Nanoparticulate cathode thin films with high electrochemical activity for low temperature SOFC applications

Nanocrystalline La_0.6Sr_0.4Co_0.2Fe_0.8O_3 − δ (LSCF) and La_0.25Ba_0.25Sr_0.5Co_0.2Fe_0.8O_3 − δ (LBSCF) with a high specific surface area (~ 40 m²/g) were synthesized by spray pyrolysis. The as prepared powder was characterized by X-ray diffraction, nitrogen adsorption, and high-resolution electron microscopy. Water-based dispersions of pure LSCF, LBSCF and mixtures containing gadolinium doped ceria (GDC) with agglomerate sizes of approx. 50 nm were prepared by application of ultrasonic energy. Spin coating was employed to prepare porous thin films. The thickness of the films (≤1 μm) was more than 10–20 times lower than conventional cathode layers. The interfacial polarization resistances of LBSCF cathodes are 19, 38, and 101 mΩ cm² at 650, 600, and 550 °C, respectively. The high performance is attributed to the nanometer-sized grain dimensions, the nanoporosity, and the large specific surface area within the cathode layer. The novel approach of preparing nanoparticulate thin film cathodes suggests strong benefit for Micro Solid Oxide Fuel Cells operating below 500 °C.     

Developing implicit pressure‐weighted upwinding scheme to calculate steady and unsteady flows on unstructured grids

The finite‐volume methods normally utilize either simple or complicated mathematical expressions to interpolate the fluxes at the cell faces of their unstructured volumes. Alternatively, we benefit from the advantages of both finite‐volume and finite‐element methods and estimate the advection terms on the cell faces using an inclusive pressure‐weighted upwinding scheme extended on unstructured grids. The present pressure‐based method treats the steady and unsteady flows on a collocated grid arrangement. However, to avoid a non‐physical spurious pressure field pattern, two mass flux per volume expressions are derived at the cell interfaces. The dual advantages of using an unstructured‐based discretization and a pressure‐weighted upwinding scheme result in obtaining high accurate solutions with noticeable progress in the performance of the primitive method extended on the structured grids. The accuracy and performance of the extended formulations are demonstrated by solving different standard and benchmark problems. The results show that there are excellent agreements with both benchmark and analytical solutions as well as experimental data. Copyright © 2007 John Wiley & Sons, Ltd.     

Recommendations on performance of parallel DSMC algorithm in solving subsonic nanoflows

We investigate the efficiency of a parallel direct simulation Monte Carlo (PDSMC) algorithm in solving the rarefied subsonic flow through a nanochannel. We use MPI library to transfer data between the processors. It is observed that PDSMC solver shows ideal speed up if sufficient workload is provided for each of processors. Additionally, this study shows that the computational time and speed up of the extended PDSMC solver do not depend (or slightly depend) on the number of cells. In contrary, increasing the total number of particles would result in a better efficiency of the PDSMC.     

Comparison of pyrolysis-mass spectrometry with high performance liquid chromatography for the analysis of vancomycin in serum

Mass spectrometry coupled with a pyrolysis inlet system (Pyr-ms) is compared with high performance liquid chromatography (HPLC) for the determination of vancomycin and its crystal degradation products (CDP-Is) in human serum. Quantitative analysis of Pyr-ms was performed by selected ion monitoring (SIM) method at 108 mass:charge (m/z) of pyrolysis product of vancomycin. 3-Nitroaniline (138 m/z) was used as an internal standard. A mu-Bondapak C(18) column and the gradient mobile phase of triethylamine buffer (pH 6.2), acetonitrile and tetrahydrofuran and a photometric detection at 205 nm are found to be the optimum conditions for the HPLC determination of vancomycin and CDP-Is. The limit of detection (LOD=1 ng ml(-1)), linearity (1 ng ml(-1)-10 mg ml(-1)), relative standard deviation (R.S.D.=1%), time analysis (1/2 h) and sample volume (50 mul) of Pyr-ms are far better than of the HPLC method. However, the HPLC method can individually determine the concentration of vancomycin and its degradation products.     

