Nanoporous Pt with High Surface Area by Reaction-Limited Aggregation of Nanoparticles

Nanoporous structures with high active surface areas are critical for a variety of applications. Here, we present a general templateless strategy to produce such porous structures by controlled aggregation of nanostructured subunits and apply the principles for synthesizing nanoporous Pt for electrocatalytic oxidation of methanol. The nature of the aggregate produced is controlled by tuning the electrostatic interaction between surfactant-free nanoparticles in the solution phase. When the repulsive force between the particles is very large, the particles are stabilized in the solution while instantaneous aggregation leading to fractal-like structures results when the repulsive force is very low. Controlling the repulsive interaction to an optimum, intermediate value results in the formation of compact structures with very large surface areas. In the case of Pt, nanoporous clusters with an extremely high specific surface area (39 m(2)/g) and high activity for methanol oxidation have been produced. Preliminary investigations indicate that the method is general and can be easily extended to produce nanoporous structures of many inorganic materials.

Vacuum-deposited submonolayer thin films of a three-ring bent-core compound

Submonolayer thin films of a three-ring bent-core (that is, banana-shaped) compound, m-bis(4-n-octyloxystyryl)benzene (m-OSB), were prepared by the vacuum-deposition method, and their morphologies, structures, and phase behavior were investigated by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The films have island shapes ranging from compact elliptic or circular patterns at low temperatures (below 40 degreesC) to branched patterns at high temperatures (above 60 degreesC). This shape evolution is contrary to the prediction based on the traditional diffusion-limited aggregation (DLA) theory. AFM observations revealed that two different mechanisms governed the film growth, in which the compact islands were formed via a dewetting-like behavior, while the branched islands diffusion-mediated. It is suggested m-OSB forms a two-dimensional, liquid crystal at the low-temperature substrate that is responsible for the unusual formation of compact islands. All of the monolayer islands are unstable and apt to transform to slender bilayer crystals at room temperature. This phase transition results from the peculiar molecular shape and packing of the bent-core molecules and is interpreted as escaping from macroscopic net polarization by the formation of an antiferroelectric alignment.

Gold nanoparticles decorated with oligo(ethylene glycol) thiols:kinetics of colloid aggregation driven by depletion forces

We have studied the kinetics of the phase-separation process of mixtures of colloid and protein in solutions by real-time UV-vis spectroscopy. Complementary small-angle X-ray scattering (SAXS) was employed to determine the structures involved. The colloids used are gold nanoparticles functionalized with protein resistant oligo(ethylene glycol) (OEG) thiol, HS(CH(2))(11)(OCH(2)CH(2))(6)OMe (EG6OMe). After mixing with protein solution above a critical concentration, c*, SAXS measurements show that a scattering maximum appears after a short induction time at q = 0.0322 angstrom(-1) stop, which increases its intensity with time but the peak position does not change with time, protein concentration and salt addition. The peak corresponds to the distance of the nearest neighbor in the aggregates. The upturn of scattering intensities in the low q-range developed with time indicating the formation of aggregates. No Bragg peaks corresponding to the formation of colloidal crystallites could be observed before the clusters dropped out from the solution. The growth kinetics of aggregates is followed in detail by real-time UV-vis spectroscopy, using the flocculation parameter defined as the integral of the absorption in the range of 600-800 nm wavelengths. At low salt addition (<0.5 M), a kinetic crossover from reaction-limited cluster aggregation (RLCA) to diffusion-limited cluster aggregation (DLCA) growth model is observed, and interpreted as being due to the effective repulsive interaction barrier between colloids within the depletion potential. Above 0.5 M NaCl, the surface charge of proteins is screened significantly, and the repulsive potential barrier disappeared, thus the growth kinetics can be described by a DLCA model only.

Self Repair in Circuits-Automating Open Fault Repair in Integrated Circuits Using Field-Induced Aggregation of Carbon Nanotubes

This paper presents studies on the use of carbon nanotubes dispersed in an insulating fluid to serve as an automaton for healing open-circuit interconnect faults in integrated circuits. The physics behind the repair mechanism is the electric-field-induced diffusion limited aggregation. On the occurrence of an open fault, the repair is automatically triggered due to the presence of an electric field across the gap. We perform studies on the repair time as a function of the electric field and dispersion concentrations with the above application in mind.

Aggregation-based fabrication and assembly of roughened composite metallic nanoshells: Application in surface-enhanced Raman scattering

This paper reports an aggregation-based method for the fabrication of composite Au/Ag nanoshells with tunable thickness and surface roughness. It is found that the resultant roughened composite Au/Ag nanoshells can attract each other spontaneously to form films at the air-water interface. Importantly, such films can be transferred onto the solid substrates without being destroyed and show excellent surface-enhanced Raman scattering (SERS) enhancement ability. Their strong enhancement ability may stem from the unique two-dimensional structure itself.

