification including functionalized groups and structural defects; iii) the geometry: length, diameter and tortuosity. In addition to the identified nanomaterial characteristics, we pinpoint that the target cells ́ response depends on their type, which is likely to be linked to their physiological function.

EPFL2012