Mid-temperature solid oxide fuel cells with thin film ZrO<Subscript>2</Subscript>: Y<Subscript>2</Subscript>O<Subscript>3</Subscript> electrolyte

Data on the mid-temperature solid-oxide fuel cells (SOFC) with thin-film ZrO₂-Y₂O₃ (YSZ) electrolyte are shown. Such a fuel cell comprises a carrying Ni-YSZ anode, a YSZ electrolyte 3–5 μm thick formed by vacuum ion-plasma methods, and a LaSrMnO₃ cathode. It is shown that the use of a combined method of YSZ electrolyte deposition, which involves the magnetron deposition of a 0.5–1.5-μm thick sublayer and its pulse electron-beam processing allows a dense nanostructured electrolyte film to be formed and the SOFC working temperature to be lowered down as the result of a decrease in both the solid electrolyte Ohmic resistance and the Faradaic resistance to charge transfer. SOFC are studied by the methods of voltammentry and impedance spectroscopy. The maximum power density of the SOFC under study is 250 and 600 mW/cm⁻² at temperatures of 650 and 800°C, respectively.     

Crafting La0.2Sr0.8MnO3-δ membrane with dense surface from porous YSZ tube

This work reports a new design of asymmetric tubular oxygen-permeable ceramic membrane (OPCM) consisting of a porous Y₂O₃ stabilized ZrO₂ (YSZ) tube (with ∼1 μm of pore diameters and 31% porosity) as the support and a gas-tight mixed conductive membrane. The membrane has an interlocking structure composed of a host matrix, Ag(Pd) alloy (9:1 by wt) doped perovskite-type (LSM80, 90wt%), and the embedded constituent, pristine LSM80. The Ag(Pd) alloy component promotes not only electronic conductivity and mechanical strength but also reduction of both porosity and pore sizes in the layer (∼10-μm-thick) where it dopes. The porous structure in this layer could then be closed through a solution coating procedure by which ingress of an aqueous solution containing stoichiometric nitrate salts of La³⁺, Mn³⁺, and Sr²⁺ to the pore channels takes place first and the mixture of nitrate salts left after drying is subjected to pyrolysis to generate tri-metal oxides in situ. This is followed by calcinations at l,300 °C to consolidate the embedded trioxide and to cohere them with the Ag(Pd)-LSM80 host matrix. The structure formed is dubbed LSM80(S)-Ag(Pd)-LSM80, which was confirmed gas-tight by electron micrograph and N₂ permeation test. Finally, we assess the chemical compatibility between LSM80 and YSZ at the sintering temperature by X-ray diffraction and electrochemical impedance analysis. The oxygen permeation of the fabricated LSM80(S)-Ag(Pd)-LSM80-YSZ membrane is within the temperature range of 600 to 900 °C. The tests reveal good compatibility between the LSM80 and YSZ and a reasonably high oxygen permeation flux in association with this OPCM assembly.     

Structure and spectral-optical characteristics of Se,Se/CdS,and Se/Cd<Subscript>0.5</Subscript>Zn<Subscript>0.5</Subscript>S nanoparticles,stabilized in polymer-containing media

A method was proposed for the production of colloidal nanoparticles of selenium stabilized by polymers and surfactants, and their structural and optical characteristics were studied. It was shown that during the deposition of CdS and Cd_0.5Zn_0.5S on the surface of the Se nanoparticles followed by dissolution of the selenium with sodium sulfite it is possible to obtain network “nanoframeworks” with size 30–50 nm, formed by CdS or Cd_0.5Zn_0.5S particles measuring 3–5 nm. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 1, pp. 24–29, January–February, 2007.     

Options for adjustment of microstructure and conductivity of cathodic substrates of La(Sr)MnO<Subscript>3</Subscript>

The electrodes of solid-oxide fuel cells (SOFCs) must be characterized by high conductivity to decrease ohmic losses and sufficient porosity to provide high gas diffusion rate. In the cases, when the SOFC electrodes are substrates, they must be synthesized at the temperature above the temperature of formation of their solid-electrolyte coating. Herewith, manufacturing of supporting electrodes with the required micro-structure is rather complicated. The present paper studies the effect of the method of manufacturing of the initial La_0.6Sr_0.4MnO₃ (LSM) powders, their degree of dispersion, introduction of sintering additives and pore agents on their microstructure, conductivity, and possibility of adjusting the temperature of SOFC cathodic substrate formation at which the required characteristics are reached. It is shown that sintering of cathodic substrates to the relative density of 65–70% can be carried out at the temperatures from 1050 to 1350–1400°C, which would allow obtaining electrolyte films of powders with different sintering ability on such substrates. The average pore size in cathodic substrates can be varied in the range of 0.4 to 2.5 μm by using the initial LSM powder with different dispersion degree and by employing graphite as a pore agent. At 900°C, conductivity of cathodic substrates of LSM grows at an increase in their relative density from 50% to 70% approximately from 50 to 100 S/cm and weakly depends on the dispersion degree of the initial powders.     

