Reduction from Eu3+ to Eu2+ in BaAl2O4 : Eu phosphor prepared in an oxidizing atmosphere and luminescent properties of BaAl2O4 : Eu

A reduction phenomenon of Eu3+ -> Eu2+ was observed for the first time when Eu3+ ions were doped into an AlO4-tetrahedron-containing compound BaAl2O4 in an oxidizing atmosphere of air by high-temperature solid-state reaction. X-ray powder diffraction patterns and photoluminescent spectra are used to confirm the compound structure and detect the simultaneous existence of both divalent and trivalent europium ions, respectively. The abnormal Eu3+ -> Eu2+ reduction is explained by a charge compensation model. Spectroscopic properties of BaAl2O4:Eu are discussed and Eu2+ emission spectrum shows consistence with the results reported by Katsumata et a]. [J. Cryst. Growth 198/199 (1999) 869.] and Lin et al. [Mater. Chem. Phys. 70 (2001) 156.].

Single-crystalline nanowires of SiC synthesized by carbothermal reduction of electrospun PVP/TEOS composite fibres

Nanowires of SiC were synthesized by carbothermally reducing PVP/TEOS composite fibres obtained by electrospinning. High-resolution transmission electron microscopy (HRTEM) and selected-area electron diffraction (SAED) indicated that the SiC nanowires are single crystalline in nature. Both Fourier-transformed infrared spectroscopy and HRTEM indicated that a thin layer of SiO2 was formed on the outer surface of the nanowire as a result of post-heat treatment for the removal of residual carbon. Such SiO2 layer protects the inner SiC fibre from further oxidation. The formation mechanism of single-crystalline SiC nanowires was proposed based on our understanding and characterizations. The growth of the nanowire is believed to be along the ( 111) of its cubic cell.

The real role of carbon in Pt/C catalysts for oxygen reduction reaction

A new electrocatalysis of carbon materials for oxygen reduction reaction (ORR) on Pt/C catalysts was discovered. It was found that there exist two kinds of electroactive sites on these supports of carbon materials, which can effectively electrocatalyze the reduction of peroxide intermediated from oxygen reduction on Pt, as this provides continuous driving force to move the equilibrium toward the production of peroxide from ORR.

Electrocatalytic reduction of 1,2-diiodoethane by anions of supramolecular complex of (beta-CD)(2)/C-60 in DMF solution

The homogeneous electrocatalytic reduction of 1,2-diiodoethane by anions of the supramolecular complex of (beta-CD)(2)/C-60 in DMF solution is reported. The results show that the trianion of (beta-CD)(2)/C-60 exhibits electrocatalytic behavior towards the reduction of 1,2-diiodoethane, whereas the diani on is unable to reduce the diiodoethane. The second-order catalytic rate constant in DMF solution was determined to be 3.1 x 10(5) M-1 s(-1) by analysis of voltammetric responses under pseudo-first-order conditions with respect to (beta-CD)(2)/C-60. The results suggest that the host beta-cyclodextrin molecules have little effect on the electrocatalytic ability of the encapsulated C-60 toward organic halides.

Preparation of hybrid thin film modified carbon nanotubes on glassy carbon electrode and its electrocatalysis for oxygen reduction

A hybrid thin film containing Pt nanoparticles and [tetrakis(N-methylpyridyl)porphyrinato] cobalt (CoTMPyP) modified multi-walled carbon nanotubes (MWNTs) on a glassy carbon (GC) electrode surface was fabricated. This hybrid film electrode exhibited remarkable electrocatalytic activity for oxygen reduction and high stability with promising applications in fuel cells.

Synthesis of gold nanoplates by aspartate reduction of gold chloride

Single crystal nanoplates with thickness less than 30 nm, characterized by hexagonal and truncated triangular shapes bounded mainly by {111} facets, were obtained in large quantities by aspartate reduction of gold chloride.

