Anodic electrodeposition of Ag1− x Cu x O microcrystals

We demonstrate the anodic electrodeposition of copper-doped AgO at high pH using a silver counter-electrode. Precipitates from a mixture of nitrates and NaOH provided source material for the deposition, and application of a moderate anodic voltage (0.9 V) to the substrate led to deposition of crystalline nanoparticles with incorporated copper. Further increase of the NaOH concentration reduced the amount of copper in the crystals, and higher voltages degraded the crystal quality. XRD confirms the underlying structure to be that of AgO, and Auger and energy dispersive x-ray analyses confirm copper concentrations of approximately 3 % in the crystals.     

CuO/NiOx thin film–based photocathodes for photoelectrochemical water splitting

Journal of Solid State Electrochemistry - Copper oxides are considered to be very promising materials for promoting a hydrogen evolution reaction (HER). However, some CuO features, such as the...     

Nanocrystalline Zn1−x−yBexMgyO thin films synthesized by the sol–gel method: structural and near infrared photoluminescence properties

In this paper, we reports on the structural and optical properties of Zn_1?x?yBe_xMg_yO thin films prepared by sol–gel method, which are new materials for optoelectronic and ultraviolet-light-emitting devices. The crystal structure and core level spectra of these films are studied by X-ray diffraction and X-ray photoelectron spectroscopy. Surface morphology of the films is analyzed by scanning electron microscope images and the surface is composed of spherical shaped grains. Micro-photoluminescence shows a near edge band emission and the peak values tuned from 3.26 eV for the undoped to 3.4 eV for the doped ZnO film. Near infrared emission is observed in the region 1.64–1.67 eV for pure and co-doped ZnO films. In micro-Raman spectra, multiple-order Raman bands originating from ZnO-like longitudinal optical (LO) phonons are observed. A Raman shift of about 5–18 cm^?1 is observed for the first-order LO phonon. A comparative study was made on Raman band for BeZnO, MgZnO and BeMgZnO nanocrystals with the LO phonon band of bulk ZnO. The ultraviolet resonant Raman excitation at room temperature shows multi-phonon LO modes up to the fourth order. Deformation energy of all the films is calculated and BeMgZnO film has the minimum deformation energy.     

Band gap bowing of nanocrystalline Zn(1−x)CaxO thin films for blue and ultraviolet optoelectronic applications

Alloying materials having different band gaps is a tool to tailor the optical energy gaps of semiconducting materials. In the present study, the effect of alloying ZnO with CaO was investigated. Thin films of Zn_(1−x)Ca_xO (0 ≤ x ≤ 0.20) were deposited on glass substrates by spray pyrolysis technique. All the films possessed nanocrystalline grains and crystallinity deteriorated with increase in Ca²⁺ substitution level. Elemental composition analysis confirmed the presence of Ca in the samples. Films showed good optical transmission in the visible and near infrared region and the absorption edge blue-shifted with Ca²⁺ substitution. Optical energy gap enhanced by 9.89% upon 20% Ca²⁺ substitution. Photoluminescence analysis also confirmed band gap broadening with mesovalent cation substitution.     

Longitudinal conductivity of thin films of La1 − x Sr x F3 − x solid solutions on glass ceramics

The longitudinal conductivity of La_{1 ? x} Sr _x F_{3 ? x} solid solution films (x = 0–0.24) with thicknesses of 40–260 nm grown on glass ceramics at temperatures from room temperature to 300°C and frequencies of 10^?1–10⁶ Hz was studied by impedance spectroscopy. The concentration dependence of film conductivity on the SrF₂ content had a maximum near x = 0.05. An equivalent circuit was constructed on the basis of the impedance plots to describe migration processes. The DC conductivity was evaluated for all samples under study. The activation energies were estimated from the temperature dependences of the DC conductivities of the films. The resulting dependences of electrophysical parameters were compared with those for bulk materials in terms of the relaxation conductivity model.     

Effect of post-annealing on the band gap of sol–gel prepared nano-crystalline Mg x Zn1−x O (0.0 ≤ x ≤ 0.3) thin films

Polycrystalline Mg _x Zn_1?x O (MZO) thin films on glass substrates were prepared by sol–gel method. All the films retained the hexagonal wurtzite structure of ZnO. The band gap values determined from transmission spectra were found to be smaller than the values obtained from Vegard’s law for the as-deposited MZO films. For the films with x = 0.1, 0.2 and 0.3, the band gap blue-shifted initially and then red-shifted with increase in the annealing temperature. The reason for this anomalous shift in the band gap is attributed to the proper substitution of Mg atoms into the Zn lattice sites after a certain critical annealing temperature.     