Suppression of the Verwey Transition by Charge Trapping

The Verwey transition in Fe₃O₄ nanoparticles with a mean diameter of 6.3 nm is suppressed after capping the particles with a 3.5 nm thick shell of SiO₂. By X‐ray absorption spectroscopy and its associated X‐ray magnetic circular dichroism this suppression can be correlated to localized Fe²⁺ states and a reduced double exchange visible in different site‐specific magnetization behavior in high magnetic fields. The results are discussed in terms of charge trapping at defects in the Fe₃O₄/ SiO₂ interface and the consequent difficulties in the formation of the common phases of Fe₃O₄. By comparison to X‐ray absorption spectra of bare Fe₃O₄ nanoparticles in course of the Verwey transition, particular changes in the spectral shape could be correlated to changes in the number of unoccupied d states for Fe ions at different lattice sites. These findings are supported by density functional theory calculations.     

Silica encapsulation of hydrophobically ligated PbSe nanocrystals

Spherical PbSe@SiO2 nanoparticles have been successfully synthesized within reverse micelles via metal alkoxide hydrolysis and condensation within a microemulsion system. These core-shell nanoparticles were characterized by transmission electron microscopy (TEM), NIR absorption spectroscopy, energy-dispersive X-ray analysis, and TEM electron diffractions. It shows that the obtained core-shell structures have a spherical shape with narrow size distribution (average size approximately 35 nm) and smooth surfaces. The size of the particles and the thickness of the shells can be controlled by manipulating the relative rates of the hydrolysis and condensation reactions of tetraethoxysilane (TEOS) within the microemulsion.     

Silica coated quantum dots: a new tool for electrochemical and optical glucose detection

The application of silica coated quantum dots (QDs@SiO₂) in glucose detection in combination with glucose oxidase is reported. The high specific surface area of such particles can be exploited to immobilise a greater amount of the enzyme on a modified electrode. In addition to this electrochemical method, we report here an indirect optical technique based on the photoluminescence quenching of QDs by hydrogen peroxide produced during glucose oxidation. The results obtained with these two different detection methodologies are compared. Correspondence: Sara Cavaliere-Jaricot, Freiburg Materials Research Centre (FMF), Albert-Ludwig University Freiburg, Stefan-Meier-Strasse 21, D-79104 Freiburg, Germany     

Bright luminescent, colloidal stable silica coated CdSe/ZnS nanocomposite by an in situ, one-pot surface functionalization

In this article, a systematic study of the design and development of surface-modification schemes for silica coated nanocomposite via an in situ, one-pot way is presented. Silica coated CdSe/ZnS nanoparticles were prepared in a water-in-oil microemulsion and subsequently surface modified via addition of various organosilane reagents to the microemulsion system. The resulting functionalized composite nanoparticles were characterized by different techniques like Transmission Electron Microscopy (TEM), photoluminescence spectroscopy and zeta-potential measurements. The results demonstrate that depending on the sequence of addition of silica precursors and organosilanes the product can show bright luminescence or considerable colloidal stability. The organosilanes molecules which are used here, act both as a stabilizer of the microemulsion system (regarding the charge compensation) and as a functional group the final product on top of silica shell. Using these surface-modification process, silica coated nanoparticles can be more readily conjugated with biomolecules and used as highly luminescent, sensitive, and reproducible labels in bioanalytical applications. Most importantly such surface functionalization could pave the way for controlled multi-mixed nanoparticles encapsulation (for example magnetic and QD nanoparticles).     

Synthesis and characterization of nanoparticulate films for intermediate temperature solid oxide fuel cells

Nanocrystalline strontium-doped lanthanum manganite (LSM) with a high specific surface area of 70 m²/g was synthesized via spray pyrolysis. The as prepared powder was characterized by ex-situ X-ray diffraction (XRD), in-situ high temperature X-ray diffraction (HTXRD), ex-situ nitrogen adsorption and high resolution scanning electron microscopy (HRSEM). LSM nanopowders with a mean particle size of 40 nm were dispersed in water-based media using ultrasonication. Nanocomposite LSM-GDC (gadolinium doped ceria) thin films were prepared by single step spin coating of co-stabilized LSM and GDC dispersions. The thickness of these thin films (≤ 1 μm) is more than 10 times lower than conventional cathode layers prepared by screen printing. The interfacial polarization resistances were 68, 118 and 220 mΩ cm² at 850, 800 and 750 °C, respectively. The high performance is attributed to small grain size, high porosity and large specific surface area. This method offers a very cost effective approach for the preparation of electrochemically highly active porous thin films, particularly applicable for micro solid oxide fuel cells.