Electrocatalysis of oxygen reduction reaction on Nafion/platinum/gas diffusion layer electrode for PEM fuel cell

In this work a new membrane electrode based on Pt-coated Nafion membrane was fabricated. Chemical deposition process was used to coat platinum on Nafion 117 membrane and then Pt-coated Nafion membrane was hot pressed on gas diffusion layer (GDL) to make new membrane electrode. The electrochemical and chemical studies of the Pt-coated Nafions were investigated by electrochemical techniques, X-ray diffraction and scanning electron microscopy. The electrochemical results indicated that as the concentration of H₂PtCl₆ increased, the oxygen reduction reaction rate increased until the concentration was reached where the reduction reaction was limited by the problem of mass transport. The electrochemical results for oxygen reduction reaction showed that the new electrode which prepared by plating Nafion membrane with 0.06 M H₂PtCl₆ in electroless plating solution, has a higher performance than other electrodes. The XRD results showed that the average platinum particle size of the best sample was about 3 nm. The loading of platinum for this electrode was 0.153 mg cm⁻².     

Synthesis and enhanced photocatalytic activity of NaNbO3 prepared by hydrothermal and polymerized complex methods

We prepared NaNbO₃ by several methods, namely solid-state reaction (SSR), hydrothermal (HT) and polymerized complex (PC) methods, and investigated the relationships between the photocatalytic activity and the particle size and morphology. The photocatalytic activity was evaluated by H₂ evolution from an aqueous methanol solution and pure water splitting in the presence of the Pt(0.5 wt%)/NaNbO₃ and RuO₂(1.25 wt%)/NaNbO₃, respectively. It is found that the sample prepared by PC with smallest particles exhibits the highest photocatalytic activity in both reactions. Moreover, the HT sample with the cubic and rectangular shape also shows the enhanced photocatalytic activity for H₂ evolution from an aqueous methanol solution in comparison with that of the sample prepared by SSR.     

Infrared spectroscopy on size-controlled synthesized Pt-based nano-catalysts

Pt, Ru and Pt/Ru nano-particles, synthesized in ethylene glycol solutions, are studied using infrared (IR) spectroscopy and high resolution transmission electron microscopy (HRTEM). The synthesis method allows the control of the mono- and bi-metallic catalyst particle sizes between 1 and 5.5 nm. The IR spectra of CO adsorbed (CO_ads) on the Pt, Ru and bi-metallic Pt/Ru colloids are recorded as a function of the particle size. The stretching frequency of CO_ads depends on the particle size and composition. Strong IR bands due to the stretching vibration of CO_ads are observed between 2010 and 2050 cm⁻¹ for the Pt nano-particles, while two IR bands between 2030 and 2060 cm⁻¹ for linear bonded CO_ads, and at lower wavenumbers between 1950 and 1980 cm⁻¹ for bridged bonded CO_ads, are found for the Ru particles. The IR spectra for the Pt/Ru nano-sized catalyst particles show complex behaviour. For the larger particles (>2 ± 0.5 nm), two IR bands representative of CO_ads on Ru and Pt-Ru alloy phases, are observed in the range of 1970-2050 cm⁻¹. A decrease in the particle size results in the appearance of a third band at ∼2020 cm⁻¹, indicative of CO_ads on Pt. The relative intensity of the band for CO_ads on the Pt-Ru alloy vs. the Pt phase decreases with decreasing particle size. These results suggest that Ru is partially dissolved in the Pt lattice for the larger Pt/Ru nano-particles and that a separate Ru phase is also present. A Pt-Ru alloy and Ru phase is observed for all Pt/Ru particles prepared in this work. However, a decrease in particle size results in a decrease of the number of Pt and Ru atoms in the Pt-Ru alloy phase, as they are increasingly present as single Pt and Ru phases.     

Infrared and Raman spectroscopic studies on iron oxide magnetic nano-particles and their surface modifications