Electrochemical design of ultrathin platinum-coated gold nanoparticle monolayer films as a novel nanostructured electrocatalyst for oxygen reduction

The deliberate tailoring of nanostructured metallic catalysts at the monolayer-level is an ongoing challenge and could lead to new electronic and catalytic properties, since surface-catalyzed reactions are extremely sensitive to the atomic-level details of the catalytic surface. In this article, we present a novel electrochemical strategy to nanoparticle-based catalyst design using the recently developed underpotential deposition (UPD) redox replacement technique. A single UPD Cu replacement with Pt2+ yielded a uniform Pt layer on colloid gold surfaces. The ultrathin (nominally monolayer-level) Pt coating of the novel nanostructured particles was confirmed by cyclic voltammetry and X-ray photoelectron spectra (XPS). The present results demonstrate that ultrathin Pt coating effects efficiently and behaves as the nanostructured monometallic Pt for electrocatalytic oxygen reduction, and also shows size-dependent, tunable electrocatalytic ability. The as-prepared ultrathin Pt-coated Au nanoparticle monolayer electrodes reduce O-2 predominantly by four electrons to H2O, as confirmed by the rotating ring-disk electrode (RRDE) technique.

Electrocatalytic reduction of oxygen at multi-walled carbon nanotubes and cobalt porphyrin modified glassy carbon electrode

The multi-walled carbon nanotubes (MWNTs) modified glassy carbon electrode exhibited electrocatalytic activity to the reduction of oxygen in 0.1 M HAc-NaAc (pH 3.8) buffer solution. Further modification with cobalt porphyrin film on the MWNTs by adsorption, the resulted modified electrode showed more efficient catalytic activity to O-2 reduction. The reduction peak potential of O-2 is shifted much more positively to 0.12 V (vs. Ag/AgCl), and the peak current is increased greatly. Cyclic voltammetry (CV), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), were used to characterize the material and the modified film on electrode surface. Electrochemical experiments gave the total number of electron transfer for oxygen reduction as about 3, which indicated a co-exist process of 2 electrons and 4 electrons for reduction of oxygen at this modified electrode. Meanwhile, the catalytic activities of the multilayer film (MVVNTs/CoTMPyP)(n) prepared by layer-by-layer method were investigated, and the results showed that the peak current of O-2 reduction increased and the peak potential shifted to a positive direction with the increase of layer numbers.

Hydrothermal synthesis and crystal structure of a sulfur-bridged binuclear copper(II) coordination polymer generated by a spontaneous reduction

A simultaneous reduction SO42- to S2- by 2,5-pyridinedicarboxylate under hydrothermal conditions produced a new binuclear copper(II) coordination polymer [CuS(4,4'-bipy)](n) (4,4-bipy = 4,4'-bipyridine) (1). Single crystal X-ray analysis revealed that compound I consisted of sulfur-bridged binuclear copper(II) units with Cu-Cu bonding which were combined with 4,4-bipy to generate a three-dimensional network constructed from mutual interpenetration of two-dimensional (6,3) nets. Crystal data for 1:C10H8CuN2S, tetragonal 14(1)/acd, a = 14.0686(5) Angstrom, b = 14.0686(5) Angstrom, c = 38.759(2) Angstrom, Z = 32. Other characterizations by elemental analysis, IR, EPR and TGA analysis were also described in this paper.

Fabrication of a metalloporphyrin - Polyoxometalate hybrid film by a layer-by-layer method and its catalysis for hydrogen evolution and dioxygen reduction

Tetrakis (N-methylpyridyl) porphyrinato] cobalt (CoTMPyP) and 1:12 silicotungstic acid (SiW12) were alternately deposited on a 4-aminobenzoic acid (4-ABA)-modified glassy carbon electrode through a layer-by-layer method. The resulting organic-inorganic hybrid films were characterized by cyclic voltammetry (CV) and UV/vis absorption spectroscopy. We proved that the prepared multilayer films are uniform and stable. SiW12-containing multilayer films (SiW12 as the outermost layer) exhibit remarkable electrocatalytic activity for the hydrogen evolution reaction (HER). The kinetic constants for HER were comparatively investigated at different layers Of SiW12/CoTMPyP multilayer film-modified electrodes by hydrogen evolution voltammetry. In addition, rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) voltammetric methods confirm that SiW12/CoTMPyP (CoTMPyP as the outermost layer) multilayer films catalyze almost a two-electron reduction of O-2 to H2O2 in pH 1-6 buffer solutions. Furthermore, P2W18/CoTMPyP films were also assembled, and their catalytic activity for HER is very different from that Of SiW12/CoTMPyP multilayer films.

