Highly oriented diamond growth on SixGe1−x (100) thin films

Highly oriented (100) diamond films have been successfully grown on Si_xGe_1−x (100) thin films by bias enhanced nucleation (BEN) in microwave plasma chemical vapor deposition (MPCVD) system. Raman spectra show the 1332 cm⁻¹ peak which proves the formation of diamond. Diamond nucleation density on Si_xGe_1−x substrate estimated by scanning electron microscopy is higher than 10⁹ cm⁻². The interface between diamond and Si_xGe_1−x substrate was characterized by transmission electron microscopy (TEM). About 20 nm decrease in thickness of the Si_xGe_1−x film was observed after bias enhanced nucleation step. TEM shows the existence of silicon carbide and heteroepitaxial diamond grains grown on Si_xGe_1−x substrate. Characterization from high-resolution TEM on the specimen of short time deposition reveals that a number of epitaxial diamond grains were directly nucleated on Si_xGe_1−x with {111} interplanar spacing ratio of diamond and Si_xGe_1−x of 2:3. The diamond nucleation is found to be preferred on the ridge position of the rough substrate surface. Diamond {100} facets were quickly developed in the early stage of growth.     

La(1−x)SrxCo1−yFeyO3 perovskites prepared by sol–gel method: Characterization and relationships with catalytic properties for total oxidation of toluene

La_(1−x)Sr_xCo_(1−y)Fe_yO₃ samples have been prepared by sol–gel method using EDTA and citric acid as complexing agents. For the first time, Raman mappings were achieved on this type of samples especially to look for traces of Co₃O₄ that can be present as additional phase and not detect by XRD. The prepared samples were pure perovskites with good structural homogeneity. All these perovskites were very active for total oxidation of toluene above 200 °C. The ageing procedure used indicated good thermal stability of the samples. A strong improvement of catalytic properties was obtained substituting 30% of La³⁺ by Sr²⁺ cations and a slight additional improvement was observed substituting 20% of cobalt by iron. Hence, the optimized composition was La_0.7Sr_0.3Co_0.8Fe_0.2O₃. The samples were also characterized by BET measurements, SEM and XRD techniques. Iron oxidation states were determined by Mössbauer spectroscopy. Cobalt oxidation states and the amount of O⁻ electrophilic species were analyzed from XPS achieved after treatment without re-exposition to ambient air. Textural characterization revealed a strong increase in the specific surface area and a complete change of the shape of primary particles substituting La³⁺ by Sr²⁺. The strong lowering of the temperature at conversion 20% for the La_0.7Sr_0.3Co_(1−y)Fe_yO₃ samples can be explained by these changes. X photoelectron spectra obtained with our procedure evidenced very high amount of O⁻ electrophilic species for the La_0.7Sr_0.3Co_(1−y)Fe_yO₃ samples. These species able to activate hydrocarbons could be the active sites. The partial substitution of cobalt by iron has only a limited effect on the textural properties and the amount of O⁻ species. However, Raman spectroscopy revealed a strong dynamic structural distortion by Jahn–Teller effect and Mössbauer spectroscopy evidenced the presence of Fe⁴⁺ cations in the iron containing samples. These structural modifications could improve the reactivity of the active sites explaining the better specific activity rate of the La_0.7Sr_0.3Co_0.8Fe_0.2O₃ sample. Finally, an additional improvement of catalytic properties was obtained by the addition of 5% of cobalt cations in the solution of preparation. As evidenced by Raman mappings and TEM images, this method of preparation allowed to well-dispersed small Co₃O₄ particles that are very efficient for total oxidation of toluene with good thermal stability contrary to bulk Co₃O₄.     

