Syntheses, structures and near-IR luminescent studies on ternary lanthanide (Er-III, Ho-III, Yb-III, Nd-III) complexes containing 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dionate

The ligand Hhfth [4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dione], which contains a heptafluoropropyl group, has been used to synthesize several new ternary lanthanide complexes (Ln = Er, Ho, Yb, Nd) in which the synergistic ligand is 1,10-phenanthroline (phen) or 2,2'-bipyridine (bipy). The two series of complexes are [Ln(hfth)(3)phen] [abbreviated as (Ln)1, where Ln = Er, Ho, Yb] and [Ln(hfth)(3)bipy] [abbreviated as (Ln)2, where Ln = Er, Ho, Yb, Nd]. Members of the two series have been structurally characterized. The growth morphology, diffuse reflectance (DR) spectra, thermogravimetric analyses, and photophysical studies of these complexes are described in detail. After ligand-mediated excitation of the complexes, they all show the characteristic near-infrared (NIR) luminescence of the corresponding Ln(3+) ions (Ln = Er, Ho, Yb, Nd). This is attributed to efficient energy transfer from the ligands to the central Ln(3+) ions, i.e. an antenna effect. The heptafluorinated substituent in the main hfth sensitizer serves to reduce the degree of vibrational quenching. With these NIR-luminescent lanthanide complexes, the luminescent spectral region from 1300 to 1600 nm, which is of particular interest for telecommunication applications, can be covered completely.

Facile preparation of ZnTiO3 ceramic powders in sodium/potassium chloride melts

A facile molten salt synthesis route was developed to prepare ZnTiO3 ceramic powders with simple oxides ZnO and TiO2 using sodium and potassium chloride eutectic salts as flux. The role of calcination temperature and time and the amount of salt addition to ZnTiO3 formation was investigated by thermogravimetry-differential thermal analysis, X-ray diffraction and Fourier transformation-infrared spectroscopy measurements. Pure hexagonal phase of ZnTiO3 could be obtained from the mixture of the simple oxides and the chlorides (50 mol% KCl, 20 times to oxides in molar ratio) heating at 800 degrees C for 6 h. The scanning electron microscopy images revealed the products were hexagonal sheets of about 1-3 mu m size. Increasing the amount of salt aids in reducing the crystal sizes of final ceramic powders because of diluting the solution.

New double-ceramic-layer thermal barrier coatings based on zirconia-rare earth composite oxides

A series of La2O3-ZrO2-CeO2 composite oxides were synthesized by solid-state reaction. The final product keeps fluorite structure when the molar ratio Ce/Zr >= 0.7/0.3, and below this ratio only mixtures of La2Zr2O7 (pyrochlore) and La2O3-CeO2 (fluorite) exist. Averagely speaking, the increase of CeO2 content gives rise to the increase of thermal expansion coefficient and the reduction of thermal conductivity, but La-2(Zr0.7Ce0.3)(2)O-7 has the lowest sintering ability and the lowest thermal conductivity which could be explained by the theory of phonon scattering. Based on the large thermal expansion coefficient of La2Ce3.25O9.5, the low thermal conductivities and low sintering abilities of La2Zr2O7 and La-2(Zr0.7Ce0.3)(2)O-7, double-ceramic-layer thermal barrier coatings were prepared. The thermal cycling tests indicate that such a design can largely improve the thermal cycling lives of the coatings. Since no single material that has been studied so far satisfies all the requirements for high temperature thermal barrier coatings, double-ceramic-layer coating may be an important development direction of thermal barrier coatings.

Spectral properties of rare-earth ions in nanocrystalline YAG : Re (Re = Ce3+, Pr3+, Tb3+)

Bulk and nanoscale powders of YAG:Re (Re = Ce, Pr, Tb) were synthesized by solid-state and sol-gel method. The changes of spectra and energy level were studied. Compared with the bulk YAG:Re (Re = Ce, Pr, Tb) crystals, the lattice parameter of YAG:Re (Re = Ce, Pr, Tb) nanocrystals decreases. It is also found that the excitation peaks of 5d energy levels shift in nanocrystals. The physical reason for spectral and energy level changes is a comprehensive result from the shift of energy centroid of the 5d orbit, the Coulomb interaction between 4f and 5d electrons and the crystal field splitting of the 5d energy level.