Preparation of multilayer films containing pt nanoparticles on a glassy carbon electrode and application as an electrocatalyst for dioxygen reduction

In this paper, a simple route for the preparation of Pt nanoparticles is described. PtCl62- and [tetrakis-(N-methylpyridyl)porphyrinato] cobalt (CoTMPyP) were assembled on a 4-aminobenzoic acid modified glassy carbon electrode through the layer-by-layer method. The three-dimensional Pt nanoparticle films are directly formed on an electrode surface by electrochemical reduction of PtCl62- sandwiched between CoTMPyP layers. Regular growth of the multilayer films is monitored by UV-vis spectroscopy. X-ray photoelectron spectroscopy verifies the constant composition of the multilayer films containing Pt nanoparticles. Atomic force microscopy proves that the as-prepared Pt nanoparticles are uniformily distributed with average particle diameters of 6-10 nm. The resulting multilayer films containing Pt nanoparticles on the modified electrode possess catalytic activity for the reduction of dissolved oxygen. Rotating disk electrode voltammetry and rotating ring-disk electrode voltammetry confirm that Pt nanoparticle containing films can catalyze an almost four-electron reduction of O-2 to water in 0.5 M H2SO4 solution.

Simple preparation method of Pd nanoparticles on an Au electrode and its catalysis for dioxygen reduction

A simple method for the fabrication of Pd nanoparticles is described. The three-dimensional Pd nanoparticle films are directly formed on a gold electrode surface by simple electrodeposition at -200 mV from a solution of 1 M H2SO4+0.01 mM K2PdCl4. X-Ray photoelectron spectroscopy verifies the constant composition of the Pd nanoparticle films. Atomic force microscopy proves that the as-prepared Pd nanoparticles are uniformly distributed with an average particle diameter of 45-60 nm. It is confirmed that the morphology of the Pd nanoparticle films are correlated with the electrodeposition time and the state of the Au substrate. The resulting Pd-nanoparticle-film-modified electrode possesses high catalytic activity for the reduction of dissolved oxygen in 0.1 M KCl solution. Freshly prepared Pd nanoparticles can catalyze the reduction of O-2 by a 4-electron process at -200 mV in 0.1 M KCl, but this system is not very stable. The cathodic peaks corresponding to the reduction of O-2 gradually decrease with potential cycling and at last reach a steady state. Then two well-defined reduction peaks are observed at -390 and -600 mV vs. Ag/AgCl/KCl (sat.). Those two peaks correspond to a 2-step process for the 4-electron reduction pathway of O-2 in this neutral medium.

The reduction of Eu3+ to Eu2+ in BaMgSiO4 : Eu prepared in air and the luminescence of BaMgSiO4 : Eu2+ phosphor

The reduction of Eu3+ to Eu2+ in air has been observed in a silicate matrix for the first time in BaMgSiO4:Eu prepared by high-temperature solid-state reaction. Emission and excitation spectra were employed to detect the presence of Eu2+ ions in the compound and this reduction was explained by a charge compensation model proposed previously. In BaMgSiO4 : Eu2+, Eu2+ ions occupy three different lattice sites by substitution for Ba2+ ions. Eu2+ ions on Ba(1) and Ba(2) sites gave emissions at about 500 nm while that on Ba(3) site showed an emission band at 398 nm. All the emissions of Eu2+ ions in BaMgSiO4 : Eu2+ were not quenched at room temperature.

Study on the reduction of Eu3+ -> Eu2+ in Sr4Al14O25: Eu prepared in air atmosphere

Compounds of Sr4Al14O15: Eu were prepared in air atmosphere by high temperature solid state reaction. The reduction of Eu3+--> Eu2+ was firstly observed in the aluminate phosphor of Sr4Al14O25: Eu synthesized in air condition. This made aluminate a new family and Sr4Al14O25 a new member of compounds in which Eu3+ ion could be reduced to Eu2+ form when fired in air atmosphere. The reduction of Eu3+ --> Eu2+ in Sr4Al14O25: Eu was explained by means of a charge compensation model. Experiments based on the model were designed and carried out, and the results supported this model.