Decolorization of methylene blue by heterogeneous Fenton reaction using Fe3−xTixO4 (0 ≤ x ≤ 0.78) at neutral pH values

In this work, a series of Fe_3−xTi_xO₄ (0 ≤ x ≤ 0.78) was synthesized using a new soft chemical method. The synthetic Fe_3−xTi_xO₄ were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Mössbauer spectroscopy, thermogravimetric and differential scanning calorimetry (TG–DSC) analyses. The results showed that they were spinel structures and Ti was introduced into their structures.Then, decolorization of methylene blue (MB) by Fe_3−xTi_xO₄ in the presence of H₂O₂ at neutral pH values was studied using UV–vis spectra, dissolved organic carbon (DOC) and element C analyses. Furthermore, the degradation products remained in reaction solution after the decolorization were identified using ionic chromatography (IC), ¹³C nuclear magnetic resonance spectra (NMR), liquid chromatography and mass spectrometry (LC–MS). Although small amounts of MB were mineralized, the aromatic rings in MB were destroyed completely after the decolorization. Decolorization of MB by Fe_3−xTi_xO₄ in the presence of H₂O₂ was promoted remarkably with the increase of Ti content in Fe_3−xTi_xO₄ due to the enhancement of both adsorption and degradation of MB on Fe_3−xTi_xO₄.     

Highly active TiO2−x−yNxFy visible photocatalyst prepared under supercritical conditions in NH4F/EtOH fluid

A novel N and F co-doped TiO₂ (TiO_2−x−yN_xF_y) photocatalyst is prepared by treating the TiO₂ precursor in NH₄F/ethanol fluid under supercritical conditions. During photocatalytic degradation of methylene blue under visible light irradiation, the as-prepared TiO_2−x−yN_xF_y exhibits higher activity than the undoped TiO₂, N-doped TiO₂ (TiO_2−xN_x), and F-doped TiO₂ (TiO_2−yF_y). Based on the characterizations including XRD, Raman, FTIR, TEM, PLS, UV–vis DRS, N₂ adsorption–desorption isotherms, XPS and NH₃-TPD, the synergetic promotions of N- and F-dopants incorporated into the TiO₂ lattice are discussed based on the enhanced spectral response in visible region, oxygen vacancies, and surface acidic sites. Meanwhile, the supercritical treatment also promotes the activity owing to the increase in both the surface area and the crystallization degree of anatase, and the enhanced incorporation of N- and F-dopants into the TiO₂ lattice.     

Self-assembly of BixTi1−xO2 visible photocatalyst with core–shell structure and enhanced activity

Mesoporous Bi_xTi_1−xO₂ spheres with core–shell chamber were prepared by alcoholysis under solvothermal conditions. The cross-condensation between Ti–OH and Bi–OH ensured complete incorporation of Bi-dopants into TiO₂ lattice, though Bi atom is much bigger than Ti. Meanwhile, the aggregation of titania building clusters into spheres and their subsequent reactions including dissolution and re-deposition processes lead to the hollow spheres with tunable interior structure. The Bi-doping induced strong spectral response in visible region owing to the formation of narrow intermediate energy band gaps. Meanwhile, multiple reflections within the sphere interior voids promoted the light absorbance. As a result, the as-prepared Bi_xTi_1−xO₂ spheres exhibited much higher activity than the undoped TiO₂, the Bi₂O₃/TiO₂ obtained by impregnating the TiO₂ with Bi(NO₃)₃ solution, and the Bi_xTi_1−xO₂ after being ground during photodegradation of p-chlorophenol under visible light irradiation. Meanwhile, the Bi_xTi_1−xO₂ could be used repetitively for 10 times owing to the high hydrothermal stability and the absence of Bi-leaching.     

Study of IrxRu1−xO2 oxides as anodic electrocatalysts for solid polymer electrolyte water electrolysis

Electrocatalysts of the general formula Ir_xRu_1−xO₂ were prepared using Adams’ fusion method. The crystallite characterization was examined via XRD, and the electrochemical properties were examined via cyclic voltammetry (CV) in, linear sweep voltammetry (LSV) and chronopotentiometry measurements in 0.5 M H₂SO₄. The electrocatalysts were applied to a membrane electrode assembly (MEA) and studied in situ in an electrolysis cell through electrochemical impedance spectroscopy (EIS) and stationary current density–potential relations were investigated. The Ir_xRu_1−xO₂ (x = 0.2, 0.4, 0.6) compounds were found to be more active than pure IrO₂ and more stable than pure RuO₂. The most active electrocatalyst obtained had a composition of Ir_0.2Ru_0.8O₂. With an Ir_0.2Ru_0.8O₂ anode, a 28.4% Pt/C cathode and the total noble metal loading of 1.7 mg cm⁻², the potential of water electrolysis was 1.622 V at 1 A cm⁻² and 80 °C.     

