Effects of peak current density on the structure and property of PbO<Subscript>2</Subscript>–CeO<Subscript>2</Subscript> nanocomposite electrodes prepared by pulse electrodeposition

PbO₂–CeO₂ nanocomposite electrodes were prepared by pulse electrodeposition method in the lead nitrate solution containing CeO₂ nanoparticles with different peak current density. The content of CeO₂ nanoparticles in the electrodes increase with the increase of peak current density. The effects of peak current density on the morphology and structure of PbO₂–CeO₂ nanocomposite electrodes were studied by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The SEM and XRD results show that the increase of peak current density can make the morphology finer and more compact, and the crystal size decreases with the increase of peak current density. The oxygen evolution overpotential and stability of PbO₂–CeO₂ nanocomposite electrodes enhance with the increase of peak current density. The electrocatalytic property of PbO₂–CeO₂ nanocomposite electrodes was examined for the electrochemical oxidation of rhodamine B (RhB). The results show that the RhB removal efficiency on PbO₂–CeO₂ nanocomposite electrodes increase with the increase of peak current density, which can be attributed to the higher oxygen evolution overpotential and CeO₂ content in the composite electrodes.     

Electrodeposition of PbO<Subscript>2</Subscript>-ZrO<Subscript>2</Subscript> composite materials

The regularities of electrodeposition of composite materials based on PbO₂ containing zirconium dioxide particles are studied. The contents of various phases in the composite depend on the electrolyte composition and conditions of deposition. When a dispersed phase is incorporated into the composite coating, the dimensions of lead dioxide crystals decrease to submicrons.     

PbO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> composites: Electrosynthesis and physicochemical properties

Fundamental aspects of electro deposition of PbO₂-based composites containing titanium dioxide particles were studied. The content of the dispersed phase in the composite depends on the electrolyte composition and deposition conditions. Incorporation of titanium dioxide particles into PbO₂ leads to significant changes in the morphology and structure of the deposit.     

Electrochemical preparation of PMeT/TiO<Subscript>2</Subscript> nanocomposite electrochromic electrodes with enhanced long-term stability

In this work, 3-methylthiophene (MeT) was electrochemically incorporated with nano- and mesoporous TiO₂ films to form poly(3-methylthiophene) (PMeT)/TiO₂ nanocomposite electrochromic electrodes. TiO₂ films, which were previously coated on the ITO glass sheets through a well-established technique, were introduced to enhance the adhesion of the polymers to the substrates and thus increase the long-term stability of the devices. With this effort, the nanocomposite electrodes were found to retain up to 60% of their optical response after 3,500 deep and double potential steps and retain up to 50% of their electroactivity after 10⁴ same steps, exhibiting enhanced long-term stability. Switching time and the maximum optical contrast (ΔT%) of the nanocomposite electrodes were found to be 0.6 s and 45%, respectively. Moreover, our work showed that electrochemically incorporating conductive polymers (CPs) with TiO₂ mesoporous films was an effective method to form high-quality CP/TiO₂ nanocomposite electrodes, which can be used widely in battery cathodes, photovoltaic cells, photocatalytic reaction, and photoelectrochromic cells and were supposed to enhance their performances.     

PbO<Subscript>2</Subscript>-SnO<Subscript>2</Subscript> composite anode with interconnected structure for the electrochemical incineration of phenol

A PbO₂-SnO₂ composite anode with interconnected structure is prepared for organics electro-incineration through a two-step method, thermal-decomposition process and subsequent low-current density electrodeposition process. The element mapping, together with the impedance spectra of the composite electrode, confirms that an interconnected architecture of SnO₂ and PbO₂ grains, instead of a lamellar structure, was obtained on the Ti substrate. A lower electrodeposition current density (≤10 mA cm⁻²) is very crucial for the formation of a porous surface and an interconnected architecture of two oxides inside. The asprepared electrode exhibits an enhanced electrocatalytic activity on the mineralization of phenol and a long service life due to the interconnected architecture, which helps to utilize the merits of these two metal oxides simultaneously. This two-step method also provides us a novel and facile way to fabricate a series of composite material such as oxide-oxide, oxide-metal composite electrodes.     

pH-sensing properties of PbO<Subscript>2</Subscript> thin film electrodeposited on carbon ceramic electrode