Facile preparation and electrochemical properties of large-scale Li<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>V<Subscript>3</Subscript>O<Subscript>8</Subscript> nanobelts

Large-scale Li_1+x V₃O₈ nanobelts were successfully fabricated using filter paper as deposition substrate through a simple surface sol–gel method. The nanobelts were as long as tens of micrometers with widths of 0.4–1.0 μm and thickness of 50–100 nm. The nanobelts were characterized by X-ray diffration (XRD), Fourier infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM). The formation mechanism of the nanobelts was investigated, showing that the morphology of the nanobelts is mainly determined by the calcination temperature. Electrochemical properties of the Li_1+x V₃O₈ nanobelts were characterized by charge–discharge experiments, and the results demonstrate that the Li_1+x V₃O₈ nanobelts exhibit a high discharge capacity (278 mAh g⁻¹) and excellent cycling stability.     

Nano-architecture platinum catalyst layer prepared by electrophoresis deposition for PEM fuel cells

A Pt-loaded carbon black electrode was prepared by pulsed electrophoresis deposition in a Pt colloid solution as a plating bath to overcome the growth problem of a Pt catalyst during deposition in an electrochemical process. This method is a promising technique for preparing Pt catalyst layers at the polymer electrolyte/electrode interface. The particle size of the Pt catalyst loaded by electrophoresis deposition was the same as that of Pt nanoparticles (3–4 nm) in a colloid and the particle size was maintained even during deposition. The loading of the Pt catalyst was controlled by the pH of the Pt colloid and deposition time. The Pt nanoparticles were deposited on a carbon black electrode to a depth of 2.5 μm.     

NiTiO<Subscript>3</Subscript> nanoparticles encapsulated with SiO<Subscript>2</Subscript> prepared by sol–gel method

NiTiO₃ (NTO) nanoparticles encapsulated with SiO₂ were prepared by the sol–gel method resulting on core-shell structure. Changes on isoelectric point as a function of silica were evaluated by means of zeta potential. The NTO nanoparticles heat treated at 600°C were characterized by X-ray diffraction, transmission electron microscopy (TEM) and energy dispersive X-ray analysis. TEM observations showed that the mean size of NTO is in the range of 2.5–42.5 nm while the thickness of SiO₂ shell attained 1.5–3.5 nm approximately.     

Electrochemical cell with solid oxide electrolyte and oxygen pump thereof

The paper presents the scientific basis and technical implementation of a method for obtaining oxygen by extraction from air using an electrochemical cell based on a solid oxide cell (SOC) with anion-conducting solid electrolyte. A nanopowder of a weak aggregate of the YSZ solid electrolyte and LSM fine powder was used to manufacture SOC. The electrolyte-electrode SOC structure was formed as a tube by joint pressing of functional layers and the further co-sintering at the temperature of 1200°C. The characteristics of an electrochemical cell of the oxygen pump based on a thin-wall tube of the YSZ supporting electrolyte (150 μm) with symmetrical electrodes based on LSM (∼20 μm) are studied. A prototype of a compact oxygen generator (oxygen pump) is developed and manufactured with an electrochemical part based on three serially connected SOCs. The connection is implemented in the form of metallic couplings of the Crofer 22 APU steel. The method of reaction magnetron sputtering was used to protect current leads from corrosion by applying a coating based on a Mn _x Co_{3 − x} O₄ spinel. The efficiency of a demonstration prototype at 800°C was 9 l/h at the power consumption of 50 W. The current density through SOC was 1.1 A/cm². The prototype was designed to contain no noble metal components. It is shown that the engineering approach applied allows manufacturing effective nanostructural SOCs and devices on their basis.     