Dielectric properties and microstructures of CaSiO3 ceramics with B2O3 addition

The effects of B₂O₃ additives on the sintering behavior, microstructure and dielectric properties of CaSiO₃ ceramics have been investigated. The B₂O₃ addition resulted in the emergence of CaO–B₂O₃–SiO₂ glass phase, which was advantageous to lower the synthesis temperature of CaSiO₃ crystal phase, and could effectively lower the densification temperature of CaSiO₃ ceramic to as low as 1100 °C. The 6 wt% B₂O₃-doped CaSiO₃ ceramic sintered at 1100 °C possessed good dielectric properties: _r = 6.84 and tan δ = 6.9 × 10⁻⁴ (1 MHz).     

Dynamics and selectivity of NOx reduction in NOx storage catalytic monolith

Several nitrogen compounds can be produced during the regeneration phase in periodically operated NO_x storage and reduction catalyst (NSRC) for conversion of automobile exhaust gases. Besides the main product N₂, also NO, N₂O, and NH₃ can be formed, depending on the regeneration phase length, temperature, and gas composition. This contribution focuses on experimental evaluation of the NO_x reduction dynamics and selectivity towards the main products (NO, N₂ and NH₃) within the short rich phase, and consequent development of the corresponding global reaction-kinetic model. An industrial NSRC monolith sample of PtRh/Ba/CeO₂/ -Al₂O₃ type is employed in nearly isothermal laboratory micro-reactor. The oxygen and NO_x storage/reduction experiments are performed in the temperature range 100–500 °C in the presence of CO₂ and H₂O, using H₂, CO and C₃H₆ as the reducing agents.The spatially distributed NSRC model developed earlier is extended by the following reactions: NH₃ is formed by the reaction of H₂ with NO_x and it can further react with oxygen and NO_x deposited on the catalyst surface, producing N₂. Considering this scheme with ammonia as an active intermediate of the NO_x reduction, a good agreement with experiments is obtained in terms of the NO_x reduction dynamics and selectivity. A reduction front travelling in the flow direction along the reactor is predicted, with the NH₃ maximum on the moving boundary. When the front reaches the reactor outlet, the NH₃ peak is observed in the exhaust gas. It is assumed that the ammonia formation during the NO_x reduction by CO and HCs at higher temperatures proceed via the water gas shift and steam reforming reactions producing hydrogen. It is further demonstrated that oxygen storage effects influence the dynamics of the stored NO_x reduction. The temperature dependences of the outlet ammonia peak delay and the selectivity towards NH₃ are correlated with the effective oxygen and NO_x storage capacity.     

Improving the oxygen permeability of Ba0.5Sr0.5Co0.8Fe0.2O3−δ membranes by a surface-coating layer of GdBaCo2O5+δ

A GdBaCo₂O_5+δ layer was coated on the Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ membranes to enhance their oxygen permeability by employing the fast oxygen adsorption/desorption surface-exchange properties of the GdBaCo₂O_5+δ material. The oxygen flux of the coated and uncoated Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ membranes was measured in the temperature range of 600–850 °C. The results reveal that the oxygen-permeation flux of the Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ membranes coated by a GdBaCo₂O_5+δ layer shows significant enhancement. The GdBaCo₂O_5+δ layer coated on the oxygen desorption side (He side) has much effect than that coated on the oxygen adsorption side (air side). At 850 °C, the oxygen flux with a single coating layer on the air side can rise 16%, while a single coating on the helium side will result into a rise of 23%.     