Iron oxide magnetic nano-particles (MNPs) have been prepared in aqueous solution by a modified co-precipitation method. Surface modifications have been carried out using tetraethoxysilane (TEOS), triethoxysilane (TES) and 3-aminopropyltrimethoxysilane (APTMS). The uncoated and coated particle products have been characterized with transmission electron microscope (TEM), energy dispersive X-ray (EDX) spectroscopy, infrared (IR) and Raman spectroscopy, and thermal gravimetric analysis (TGA). The particle sizes were determined from TEM images and found to have mean diameters of 13, 16 and 14 nm for Fe₃O₄, TES/Fe₃O₄ and APTMS/Fe₃O₄, respectively. IR and Raman spectroscopy has been applied to study the effect of thermal annealing on the uncoated and coated particles. The results have shown that magnetite nano-particles are converted to maghemite at 109 °C and then to hematite by 500 °C. In contrast, the study of the effect of thermal annealing of micro-crystalline magnetite by IR spectroscopy revealed that the conversion to hematite began by 300 °C and that no maghemite could be identified as an intermediate phase. IR spectra and TGA measurements revealed that the Si-H and 3-aminopropyl functional groups in TES and APTMS coated magnetite nano-particles decomposed below 500 °C while the silica layer around the iron oxide core remained unchanged. The molecular ratio of APTMS coating to iron oxide core was determined to be 1:7 from the TGA data. Raman scattering signals have indicated that MNPs could be converted to maghemite and then to hematite using increasing power of laser irradiation in a manner similar to that observed for thermal annealing.     

Direct micropatterning of high dielectric BaTiO3 films by laser-induced pyrolysis with a nano-crystalline seeding technique

A direct patterning method of dielectric BaTiO₃ (BT) films is proposed, which applies laser-induced pyrolysis in combination with nano-crystalline seeding technique. A precursor solution of a BT complex alkoxide containing BT nano-crystalline particles with polyvinylpyrollidone (PVP) as dispersion stabilizer was spin-coated on Pt substrate. An Ar⁺ laser beam was focused and scanned on spin-coated BT films, which induced pyrolysis and crystallization of the films with spatial selectivity. Micropatterns were obtained by striping laser-unirradiated regions on the films with HCl aqueous solution. Raman spectra of the micropattern confirmed that the structures were tetragonal crystalline BT. Clear micropatterns with a line width of ca. 3 μm and an interval of 5 μm were formed at PVP concentrations of 25 and 50 kg/m³. The dielectric constant and dissipation factor of the film fabricated at a laser energy density of 27 MW/cm² and a scanning speed of 25 μm/s attained 76.2 and 0.07, respectively, for a measurement frequency of 100 kHz.     

Improvement of erosion and erosion-corrosion resistance of AISI420 stainless steel by low temperature plasma nitriding

Plasma nitriding experiments were carried out with DC-pulsed plasma in 25% N₂ + 75% H₂ atmosphere at low temperature (350 °C) and normal temperature (550 °C) for 15 h. The composition, microstructure, microhardness profiles, residual stress profiles and electrochemical impedance spectrum analyses of the nitrided samples were examined. The influence of plasma nitriding on the erosion and erosion-corrosion resistance of AISI 420 martensitic stainless steel was investigated using a jet solid particle erosion tester and a slurry erosion-corrosion tester.Results showed that the 350 °C nitriding layer was dominated by ?-Fe₃N and α_N phase, a supersaturated nitrogen solid solution. However, nitrogen would react with Cr in the steel to form CrN precipitates directly during 550 °C nitriding, which would lead to the depletion of Cr in the solid solution phase of the nitrided layer. Both 350 and 550 °C plasma nitriding could improve the erosion resistance of AISI420 stainless steel under dry erosion, but the former showed better results. In both neutral and acid environment, while the erosion-corrosion resistance of AISI 420 was improved by means of 350 °C nitriding, it was decreased through 550 °C nitriding.     

Dispersion of iron nano-particles on expanded graphite for the shielding of electromagnetic radiation

Composite materials containing electrically conductive expanded graphite (EG) and magnetic iron nano-particles for electromagnetic shielding were prepared by impregnating EG with an ethanol solution containing iron nitrate and acetic acid, followed by drying and reduction in H₂. Magnetic nano-iron particles were found to be highly dispersed on the surface of EG in the Fe/EG composites, and played the role of enhancing the electromagnetic shielding effectiveness (SE) at low frequencies (0.3-10 MHz), which seemed to depend proportionally on magnetic hysteresis loss of loaded iron nano-particles.     