Characterization of superparamagnetic Mg x Zn1−x Fe2O4 powders

Structural and magnetic properties of Mg _x Zn_1−x Fe₂O₄ powders have been studied with respect to the application for thermal cancer therapy (magnetic hyperthermia). Mg _x Zn_1−x Fe₂O₄ (x=0.1–0.5) powders with particle sizes between 5 and 8 nm were produced by citrate method. The X-ray diffraction patterns of the samples correspond to a spinel phase. The lattice constant and the volume of the elementary cell increase when x changes from 0.1 to 0.5. The FTIR-spectra ascertain the spinel phase formation. The Mossbauer studies reveal the presence of extremely small particles, which undergo superparamagnetic relaxation at room temperature. The core-shell model has been applied to explain quadruple doublets. The quadruple splitting at “shells” is bigger than those at “cores” whereas the isomer shifts remain close. Magnetic studies confirm the presence of extremely small particles that behave as superparamagnetic ones.      

Electrochemical preparation of crystalline γ-CuI thin films through potential-controlled anodization of copper and its photoelectrochemical investigations

Journal of Solid State Electrochemistry - Copper iodide (CuI) thin film has been fabricated by controlled potential anodization of copper (Cu) in the potassium iodide (KI) electrolyte. Thin film...     

Recent advances in layered LiNi x CoyMn1−x−y O2 cathode materials for lithium ion batteries

Lithium cobalt oxide, LiCoO₂, has been the most widely used cathode material in commercial lithium ion batteries. Nevertheless, cobalt has economic and environmental problems that leave the door open to exploit alternative cathode materials, among which LiNi _x Co_yMn_{1 − x − y} O₂ may have improved performances, such as thermal stability, due to the synergistic effect of the three ions. Recently, intensive effort has been directed towards the development of LiNi _x Co _y Mn_{1 − x − y} O₂ as a possible replacement for LiCoO₂. Recent advances in layered LiNi _x Co_yMn_{1 − x − y} O₂ cathode materials are summarized in this paper. The preparation and the performance are reviewed, and the future promising cathode materials are also prospected.     

The promotion effect of catalytic activity by Ru substitution at the B site of La1−x Sr x Cr1−y Ru y O3−z for propane steam reforming

A series of La_1?x Sr _x Cr_1?y Ru _y O_3?δ (0.1 ≤ x ≤ 0.5, 0.05 ≤ y ≤ 0.15) materials was prepared by the sol–gel method to develop alternative catalysts for propane steam reforming. Catalyst characteristics were evaluated using physicochemical methods including X-ray diffraction, Brunauer–Emmett–Teller methods, H₂ temperature-programmed reduction, and thermogravimetry analysis (TGA). Effects of the amount of ruthenium (Ru) and strontium and the steam-to-carbon ratio (S/C) were investigated. An increase in Ru content led to increased propane conversion and H₂ yield, especially below 700 °C. Dramatic enhancement of catalytic activity was observed with La_0.8Sr_0.2Cr_0.85Ru_0.15O₃ under 600 °C, achieving propane conversion over 79% between 600 and 800 °C with maximum propane conversion and H₂ yield of 98.3% and 63.3%, respectively. Also, good resistance to carbon formation for the La_0.8Sr_0.2Cr_0.85Ru_0.15O₃ catalyst was confirmed by long-term testing and TGA analysis.

     

Enhanced photoelectrochemical performance of P-doped g‑C3N4/Zn0.5Cd0.5S heterojunction photocathode for water splitting

Photoelectrochemical (PEC) hydrogen evolution reaction at semiconductor photocathode in the presence of visible light is a promising way to harvest renewable energy. Graphitic carbon nitride (g-C₃N₄) has intriguing properties, making it highly favorable for photoelectrode engineering. This work demonstrated P-doped g-C₃N₄ nanosheets (PCN-Nss) and Zn_0.5Cd_0.5S heterojunction (PCN-Nss/ZCS-40) for PEC hydrogen evolution reaction using simulated sunlight. A facile and simple two-step strategy developed PCN-Nss/ZCS-40 photocathode; including co-precipitation of ZnCdS in the highly dispersed suspension of PCN-Nss and then drop-casting it on the surface of a conductive substrate. The intimate contact between PCN-Nss and ZnCdS at the molecular level due to the formation of heterojunction efficiently triggers charge separation, suppressing electron-hole pair recombination and easing the movement of photo-generated holes towards the conductive substrate. PCN-Nss/ZCS-40 (40% P-C₃N₄ by weight) showed substantially improved photocurrent response (?12 µA cm^?2) at ?0.6 V vs Ag/AgCl reference electrode in 0.2 M Na₂S solution, which is almost 40 times greater than simple P-C₃N₄ nanosheets under the same conditions. This work will expose new applications for P-doped graphitic carbon nitride-based heterostructures for PEC water splitting.     