Paper like free-standing hybrid single-walled carbon nanotubes air electrodes for zinc–air batteries

Flexible electrode architectures based on non-functionalized (P2) and functionalized (P3) single-walled carbon nanotubes (SWNTs) were fabricated via a simple vacuum filtration process. A hybrid layer of various compositions of P2- and P3-SWNTs forms free-standing membranes (~80 μm in thickness), and their electrochemical performance was evaluated as an air electrode AEP_2/P3 in zinc–air batteries. Such bifunctionalized air electrodes showed uniform surface morphology with interconnected micron-sized porous structure with high porosity (~70%). The N₂ adsorption isotherms at 77 K are of type IV with BET-specific surface areas of AE_(60/40) and AE_(80/20) to be 130.54 and 158.76 m² g⁻¹, respectively, thus facilitates high active surface area for active oxygen reduction/evolution reactions. BJH pore size distribution of AE_(60/40) and AE_(80/20) shows maximum pores with diameter <15 nm. The zigzag interlaying of the SWNTs imparts mechanical stability and flexibility in zinc–air batteries. Zinc–air batteries with optimized compositions of P2- and P3-SWNTs in air electrode AE_(60/40) had ionic conductivity ~1 × 10⁻² S cm⁻¹ and delivered higher discharge capacity ~300 mAh g⁻¹ as compared to AE_(80/20) composition. The unique properties of AE_(P2/P3) studied in this work would enable flexible air electrode architectures in future metal–air batteries.     

Construction of inorganic nanoparticles by micro-nano-porous structure of cellulose matrix

In our previous work, the CdS nanoparticles/cellulose films exhibited significantly high photocatalytic H₂ production efficiency under visible light irradiation than the ordinary CdS photocatalyst. In present paper, the CdS nanoparticles were synthesized in situ in pores of the regenerated cellulose substrate and the porous structure of cellulose, formation of the CdS nanoparticles and interactions between CdS and cellulose matrix in the composite films were investigated deeply. The experimental results indicated that the micro-nano-porous structure of the cellulose matrix could be used easily to create inorganic nanoparticles, which supplied not only cavities for the formation of nanoparticles, but also a shell (semi-stiff cellulose molecules support the pore wall) to protect their nano-structure. When the cellulose films with porous structure at wet state were immersed into inorganic ions solution, the ions interacted immediately with the –OH groups of cellulose, and then transformed into inorganic composite via another treatment, finally inorganic nanoparticles formed during the dry. The pore size of the cellulose matrix decreased from 180 nm (at wet state) to about 18 nm (at dry state), leading to the formation of nanoparticles. The results revealed that the CdS nanoparticles with a mean particle diameter about 6 nm were dispersed well, and were immobilized tightly in the cellulose matrix, resulting in a portable photocatalyst with high efficiency for photocatalytic for H₂ evolution. This is simple and “green” pathway to prepare the organic–inorganic hybrid materials.     

A simple template-free sol–gel synthesis of spherical nanosilica from agricultural biomass

Mesoporous silica nanoparticles with a spherical morphology have been synthesized from rice husk (agricultural biomass) by a simple, template-free synthetic approach, which was carried out via sol–gel technique at ambient condition. Transmission electron micrographs revealed the formation of spherical silica nanoparticles with an average diameter of 50.9 nm. From the nitrogen adsorption–desorption analysis, the rice husk silica shows a high specific BET surface area of 245 m² g⁻¹. The silica nanoparticles have a narrow pore size distribution of 5.6–9.6 nm.     

Preparation and characterization of La<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>Co<Subscript>0.2</Subscript>Fe<Subscript>0.8</Subscript>O<Subscript>3-δ</Subscript> thin-film membrane on porous support by dip-coating method

Perovskite-type La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF6428) thin-film membrane prepared by modified Pechini sol–gel process, was successfully deposited on porous support of similar composition using dip-coating method. Fine grain and crack-free film with perovskite structure was obtained at sintering temperature of 800 °C and dwelling time of 60 min. The cross-sectional image indicated that LSCF6428 thin-film membrane coated on the porous support showed excellent adhesion to the support with uniform thickness. The minimum dense layer thickness obtained by dip-coating method was around 0.5 μm. It was found that the oxygen permeability of the supported thin film was lower than that of the perovskite support, which indicated that the pores of the support were reduced by thin-film deposition on the support surface. The reduction in the pore size led to the more selective permeation mechanism contributes to the overall permeation. Successful deposition of LSCF6428 thin-film membrane on porous support can be considered as a promising technique for the preparation of oxygen separation membrane.     