In this paper, a new highly sensitive potentiometric pH electrode is proposed based on the solid-state PbO₂ film electrodeposited on carbon ceramic electrode (CCE). Two different crystal structures of PbO₂, α and β were examined and the similar results were obtained. Moreover, the experimental results obtained for the proposed pH sensor and a conventional glass pH electrode were in good agreement. The electromotive force (emf) signal between the pH-sensitive PbO₂-coated CCE and SCE reference electrode was linear over the pH range of 1.5–12.5. Near-Nernstian slopes of −64.82 and −57.85 mV/pH unit were obtained for α- and β-PbO₂ electrodes, respectively. The interferences of some mono-valence and multi-valence ions on potentiometric response of the sensor were studied. The proposed pH sensor displayed high ion selectivity with respect to K⁺, Na⁺, Ca²⁺, and Li⁺, with log values around −12 and has a working lifetime of about 30 days. Key parameters important for the pH sensor performance, including kind of PbO₂ film, selectivity, response time, stability, and reproducibility, have been characterized. The proposed electrode showed a good efficiency for direct pH-metry after calibration and pH-metric titrations without calibration step. The response time was about 1 s in acidic medium and less than 30 s in alkaline solutions. The pH values of complex matrix samples such as fruit juices measured by the proposed sensor and a conventional glass pH electrode were in good agreement.     

Electrodeposition of composite materials PbO<Subscript>2</Subscript>-Ti and their physicochemical properties

In the work, the regularities of electrodeposition of composite materials based on PbO₂ containing the valve metal particles are considered. The content of dispersed phase in the composite depends on the electrolyte composition and conditions of deposition. The incorporation of titanium particles into PbO₂ considerably changes the deposit morphology. It is found that the service life of electrodes containing dispersed Ti phase increases by 4 times as compared with the conventional anodes made of pure PbO₂.     

Nitrite oxidation on RuO<Subscript>2</Subscript> electrodes

An electrochemical kinetic investigation of nitrite oxidation to nitrate on RuO₂ is discussed. The process is studied by cyclic voltammetry, steady-state measurements and potential step measurements. The overall oxidation reaction is a two-electron process where the first step involves a reversible charge transfer: NO₂⁻ ⇔ NO₂ + e⁻ The one-electron oxidation of nitrite yields adsorbed NO₂ which is further oxidized to adsorbed (NO₂)⁺ and subsequently desorbed via a chemical reaction. In the general case, fit of experimental data is obtained with adsorption described by a Temkin isotherm unless the electrode is pre-treated at a cathodic potential where the (NO₂)_ads is removed. This treatment lowers the degree of coverage by intermediates but not the nature of the slow step. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 1, pp. 142–149. The text was submitted by the authors in English.     

Sb<Subscript>2</Subscript>S<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> nanocomposite layers synthesized using the layer-by-layer technique

Possibility of layer-by-layer synthesis by colloidal layering of Sb₂S₃-SiO₂ nanocomposite layers from colloid solutions of {[H _x Sb₂S₅] ^m ?}mNa⁺ and SiO₂ was studied. The composition of the layers synthesized was examined by Raman spectroscopy, transmission spectroscopy in the UV and visible spectral ranges, energy-dispersion micro analysis, and scanning electron microscopy.     

Effects of acetoin as chelating agent on the preparation of SrBi<Subscript>2</Subscript>Ta<Subscript>2</Subscript>O<Subscript>9</Subscript> thin films from non-hydrolyzing precursors

Ferroelectric thin films of strontium bismuth tantalate (SBT) have been fabricated by a chemical solution deposition technique using non-hydrolyzing precursors. Strontium acetate, bismuth nitrate and tantalum ethoxide were used as precursor materials, with methanol and glacial acetic as solvents. We investigate the effects of the precursor chemistry, by the selection of the chelating agent, on the elimination of residual organic compounds, thermal evolution of phase formation, and microstructure evolution of derived films. We found that the utilization of alkanolamines as chelating agent produce the segregation of metallic bismuth in as-prepared powders. On the other hand, acetoin, one of the hydroxyketones, showed the elimination of residual organics at low temperature, an earlier onset of crystallization, and no segregation of secondary phases during the whole crystallization process. A comparative investigation of the surface microstructure, grain size distribution, crystallinity, and degree of crystal orientation of films fabricated with the different chelating agents is presented. The dielectric and ferroelectric properties of films prepared with acetoin are investigated.     

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.     

Hydrothermal synthesis,structure and photocatalytic property of nano-TiO<Subscript>2</Subscript>-MnO<Subscript>2</Subscript>

TiCl₄ and MnSO₄· H₂O as raw materials are hydrolyzed stiochiometrically, following the intermediate of oxide hydrating reacts at 150°C, 0.5 MPa in high-pressure reactor, after filtering, washing and drying, nanometric TiO₂-MnO₂ (Ti_1-X Mn _X O₂) is prepared. The effects of the reaction temperature and time on nanometric TiO₂-MnO₂ are also discussed. XRD shows that the product is TiO₂-MnO₂ with amorphous phase. After being sintered at above 780 °C, it transfers into Ti_1-X Mn _X O₂ with a rutile structure. TEM shows that TiO₂-MnO₂ is the spherical particle. And the average diameter of the particles is 20 nm. The optical absorbance was determined by UV-265 spectrophotometer after dispersing the sample in the mixture of water and glycerol with the ratio of 1 : 1 equably. It is found that the nano-material possesses the advantages of both nano-TiO₂ and nano-MnO₂, and it has strong absorption in the UV and visible region. Photodegradation of dyes in an aqueous solution is investigated using nanometricTiO₂-MnO₂ as a photocatalyst. The results show that after 60 min illumination, the decolorization rate of the acidic red B and acidic black 234 dye can be as high as 100%.     