Catalytic NO–H2–CO–O2 reactions over Pt-supported mesoporous yttrium oxide

Catalytic light-off of a stream of NO, H₂, CO in an excess O₂ has been studied over various metal oxides loading 1 wt% Pt. Because a low-surface area Y₂O₃ (<5 m² g⁻¹) was found to exhibit the highest de-NO_x activity, a mesoporous Y₂O₃ was then synthesized from an yttrium-based surfactant mesophase templated by dodecyl sulfate , which was anion-exchanged by acetate (AcO = CH₃COO⁻). The product showed a 3-D mesoporosity with a large surface area (396 m² g⁻¹) and the Pt-supported catalyst achieved much improved light-off characteristics suitable for the low-temperature de-NO_x in the presence of CO and excess O₂.     

In situ Raman microspectrometry investigation of electrochemical lithium intercalation into sputtered crystalline V2O5 thin films

We report here the first in situ Raman microspectrometry study of the electrochemical lithium insertion and de-insertion reaction into crystalline sputtered Li_xV₂O₅ thin films (0 ≤ x ≤ 0.94) in liquid electrolyte. We show that the orthorhombic Pmmn symmetry of the pristine material is kept upon lithium intercalation in the Li_xV₂O₅ film (0 ≤ x ≤  0.94). In fact, a subsequent and unexpected solid solution behaviour is evidenced, leading to the typical Raman fingerprint of the -LiV₂O₅ phase for the Li₀.₉₄V₂O₅ composition. After the charge, a complete recovery of the local structure is found, in good accord with the excellent electrochemical reversibility exhibited by these thin films. Such limited structural changes differ from that usually observed for the bulk material, which emphasizes the key role of the microstructure and morphology on the nature and magnitude of the structural rearrangements induced by the lithium insertion process.     

Efficient growth of MWCNTs from decomposition of liquefied petroleum gas on a NixMg1−xO catalyst

With a solid-solution type of Ni_xMg_1−xO as catalyst, low-cost and easy-handling LPG was used as the carbon-source to efficiently synthesize CNTs of high purity. The prepared CNTs were “Herringbone-type” MWCNTs, with the outer diameters in the range of 10–40 nm and the inner diameters of 3–7 nm. The CNTs were almost the only species in the purified products. The structures of the nanocarbon were predominantly graphite-like, and the content of amorphous carbon was considerably low (6% estimated). The present study provides an alternative route to efficiently synthesize Herringbone-type CNTs of high purity without using CH₄.     

Surface properties and catalytic performance of La1−xSrxCrO3 perovskite-type oxides for CO and C3H6 combustion

Catalytic CO oxidation and C₃H₆ combustion have been studied over La_1−xSr_xCrO₃ (x = 0.0–0.3) oxides prepared by solid-state reaction and characterised by X-ray diffraction (XRD), nitrogen adsorption (BET analysis) and X-ray photoelectron spectroscopy (XPS). The expected orthorhombic perovskite structure of the chromite is observed for all levels of substitution. However, surface segregation of strontium along with a chromium oxidation process, leading to formation of Cr⁶⁺-containing phases, is produced upon increasing x and shown to be detrimental to the catalytic activity. Maximum activity is achieved for the catalyst with x = 0.1 in which mixed oxide formation upon substitution of lanthanum by strontium in the chromite becomes maximised.     

Excellent sulfur resistance of Pt/BaO/CeO2 lean NOx trap catalysts

In this work, we investigated the NO_x storage behavior of Pt/BaO/CeO₂ catalysts, especially in the presence of SO₂. High surface area CeO₂ (110 m²/g) with a rod like morphology was synthesized and used as a support. The Pt/BaO/CeO₂ sample demonstrated slightly higher NO_x uptake in the entire temperature range studied compared with Pt/BaO/γ-Al₂O₃. More importantly, this ceria-based catalyst showed higher sulfur tolerance than the alumina-based one. The time of complete NO_x uptake was maintained even after exposing the sample to 3 g/L of SO₂. The same sulfur exposure, on the other hand, eliminated the complete NO_x uptake time on the alumina-based NO_x storage catalysts. TEM images show no evidence of either Pt sintering or BaS phase formation during reductive de-sulfation up to 600 °C on the ceria-based catalyst, while the same process over the alumina-based catalyst resulted in both a significant increase in the average Pt cluster size and the agglomeration of a newly formed BaS phase into large crystallites. XPS results revealed the presence of about five times more residual sulfur after reductive de-sulfation at 600 °C on the alumina-based catalysts in comparison with the ceria-based ones. All of these results strongly support that, besides their superior intrinsic NO_x uptake properties, ceria-based catalysts have (a) much higher sulfur tolerance and (b) excellent resistance against Pt sintering when they are compared to the widely used alumina-based catalysts.     