Fabrication and characterization of TiO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript> composite nanoparticles and polyurethane/(TiO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript>) nanocomposite films

TiO₂–SiO₂ composite nanoparticles were prepared by a sol–gel process. To obtain the assembly of TiO₂–SiO₂ composite nanoparticles, different molar ratios of Ti/Si were investigated. Polyurethane (PU)/(TiO₂–SiO₂) hybrid films were synthesized using the “grafting from” technique by incorporation of modified TiO₂–SiO₂ composite nanoparticles building blocks into PU matrix. Firstly, 3-aminopropyltriethysilane was employed to encapsulate TiO₂–SiO₂ composite nanoparticles’ surface. Secondly, the PU shell was tethered to the TiO₂–SiO₂ core surface via surface functionalized reaction. The particle size of TiO₂–SiO₂ composite sol was performed on dynamic light scattering, and the microstructure was characterized by X-ray diffraction and Fourier transform infrared. Thermogravimetric analysis and transmission electron microscopy (TEM) employed to study the hybrid films. The average particle size of the TiO₂–SiO₂ composite particles is about 38 nm when the molar ratio of Ti/Si reaches to1:1. The TEM image indicates that TiO₂–SiO₂ composite nanoparticles are well dispersed in the PU matrix.     

Size effect of silica nanoparticles on thermal decomposition of PMMA

The size effect of silica nanoparticles (SiO₂) on thermal decomposition of poly(methylmethacrylate) (PMMA) was investigated by the controlled rate thermogravimetry. Thermal degradation temperature of PMMA–SiO₂ composites depended on both fraction and size of SiO₂, the thermal degradation temperature of 23 nm (diameter) SiO₂–PMMA (6.1 wt%) was 13.5 °C higher than that of PMMA. The thermal stabilities of 17 nm SiO₂–PMMA (3.2 wt%) and 13 nm SiO₂–PMMA (4.8 wt%) were 21 and 23 °C, respectively, higher than that of PMMA without SiO₂. The degree of degradation improvement was increased linearly with the surface area of SiO₂. The number of surface hydroxyl group in unit volume of SiO₂ particle increased with increasing the specific surface area of SiO₂, and the interaction between hydroxide group of SiO₂ and carbonyl group of PMMA had an important role to improve the thermal stability of PMMA.     

Glucosamine-functionalized silver glyconanoparticles: characterization and antibacterial activity

We report the analytical and in vitro antibacterial activity of glucosamine-functionalized silver glyconanoparticles. Morphological characterization ensured the surface topography and particle size distribution of both silver and glucosamine–silver nanoparticles. Surface plasmon resonance of both types of nanoparticle was determined from UV–visible spectroscopy using four different sample concentrations (10–40 μL). The resulting functionalized glyconanoparticles show maximum absorbance with a red shift of 30 ± 5 nm (390–400 nm) from their initial absorbance (425–430 nm). FT-Raman and ¹H-NMR spectroscopic measurement confirmed the surface functionalization of glucosamine on the silver surface through the carbonyl group of a secondary amide linkage (–NH–CO–), elucidated by the conjugation of N-hydroxysuccinimide (NHS)-terminated silver nanoparticles and the amino group of glucosamine. Antimicrobial experiments with well-characterized silver nanoparticles (AgNPs) and glucosamine-functionalized silver nanoparticles (GlcN-AgNPs) demonstrate that GlcN-AgNPs have similar and enhanced minimum inhibitory concentration (MIC) against eight gram-negative and eight gram-positive bacteria compared with AgNPs. MIC data shows that Klebsiella pneumoniae (ATCC 700603) and Bacillus cereus isolate express high levels of inhibition, with the quantity and magnitude of inhibition being higher in the presence of GlcN-AgNPs.     

The spatial distribution of poly(methyloctylsiloxane) deposited by solvent evaporation in the pores of HPLC silica particles

Summary Poly(methyloctylsiloxane) (PMOS), sorbed into the pores of HPLC silica particles by solvent evaporation, can function as a useful stationary phase for reversed-phase chromatography. The present work addresses the question of how the PMOS is distributed in the pores. Measurements of the surface area (BET, N₂) of a series of partially loaded samples (0–40% PMOS, m/m) using a typical batch of HPLC silica (10 μm irregular particles with 6 nm pores) show that the specific surface area of the samples decreases linearly with the specific loading (mass of PMOS per gram of silica). This result is not consistent with a “film” model in which the PMOS is deposited uniformly on the pore walls, but is consistent with a model in which long segmented “plugs” of PMOS are deposited within the pore system. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996     

Synthesis and Characterization of Hyperbranched RuO2 Nanostructures

RuO₂ nanostructures were synthesized by heating Ru nanoparticles in air at 280°C using Cu as catalyst. The Ru nanoparticles were prepared by the pyrolysis of ruthenium precursors in a vacuum using multi-walled carbon nanotubes as templates. The RuO₂ nanostructures grew radically with diameters of 50–150 nm, and lengths of 0.5–2.0 μm. The growth of nanostructure mainly depends on the dispersivity of Ru nanoparticles on MWNTs. The electrochemical property of these nanostructures was studied by cyclic voltammetry. Electronic Supplementary Material Supplementary material for this article is available at and is accessible for authorized users.     