Pulsed current electrodeposition of Zn–Ag2S/TiO2 nanocomposite films as potential photoelectrodes

Nanocomposite Zn–Ag₂S/TiO₂ and Zn–TiO₂ films were prepared by pulsed current electrolysis from acidic zinc sulphate solutions on a titanium substrate. The influence of the nanoparticles' nature on the structural and morphological characteristics of the metallic electrodeposit was also investigated. The electrodeposits were characterized by X-ray diffraction and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy. Using transmission electron microscopy, it was possible to conclude that the chemical treatment applied to the commercial TiO₂ particles promotes the formation of Ag₂S/TiO₂ composite nanoparticles, with Ti, Ag, S and O in its composition. This was also was confirmed by X-ray fluorescence spectrometry. These particles absorb visible light radiation which makes them promising materials for photoelectrocatalytic processes. Moreover, the modification in nanoparticle composition plays a remarkable influence on the coating morphology and Zn crystallite size. When TiO₂ is added, a change of Zn texture was observed along with a decrease in crystallite size. In contrast, the metal matrix nanocomposites prepared with Ag₂S/TiO₂ exhibit a spongy Zn morphology with a lower average Zn crystallite size. The nanocomposite films were tested in the photoelectrodegradation of ibuprofen and the best results were obtained for Zn–Ag₂S/ TiO₂ photoelectrodes.     

Electrophysical properties of solid solutions of Zn2 − x (Zr a Sn b )1 − x Fe2x O4 compositions

The electrophysical properties of the multicomponent Zn₂ZrO₄ ? Zn₂SnO₄ ? ZnFe₂O₄ system are studied. The electrophysical parameters of solid solutions of Zn_{2 ? x} (Zr _a Sn _b )_{1 ? x} Fe_2x O₄ (x = 0–1.0, Δx = 0.1, a + b = 1) are determined. It is found that the formed solid solutions are semiconductors with electrophysical properties that change in a regular fashion with composition and are distinguished by high values of resistivity (107–1012 Ω cm).     

Electrochemical study of spinel oxide systems with nominal compositions Ni1− x Cu x Co2O4 and NiCo2− y Cu y O4

Studies on the electrochemical behaviour of Ni_{1− x} Cu _x Co₂O₄ (x ≤ 0.75) and NiCo_{2− y} Cu _y O₄ (y ≤ 0.30) electrodes in 5 mol dm⁻³ KOH aqueous solutions are presented. The oxide layers have been prepared by thermal decomposition of aqueous nitrate solutions on nickel supports at 623 K. Powder samples were also prepared by thermal decomposition under the same conditions. The powder samples and the oxide layers were characterised by X-ray powder diffraction. The influence of the copper content on the voltammetric response of the electrodes and activity towards oxygen evolution reaction is analysed and correlated with the surface composition of the electrodes by means of X-ray photoelectron spectroscopy data. The analysis of the results reveals that the presence of Cu affects the electrode behaviour and its influence depends on which cation has been replaced. Received: 22 February 1999 / Accepted: 26 October 1999     

Preparation and properties of highly conductive La1−x M x MnO3−y thin film showing magnetic effect from sol-gel process

The sol-gel synthesis of Sr-doped-LaMnO₃ thin film was investigated. The optimum condition was obtained when strontium, lanthanum and manganese nitrates were used as raw materials and diethylene or propylene glycol was used as solvent. An alumina plate was used as a substrate. The film thickness was about 0.2 m for one dip coating. The conductivity of Sr-substituted-LaMnO₃ increased with increasing Sr content and showed ferromagnetic properties. The conduction mechanism was a hopping conduction due to the small polaron. The metal-semiconductor transition at around room temperature was considered to be caused by the Jahn-Teller effect.     

Electroconductivity and nature of ion transfer in La1 − x Sr x Sc1 − y Mg y O3 − α system (0.01 ≤ x = y ≤ 0.20) in dry and humid air

The conductivity and ion and proton transfer numbers were measured in La_{1 ? x} Sr _x Sc_{1 ? y} Mg _y O_{3 ? α} system (x = y = 0.10–0.20). The partial conductivities (total ion, proton, oxygen, hole) and their effective activation energies were calculated. The measurements were carried out in air with respect to humidity (pH₂O = 0.04?2.65 kPa) within the temperature range from 630 to 920°C.