Synthesis and hyperthermia property of hydroxyapatite-ferrite hybrid particles by ultrasonic spray pyrolysis

Biocompatible hybrid particles composed of hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂, HAp) and ferrite (γ-Fe₂O₃ and Fe₃O₄) were synthesized using a two-step procedure. First, the ferrite particles were synthesized by co-precipitation. Second, the suspension, which was composed of ferrite particles by a co-precipitation method, Ca(NO₃)₂, and H₃PO₄ aqueous solution with surfactant, was nebulized into mist ultrasonically. Then the mist was pyrolyzed at 1000 °C to synthesize HAp-ferrite hybrid particles. The molar ratio of Fe ion and HAp was (Fe²⁺ and Fe³⁺)/HAp=6. The synthesized hybrid particle was round and dimpled, and the average diameter of a secondary particle was 740 nm. The cross section of the synthesized hybrid particles revealed two phases: HAp and ferrite. The ferrite was coated with HAp. The synthesized hybrid particles show a saturation magnetization of 11.8 emu/g. The net saturation magnetization of the ferrite component was calculated as 32.5 emu/g. The temperature increase in the AC-magnetic field (370 kHz, 1.77 kA/m) was 9 °C with 3.4 g (the ferrite component was 1.0 g). These results show that synthesized hybrid particles are biocompatible and might be useful for magnetic transport and hyperthermia studies.     

Upconversion luminescence of colloidal solution of Y2O3 nano-particles doped with trivalent rare-earth ions

We have studied upconversion luminescence of colloidal solution of Y₂O₃ nano-particles codoped with 1 mol% Er³⁺ and 5 mol% Yb³⁺. Y₂O₃ nano-particles codoped with 1 mol% Er³⁺ and 5 mol% Yb³⁺ show sintering and agglomeration, because they are synthesized by firing a hydroxy carbonate precursor. Colloidal solution of Y₂O₃ nano-particles codoped with 1 mol% Er³⁺ and 5 mol% Yb³⁺ is prepared through two-step dispersion process and the average diameter of the primary nano-particles is about 50 nm. Under excitation with 980-nm laser diode, upconversion luminescence of colloidal solution of the primary Y₂O₃ nano-particles codoped with 1 mol% Er³⁺ and 5 mol% Yb³⁺ in methyl isobuthyl ketone strongly appeared near 660 nm and weakly near 550 nm.     

Position-controlled synthesis of single-walled carbon nanotubes on a transparent substrate by laser-induced chemical vapor deposition

The synthesis of single-walled carbon nanotubes (SWCNTs) on a transparent substrate with multiple-catalyst layer (Fe/Al/Cr: 0.5/15/500 nm) using laser-induced chemical vapor deposition is reported. Ethylene (C₂H₄) mixed with hydrogen (H₂) and a continuous wave Nd:YVO₄ laser (532 nm) were used as the precursor gas and the irradiation source, respectively. It was found that the density and quality of the SWCNT dots varied sensitively to laser irradiance and chamber pressure. From subsequent micro-Raman analyses at different excitation sources (488, 514, 633, and 785 nm), the diameters of the SWCNTs were estimated to be within the range of 0.8-2 nm and that the SWCNT dots were composed of both semiconducting and metallic SWCNTs. It is demonstrated that an array of SWCNT dots can be fabricated at precisely controlled positions of a transparent substrate at room temperature with no need of catalysis patterning.     

Synthesis of cobalt ferrite nano-particles and their magnetic characterization

Cobalt ferrite nano-particles (CoFe₂O₄) were synthesized by the co-precipitation method with ammonium hydroxide as an alkaline solution. The reactions were carried out at different temperatures between 20 and 80 °C. The nano-particles have been investigated by magnetic measurements, X-ray powder diffraction and transmission electron microscopy. The average crystallite size of the synthesized samples was between 11 and 45 nm, which was found to be dependent on both pH value of the reaction and annealing temperatures. However, lattice parameters, interplane spacing and grain size were controlled by varying the annealing temperature. Magnetic characterization of the nano-samples were carried out using a vibrating sample magnetometer at room temperature. The saturation magnetization was computed and found to lie between 5 and 67 emu/g depending on the particle size of the studied sample. The coercivity was found to exhibit non-monotonic behavior with the particle size. Such behavior can be accounted for by the combination between surface anisotropy and thermal energies. The ratio of remanence magnetization to saturation magnetization was found to exhibit almost linear dependence on the particle size.     

Synthesis of wide band gap nanocrystalline NiO powder via a sonochemical method

A sonochemistry-based synthesis method was used to produce nanocrystalline nickel oxide powder with ∼20 nm average crystallite diameter from Ni(OH)₂ precursor. Ultrasound waves were applied to the primary solution to intensify the Ni(OH)₂ precipitation. Dried precipitates were calcined at 320 °C to form nanocrystalline NiO particles. The morphology of the produced powder was characterized by transmission electron microscopy. Using sonochemical waves resulted in lowering of the size of the nickel oxide crystallites. FT-IR spectroscopy and X-ray diffraction revealed high purity well-crystallized structure of the synthesized powder. Photoluminescence spectroscopy confirmed production of a wide band-gap structure.     