Oxidation of toluene on Bi-doped PbO<Subscript>2</Subscript> studied by electrochemical impedance spectroscopy and UV spectrophotometry

Oxidation of organics in the potential region of O₂ evolution is supposed to proceed through the oxidation of water to hydroxyl radicals, which then may either be further oxidized to give molecular oxygen or interact with organic molecules in an oxygen transfer reaction. Therefore, the electrode material must ensure (1) the preferential adsorption of the organic compound, (2) the production of adsorbed hydroxyl radicals able to react with this compound in a selective oxidation reaction (with as little as possible oxygen evolution), and (3) a long-term stability. In the present paper, the oxidative decomposition of toluene in sulfuric acid solution on PbO₂ coatings deposited on Ti substrate from acidic nitrate + fluoride baths containing Pb²⁺ and Bi³⁺ is investigated by voltammetry, electrochemical impedance spectroscopy, and UV spectrophotometry. The chemical composition and structure of the catalytic coatings is characterized with X-ray photoelectron spectroscopy and X-ray diffraction. The catalytic activity is estimated both from current density vs potential and polarization resistance vs potential plots using measurements on the same electrodes in sulfuric acid without toluene to eliminate the oxygen evolution reaction that proceeds in parallel to the oxidation of toluene. A skeletal reaction mechanism of the process is proposed to account for the steady-state and transient response of the catalytic electrodes during oxidation of toluene.     

Multifunctional performances of nanocomposite SiO<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> doped cationic EBODAC film coated on natural cellulose matrix

Reverse micellar microemulsions were utilised to synthesise stable lead titanate colloids from typical sol–gel type molecular precursors. The particles of a few nanometres in diameter that formed by hydrolysis in the micelle cores demonstrated a nanocrystalline texture without the need for thermal treatment. In a chemical solution deposition routine based on the nanoparticle dispersions, ferroelectric PbTiO₃ thin films showing excellent remanent polarisation of more than 50 μC cm⁻² were derived. The electrical characteristics of the layers were correlated to their microstructure which was controlled by the precursor composition and the annealing conditions. A columnar morphology that was realised by spinning on coatings of up to 100 nm in individual thickness proved most favourable with respect to the ferroelectric performance of the films.     

Specific heat on Sr<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>7</Subscript> and Sr<Subscript>2</Subscript>Ta<Subscript>2</Subscript>O<Subscript>7</Subscript>

Summary Specific heats on the single crystals of Sr₂Nb₂O₇, Sr₂Ta₂O₇ and (Sr_1-xBa_x)₂Nb₂O₇ were measured in a wide temperature range of 2-600 K. Heat anomalies of a λ-type were observed at the incommensurate phase transition of T_INC (=495 K) on Sr₂Nb₂O₇ and at the super-lattice phase transition of T_SL (=443 K) on Sr₂Ta₂O₇; the transition enthalpies and the transition entropies were estimated. Furthermore, a small heat anomaly was observed at the low temperature ferroelectric phase transition of T_LOW (=95 K) on Sr₂Nb₂O₇. The transition temperature T_LOW decreases with increasing Ba content x and it vanishes for samples of x>2%.     

Synthesis and structure of [UO<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>){CONH<Subscript>2</Subscript>N(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>}<Subscript>2</Subscript>]

The single crystals of [UO₂(C₂O₄){CONH₂N(CH₃)₂}₂] were synthesized and studied by X-ray diffraction. The crystals are monoclinic, a = 7.461(2) Å, b = 8.828(2) Å, c = 11.756(2) Å, β = 107.21(3)°, space group Pc, Z = 2, R = 2.94%. The structure comprises infinite chains [UO₂(C₂O₄){CONH₂N(CH₃)₂}₂] extended along [001] and corresponding to the AT¹¹M ₂ ¹ crystallochemical group (A = UO ₂ ²⁺ , T¹¹ = C₂O ₄ ^2? , M¹ = N,N-CONH₂N(CH₃)₂) of uranyl complexes. The chains are connected into a three-dimensional framework by hydrogen bonds involving the oxygen atoms of oxalate and uranyl ions and the N,N-dimethylcarbamide methyl groups.