(La0.8Sr0.2)0.9MnO3–Gd0.2Ce0.8O1.9 composite cathodes prepared from (Gd, Ce)(NO3) x -modified (La0.8Sr0.2)0.9MnO3 for intermediate-temperature solid oxide fuel cells

Development of high performance cathodes with low polarization resistance is critical to the success of solid oxide fuel cell (SOFC) development and commercialization. In this paper, (La_0.8Sr_0.2)_0.9MnO₃ (LSM)–Gd_0.2Ce_0.8O_1.9(GDC) composite powder (LSM ~70 wt%, GDC ~30 wt%) was prepared through modification of LSM powder by Gd_0.2Ce_0.8(NO₃) _x solution impregnation, followed by calcination. The electrode polarization resistance of the LSM–GDC cathode prepared from the composite powder was ~0.60 Ω cm² at 750 °C, which is ~13 times lower than that of pure LSM cathode (~8.19 Ω cm² at 750 °C) on YSZ electrolyte substrates. The electrode polarization resistance of the LSM–GDC composite cathode at 700 °C under 500 mA/cm² was ~0.42 Ω cm², which is close to that of pure LSM cathode at 850 °C. Gd_0.2Ce_0.8(NO₃) _x solution impregnation modification not only inhibits the growth of LSM grains during sintering but also increases the triple-phase-boundary (TPB) area through introducing ionic conducting phase (Gd,Ce)O_2-δ, leading to the significant reduction of electrode polarization resistance of LSM cathode.     

Comparative toxicity study of Ag, Au, and Ag–Au bimetallic nanoparticles on Daphnia magna

A comparative assessment of the 48-h acute toxicity of aqueous nanoparticles synthesized using the same methodology, including Au, Ag, and Ag–Au bimetallic nanoparticles, was conducted to determine their ecological effect in freshwater environments through the use of Daphnia magna, using their mortality as a toxicological endpoint. D. magna are one of the standard organisms used for ecotoxicity studies due to their sensitivity to chemical toxicants. Particle suspensions used in toxicity testing were well-characterized through a combination of absorbance measurements, atomic force or electron microscopy, flame atomic absorption spectrometry, and dynamic light scattering to determine composition, aggregation state, and particle size. The toxicity of all nanoparticles tested was found to be dose and composition dependent. The concentration of Au nanoparticles that killed 50% of the test organisms (LC₅₀) ranged from 65–75 mg/L. In addition, three different sized Ag nanoparticles (diameters = 36, 52, and 66 nm) were studied to analyze the toxicological effects of particle size on D. magna; however, it was found that toxicity was not a function of size and ranged from 3–4 μg/L for all three sets of Ag nanoparticles tested. This was possibly due to the large degree of aggregation when these nanoparticles were suspended in standard synthetic freshwater. Moreover, the LC₅₀ values for Ag–Au bimetallic nanoparticles were found to be between that of Ag and Au but much closer to that of Ag. The bimetallic particles containing 80% Ag and 20% Au were found to have a significantly lower toxicity to Daphnia (LC₅₀ of 15 μg/L) compared to Ag nanoparticles, while the toxicity of the nanoparticles containing 20% Ag and 80% Au was greater than expected at 12 μg/L. The comparison results confirm that Ag nanoparticles were much more toxic than Au nanoparticles, and that the introduction of gold into silver nanoparticles may lower their environmental impact by lowering the amount of Ag which is bioavailable.     

Synthesis of silica nanoparticles by modified sol–gel process: the effect of mixing modes of the reactants and drying techniques

A modified preparation of silica nanoparticles via sol–gel process was described. The ability to control the particle size and distribution was found highly dependent on mixing modes of the reactants and drying techniques. The mixture of tetraethoxysilane and ethanol followed by addition of water (Mode-A) produced monodispersed powder with an average particle size of 10.6 ± 1.40 nm with a narrow size distribution. The freeze drying technique (FD) further improved the quality of powder. In addition, the freeze dried samples have shown unique TGA decomposition steps which might be related to the well-defined structure of silica nanoparticles as compared to the heat dried samples. DSC analysis showed that FD preserved the silica surface with low shrinkage and generated remarkably well-order, narrow and bigger pore size and pore volume and also large endothermic enthalpies (ΔH _FD = −688 J g⁻¹ vs. ΔH _HD = −617 J g⁻¹) that lead to easy escape of physically adsorbed water from the pore at lower temperature.