Photoluminescence and magnetic properties of Fe-doped ZnS nano-particles synthesized by chemical co-precipitation

This paper is focusing on the synthesis of Zn_1−xFe_xS nano-particles with x = 0, 0.1 and 0.2 by chemical co-precipitation method, the prepared of which are characterized by XRD, EDS, TEM, PL, magnetization versus field behavior and M-T curve. In the XRD patterns, Zn_1−xFe_xS nano-particles are shown of cubic zinc blende structure, and the broadening diffraction peaks consistent with the small-size characteristic of nano-materials. The diameter of nano-particles is between 3.3 and 5.5 nm according to the HR-TEM images. The EDS data confirm the existence of Fe ions in Fe-doped ZnS nanoparticles. There we found that Fe-doping did not import new energy bands or defect states, but reduced the intensity of PL peaks. The magnetization versus field behaviors were illustrated by the M-H curves at both 5 K and 300 K, respectively, where no remanence or coercive force was observed. This phenomenon indicates that the Zn_1−xFe_xS (x = 0.1) nano-particles are superparamagnetic. The zero-field-cooled (ZFC) and field-cooled (FC) magnetization curves further reveal that the blocking temperature (T_B) of the superparamagnetic behavior might be below 5 K.     

Hydrothermal synthesis and photoelectric properties of BiVO4 with different morphologies: An efficient visible-light photocatalyst

Different morphologies of monoclinic BiVO₄ with smaller size were hydrothermal synthesized by simply adjusting the amount of surfactant (polyvinyl pyrrolidone PVP K30) added. The detailed field emission scanning electron microscope (FESEM) analysis revealed that the amount of PVP added could significantly affect the morphology and size of BiVO₄. Their photocatalytic activities were evaluated by the decolorization of methylene blue (MB) aqueous solution under visible-light irradiation (λ > 400 nm), and the as-prepared sample with well-assembled flower-like morphology showed a much higher photocatalytic activity due to larger specific surface area and higher separation efficiency of photo-induced carriers. The relationship between the behavior of photo-induced carriers and photocatalytic activity was studied using the surface photovoltage spectroscopy (SPS) and corresponding phase spectra.     

Aggregate structure and crystallite size of platinum nanoparticles synthesized by ethanol reduction

Monodispersed platinum (Pt) nanoparticles were synthesized from reducing hydrated hydrogen hexachloroplatinic acid (H₂PtCl₆·nH₂O) with ethanol in the presence of polyvinylpyrrolidone (PVP) as a steric stabilizer. Concentration of both PVP and ethanol influenced the aggregate structure and crystallite size of the nanoparticles. When the molar ratio of monomeric unit of PVP to Pt, i.e., [PVP]/[Pt], was one, the synthesized Pt particles coagulated pronouncedly into an inter-connected particulate network or self-organized into spherical superstructures with an apparent diameter ranging from 60 to 80 nm, depending on the ethanol concentration. The geometry and structure of these complex aggregates were characterized by fractal analysis. Fractal dimensions of 2.13–2.23 in three dimensions were determined from the Richardson’s plot, which suggests that a reaction-limited cluster–cluster aggregation model (RCLA) was operative. The Pt colloids became apparently more stable when the [PVP]/[Pt] ratio was increased greater than 20. Crystallite size of the Pt nanoparticles was found to increase linearly with the ethanol concentration as the [PVP]/[Pt] was held at one. This suggests that the reduction rate of PtCl₆ ²⁻ ions in solution is critically important to the synthesized crystallite size.     

Synthesis and photocatalytic property of ZnSe flowerlike hierarchical structure

Spherical flowerlike hierarchical structure of ZnSe(en)_0.5 was synthesized via a solvothermal route in the NH₃·H₂O-ethylenediamine (en)-N₂H₄·H₂O system at 180 °C for 24 h. The hierarchical structure is assembled from lots of regular nanosheets. The ZnSe(en)_0.5 was further converted into pure hexagonal ZnSe by annealing in a flowing nitrogen gas at 500 °C for 1 h with morphology preserved. The formation mechanism of ZnSe was discussed. The UV-visible absorption spectrum and PL spectrum of the ZnSe spherical flowerlike hierarchical structure were measured. In addition, photocatalytic activity of the ZnSe flowerlike structure for the degradation of methyl orange under the irradiation of the simulated sunlight was investigated. The excellent catalytic activity for the degradation of methyl orange was found and the possible mechanism of the photocatalytic activity is also proposed.     