Structure and luminescence of Eu3+-doped class I siloxane-poly(ethylene glycol) hybrids

Transparent, flexible, and luminescent EU3+-doped siloxane-poly(ethylene glycol) (PEG) nanocomposites have been obtained by the sol-gel process. The inorganic (siloxane) and organic PEG phases are usually linked by weak bonds (hydrogen bonds or van der Waals forces), and small-angle X-ray scattering (SAXS) measurements suggest that the structure of these materials consists of fractal siloxane aggregates embedded in the PEG matrix. For low Eu3+ contents, n = 300 and n = 80, the aggregates are small and isolated and their fractal dimensions are 2.1 and 1.7, respectively. These values are close to those expected for gelation mechanisms consisting of reaction-limited cluster-cluster aggregation (RLCCA) and diffusion-limited cluster-cluster aggregation (DLCCA). For high Eu3+ content, SAYS results are consistent with a two-level structure: a primary level of siloxane aggregates and a second level, much larger, formed by the coalescence of the primary ones. The observed increase in the glass transition temperature for increasing Eu3+ content is consistent with the structural model derived from SAXS measurements. Extended X-ray absorption fine structure (EXAFS) and luminescence spectroscopy measurements indicate that under the experimental conditions utilized here Eu3+ ions do not strongly interact with the polymeric phase.

Gelation of siloxane-poly(oxypropylene) composites

The viscoelastic properties of siloxane-poly(oxypropylene) (PPO) nanocomposites prepared by the sol-gel process has been analyzed during gelation by dynamic rheological measurements. The changes of storage and loss moduli, complex viscosity and phase angle has been measured as a function of time showing the newtonian viscosity of the sol in the initial step of gelation, and its progressive transformation to a viscoelastic gel. The rheologic properties have been correlated to mass fractal, nearly linear growth models and percolation theory. This study, completed by quasi-elastic light scattering and Si-29 solid state nuclear magnetic resonance measurements, shows that the mechanisms of gelation of siloxane-PPO hybrids depend on the molecular weight of the polymer and on the pH of the hybrid sol. For hybrids prepared in acid medium, a polymerization involving silicon reactive species located at the extremity of the polymer chains and presenting a functionality f = 2 occurs, forming a fractal structure during the first stage of sol-gel transition. For samples prepared under neutral pH, the fractal growth is only observed for hybrids containing short polymer chains (M-w similar to 130 gmol(-1)). The fractal dimensionality determined from the change in the rheological properties, indicates that the fractal growth mechanism changes from reaction-limited to diffusion-limited aggregation when the molecular weight of the PPO increases from 130 to 4000 gmol(-1) and as catalyst conditions change from acidic to neutral. Near the gel point, these hybrid gels have the typical scaling behavior expected from percolation theory. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Formação e crescimento do óxido de zinco e óxido de zinco dopado com cobre

Pós-graduação em Química - IQ

Fractal Pattern Formation In Anodic Bonding Of Pyrex Glass/Al/Si

Anodic bonding of Pyrex glass/Al/Si is an important bonding technique in micro/nanoelectromechanical systems (MEMS/NEMS) industry. The anodic bonding of Pyrex 7740 glass/Aluminum film/Silicon is completed at the temperature from 300 degrees C to 375 degrees C with a bonding voltage between 150 V and 450 V. The fractal patterns are formed in the intermediate Al thin film. This pattern has the fractal dimension of the typical two-dimensional diffusion-limited aggregation (2D DLA) process, and the fractal dimension is around 1.7. The fractal patterns consist of Al and Si crystalline grains, and their occurrences are due to the limited diffusion, aggregation, and crystallization of Si and Al atoms in the intermediate Al layers. The formation of the fractal pattern is helpful to enhance the bonding strength between the Pyrex 7740 glass and the aluminum thin film coated on the crystal silicon substrates.

离子束溅射法薄膜生长中结瘤微缺陷的生长机理

用离子束溅射法制备了锆单层薄膜．用设计新型夹具和预置种子方法，对薄膜中结瘤微缺陷的生长过程进行了研究．在高分辨率光学显微镜和扫描电子显微镜下观察发现，结瘤在其生长初期呈现出分形的特征．用分子动力学和薄膜生长的扩散限制聚集模型，薄膜中结瘤微缺陷成核时的分形现象得到了很好的解释．

Characterisation of virus transport and attenuation in epikarst using short pulse and prolonged injection multi-tracer testing

Attenuation processes controlling virus fate and transport in the vadose zone of karstified systems can strongly influence groundwater quality. This research compares the breakthrough of two bacteriophage tracers (H40/1 and T7), with contrasting properties, at subsurface monitoring points following application onto an overlying composite sequence of thin organic soil and weathered limestone (epikarst). Short pulse multi-tracer test results revealed that T7 (Source concentration, Co=1.8x106pfu/mL) and H40/1(Co=5.9x106pfu/mL) could reach sampling points 10m below ground less than 30 minutes after tracer application. Contrasting deposition rates, determined from simulated tracer responses, reflected the potential of the ground to differentially attenuate viruses. Prolonged application of both T7 (Co=2.3x104pfu/mL) and H40/1 (Co=1.3x105pfu/mL) over a five hour period during a subsequent test, in which ionic strength levels observed at monitoring points rose consistently, corresponded to a rapid rise in T7 levels, followed by a gradual decline before the end of tracer injection; this reflected reaction-limited deposition in the system. T7’s response contrasted with that of H40/1, whose concentration remained constant over a three hour period before declining dramatically prior to the end of tracer injection. Subsequent application of lower ionic strength tracer-free flush water generated a rapid rise in H40/1 levels and a more gradual release of T7. Results highlight the benefits of employing prolonged injection multi-tracer tests for identifying processes not apparent from conventional short pulse tests. Study findings demonstrate that despite rapid transport rates, the epikarst is capable of physicochemical filtration of viruses and their remobilization, depending on virus type and hydrochemical conditions.