High-performance Li4Ti5−xVxO12 (0 ≤ x ≤ 0.3) as an anode material for secondary lithium-ion battery

Powders of spinel Li₄Ti_5−xV_xO₁₂ (0 ≤ x ≤ 0.3) were successfully synthesized by solid-state method. The structure and properties of Li₄Ti_5−xV_xO₁₂ (0 ≤ x ≤ 0.3) were examined by X-ray diffraction (XRD), Raman spectroscopy (RS), scanning electronic microscope (SEM), galvanostatic charge–discharge test and cyclic voltammetry (CV). XRD shows that the V⁵⁺ can partially replace Ti⁴⁺ and Li⁺ in the spinel and the doping V⁵⁺ ion does almost not affect the lattice parameter of Li₄Ti₅O₁₂. Raman spectra indicate that the Raman bands corresponding to the Li–O and Ti–O vibrations have a blue shift due to the doping vanadium ions, respectively. SEM exhibits that Li₄Ti_5−xV_xO₁₂ (0.05 ≤ x ≤ 0.25) samples have a relative uniform morphology with narrow size distribution. Charge–discharge test reveals that Li₄Ti_4.95V_0.05O₁₂ has the highest initial discharge capacity and cycling performance among all samples cycled between 1.0 and 2.0 V; Li₄Ti_4.9V_0.1O₁₂ has the highest initial discharge capacity and cycling performance among all samples cycled between 0.0 and 2.0 V or between 0.5 and 2.0 V. This excellent cycling capability is mainly due to the doping vanadium. CV reveals that electrolyte starts to decompose irreversibly below 1.0 V, and SEI film of Li₄Ti₅O₁₂ was formed at 0.7 V in the first discharge process; the Li₄Ti_4.9V_0.1O₁₂ sample has a good reversibility and its structure is very advantageous for the transportation of lithium-ions.     

Role of Support in Lean DeNOx Catalysis

FTIR and pulse thermal analysis were applied to investigate catalysts containing Pt (1 wt%)/Ba (17 wt%) supported on -Al₂O₃, SiO₂ and ZrO₂. The aim was to learn how the support material affects the thermal stability of barium carbonate and its activity in the reaction to bulk Ba(NO₃)₂. The lower thermal stability of BaCO₃ in alumina supported samples was found to influence the formation of barium nitrate during the NO _x storage process. Quantification of Ba(NO₃)₂ formed during NO _x storage indicated that for alumina supported catalysts only ca. 30% of barium present in the sample is involved in the storage process. The low thermal stability found for alumina supported barium nitrite excludes its role in the formation of barium nitrate during interaction of NO _x with the catalyst at 300 °C. The studies indicate that -Al₂O₃ plays a major role in influencing the thermal stability of BaCO₃ and Ba(NO₃)₂. This finding seems to be relevant for the higher activity of -Al₂O₃-supported catalysts in NO _x storage reduction reactions.     

Ordered CoFe2O4 nanowire arrays with preferred crystal orientation and magnetic anisotropy

CoFe₂O₄ nanowire arrays were fabricated by electrodeposition of Fe²⁺ and Co²⁺ into anodic aluminum oxide (AAO) templates and further oxidization. The phase structure of the nanowires is cubic spinel-type, and the XRD result exhibits perfect preferred crystallite orientation along the nanowire axes. Compared with CoFe₂O₄ nanowire arrays synthesized by other methods, the magnetic hysteresis loops demonstrate that the arrays of nanowires exhibit uniaxial magnetic anisotropy with easy magnetization direction along the nanowire axes owing to the large shape anisotropy. This approach provides a facile technology to fabricate oxide nanowires with uniaxial magnetic anisotropy.     