Effect of cross-linkable polymer on the morphology and properties of transparent multi-walled carbon nanotube conductive films

In this study, we fabricated optically transparent and electrically conductive multi-walled carbon nanotube (MWCNT) thin films using a spray-coating technique. The transparency and the electrical resistance of thin film are dependent on the nanotube content deposited on the polyethylene terephthalate (PET) substrate. Poly(acrylic acid) (PAA) and poly(N-vinyl pyrrolidone) (PVP) were used as adhesion promoters to improve MWCNT coating more significantly. The cross-linked polymer resulted in a superior bond between the MWCNTs and the substrates. The surface electrical resistance was significantly lower than the original sheet after nitric acid (HNO₃) treatment because of the removed surfactant and the increased interconnecting networks of MWCNT bundles, thus improving the electrical and optical properties of the films. Stronger interaction between the MWCNTs and the substrates resulted in lower decomposition of the polymer chain and less amounts of MWCNTs separated into the HNO₃ solution. The lower sheet electrical resistance of PVP/PAA-g-MWCNT conductive films on the PET substrate was because of a more complete conductive path with the cross-linked polymer than that without. Such an improved sheet of electrical resistance varied from 8.83 × 10⁴ Ω/□ to 2.65 × 10³ Ω/□ with 5.0 wt.% PVP/PAA-g-MWCNT sprayed on the PET after acid treatment.     

Optimization of electromagnetic matching of carbonyl iron/BaTiO3 composites for microwave absorption

Microwave absorbing materials filled with BaTiO₃ and carbonyl iron (CI) particles with various weight fractions (BaTiO₃/CI particles=100/0 to 0/100) are investigated. The dielectric and magnetic properties of the absorbers can be tuned by changing the weight ratio of BaTiO₃/CI particles in the frequency range of 2-18 GHz. Numerical simulations are also performed to design a single-layer and double-layer absorber. The minimum reflection loss of the composite filled with 20 wt% BaTiO₃ and 60 wt% CI particles at 2.0 mm thickness can be reached to −42 dB at 4.1 GHz. With the weight ratio of CI particles in the composite increased, the microwave absorption peak shifted to the lower frequency region. By using a double-layer absorber structure, the microwave absorption performance of the absorber is enhanced. The result shows that the total thickness of the absorber can be reduced below 1.4 mm by using a matching layer filled with 50 wt% BaTiO₃, and an absorption layer filled with 60 wt% BaTiO₃ and 20 wt% CI particles, whereas the reflection loss below −10 dB can be obtained in the frequency range of 10.8-14.8 GHz and the minimum reflection loss of −59 dB can be obtained at 12.5 GHz.     

Development of film sensors based on ZnO nanoparticles for amine gas detection

A novel ZnO fluorescent film has been successfully fabricated by dipping a glass substrate into the N,N-dimethylformamide aqueous solution of Zn(Ac)₂ at low temperature (50 °C), then aged for 24 h in ZnO colloid dispersion. The morphology, structure, room-temperature photoluminescence (PL) spectra and gas sensing measurement were used to characterize the film. It has been demonstrated that the glass slide is the promising substrate for the deposition of ZnO particles, and there are almost uniformly distributed nano-particles on the surface of the substrates. It has been also revealed that the photo-luminescence emission of the film is selectively sensitive to the presence of amine, a possible explanation from the aspect of the sensing mechanism was proposed. The detection limit for amine vapor is calculated 162.0 ppm. Importantly, the response is reversible. Accordingly, it is anticipated that the film may be developed into amine sensor device.     

Preparation of Ru-loaded CdS/Al-HMS nanocomposites and production of hydrogen by photocatalytic degradation of formic acid

The composite of aluminum-substituted mesoporous silica (Al-HMS) molecular sieve coupled with CdS (CdS/Al-HMS) was prepared by template, ion exchange and sulfurization reactions. The result of low angle XRD patterns showed that the low content of 2.5 wt% CdS is incorporated inside Al-HMS channels. The results of diffuse reflectance UV-visible spectra and fluorescence emission spectra exhibited that the absorption edge and photoluminescence peak for CdS/Al-HMS are blue-shifted about 75 nm and 40 nm in comparison to bulk CdS, respectively. The activities of hydrogen production by photocatalytic degradation of formic acid were evaluated under visible light irradiation (λ ≥ 420 nm) and the CdS/Al-HMS loaded 0.07 wt% Ru showed the highest H₂ evolution at a rate of 3.7 mL h⁻¹ with an apparent quantum yield of 1.2% at 420 nm.