Effects of preparation methods on the oxygen nonstoichiometry, B-site cation valences and catalytic efficiency of perovskite La0.6Sr0.4Co0.2Fe0.8O3−δ

La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) powders were synthesized respectively by an EDTA (ethylenediaminetetraacetic acid)–Citrate sol–gel process and a low-temperature auto-combustion process. The samples were characterized by XRD, SEM, BET, TGA and instant temperature analysis. The iodometric titration was used to determine the average valence of Co and Fe ions and the oxygen nonstoichiometry of the prepare powders. The catalytic properties of the synthesized powders were investigated by the hydrogen peroxide catalytic decomposition. Pure-perovskite structure was formed by both synthesis methods. The oxygen nonstoichiometry of the samples prepared by the auto-combustion process is larger than that by the sol–gel process. The catalytic activities of the powders from two synthesis processes also differed largely due to the different oxygen nonstoichiometry, surface area and crystalline sizes.     

Effect of pulse reversal on the properties of pulse plated CdSe x Te1−x thin films

CdSe _x Te_1–x thin films with 0 < x < 1 were deposited on titanium and conducting glass substrates by pulse electrodeposition using microprocessor control. Formation of the solid solution takes place for values of x(0 < x < 1). The films were characterized by X-ray diffraction. While the as-deposited films are cubic in nature, those annealed at 475 °C in air indicate hexagonal structure and the lattice parameters increase with increasing value of x. From the optical absorption measurements the band gap of the material was calculated. The value of the band gap varies from 1.42 to 1.70 eV as x varies from 0 to 1. The photoelectrochemical (PEC) characteristics were obtained for all compositions of CdSe _x Te_1–x (x = 0–1). The output parameters for CdSe_0.66Te_0.34 with 9% duty cycle at an intensity of 80 mW cm^–2 using 1 M polysulphide as the redox electrolyte, are V _OC of 398 mV, J _SC of 5.59 mA cm^–2, ff of 0.45, of 4.73%, R _s of 13 , R _sh of 1.50 k. The output parameters were found to increase with 60 ms pulse reversal. After photoetching for 40 s, a V _OC of 481 mV, J _SC of 16.00 mA cm^–2, ff of 0.57, of 5.46%, R _s of 6 , R _sh of 2.16 k were obtained.     

Synthesis and electrochemical characterization of LiCoxMn1−xPO4/C nanocomposites

LiCo_xMn_1−xPO₄/C nanocomposites (0 ≤ x ≤ 1.0) were prepared by a combination of spray pyrolysis at 300 °C and wet ball-milling followed by heat treatment at 500 °C for 4 h in 3% H₂ + N₂ atmosphere. X-ray diffraction analysis indicated that all samples had the single phase olivine structures indexed by orthorhombic Pmna. The lattice parameters linearly decreased with increasing cobalt content, which confirmed the existence of solid solutions. It was clearly seen from the scanning electron microscopy observation that the LiCo_xMn_1−xPO₄/C samples were agglomerates with approximately 100 nm primary particles. The LiCo_xMn_1−xPO₄/C nanocomposites were used as cathode materials for lithium batteries, and electrochemical performance was comparatively investigated with cyclic voltammetry and galvanostatic charge–discharge test using the Li?1 M LiPF₆ in EC:DMC = 1:1?LiCo_xMn_1−xPO₄/C cells at room temperature. The cells at 0.05 C charge–discharge rate delivered first discharge capacities of 165 mAh g⁻¹ (96% of theoretical capacity) at x = 0, 136 mAh g⁻¹ at x = 0.2, 132 mAh g⁻¹ at x = 0.5, 125 mAh g⁻¹ at x = 0.8 and 132 mAh g⁻¹ (79% of theoretical capacity) at x = 1.0, respectively. While the first discharge capacity increased with the cobalt content at high charge–discharge rates more than 0.5 C due to higher electronic conductivity of LiCoPO₄ in comparison with LiMnPO₄, the cycleability of cell became worse with increasing the amount of cobalt. The existence of Mn²⁺ seemed to enhance the cycleability of LiCo_xMn_1−xPO₄/C nanocomposite cathode.