A new blue phosphorescent glass-ceramic: Rare-earth-doped calcium aluminoborate

A new blue phosphorescent glass-ceramic, Eu2+ and Nd3+, co-doped CaO-Al2O3-B2O3, was synthesized. After the irradiation with ultraviolet (UV) light, the glass-ceramic emitted blue long-lasting phosphorescence (LLP) with a spectrum peaking at about 464 nm ascribed to the characteristic 4f(6)5d(1) -> 8S(7/2) transition of Eu2+. This phosphorescence can be seen in the dark 1 h after the irradiation. However, the transparent Eu2+ and Nd3+ co-doped CaO-Al2O3-B2O3 glass did not show the phosphorescence. By the X-ray diffraction diffusion (XRD) data, alpha-CaAl2B2O7 was demonstrated to be the crystallites in the glass-ceramic. We think that alpha-CaAl2B2O7:Eu2+ Nd3+ crystallites produced during the heat treatment of the glass contribute to the LLP of the glass-ceramic.

Thermal stability of double-ceramic-layer thermal barrier coatings with various coating thickness

Double-ceramic-layer (DCL) coatings with various thickness ratios composed of YSZ (6-8 wt.% Y2O3 + ZrO2) and lanthanum zirconate (LZ, La2Zr2O7) were produced by the atmospheric plasma spraying. Chemical stability of LZ in contact with YSZ in DCL coatings was investigated by calcining powder blends at different temperatures. No obvious reaction was observed when the calcination temperature was lower than 1250 degrees C, implying that LZ and YSZ had good chemical applicability for producing DCL coating. The thermal cycling test indicate that the cycling lives of the DCL coatings are strongly dependent on the thickness ratio of LZ and YSZ, and the coatings with YSZ thickness between 150 and 200 mu m have even longer lives than the single-layer YSZ coating. When the YSZ layer is thinner than 100 mu m, the DCL coatings failed in the LZ layer close to the interface of YSZ layer and LZ layer. For the coatings with the YSZ thickness above 150 mu m, the failure mainly occurs at the interface of the YSZ layer and the bond coat.

Morphology control and luminescence properties of YAG : Eu phosphors prepared by spray pyrolysis

Starting from nitrate aqueous solutions with citric acid and polyethylene glycol (PEG) as additives, Y3Al5O12:Eu (YAG:Eu) phosphors were prepared by a two-step spray pyrolysis (SP) method. The obtained YAG:Eu phosphor particles have spherical shape, submicron size and smooth surface. The effects of process conditions of the spray pyrolysis on the crystallinity, morphology and luminescence properties of phosphor particles were investigated. The emission intensity of the phosphors increased with increasing of sintering temperature and solution concentration due to the increase of the crystallinity and particles size, respectively. Adequate amount of PEG was necessary for obtaining spherical particles, and the optimum emission intensity could be obtained when the concentration of PEG was 0.10 g/ml in the precursor solution. Compared with the YAG:Eu phosphor prepared by citrate-gel (CG) method with non-spherical morphology, spherical YAG:Eu phosphor particles showed a higher emission intensity.

Syntheses and crystal structures of bis(tetrahydrofurfurylindenyl) lanthanocene chlorides (C4H7OCH2C9H6)(2)LnCl (Ln = Nd, Sm, Dy, Ho, Er, Yb)

Reaction of anhydrous lanthanide trichlorides with tetrahydrofurfuryl indenyl lithium in THF afforded bis(tetrahydrofurfurylindenyl) lanthanocene chlorides complexes (C4H7OCH2C9H6)(2) LnCl, Ln = Nd (1), Sm (2), Dy (3), Ho (4), Er (5), Yb (6). The X-ray crystallographic structures of all the six complexes were determined and these indicate that they are unsolvated nine-coordinate monomeric complexes with a trans arrangement of both the sidearm and indenyl rings in the solid state. They belong to the same crystal system (orthorhombic) and space group (P2(1)2(1)2(1)) with the same structure. Especially, they are more stable to air and moisture than the corresponding unsubstituted indenyl lanthanide complexes.

Carbon ceramic electrodes bulk-modified with nanoparticles of ferrocenebutyrate-intercalated Mg-Al layered double hydroxide

Ferrocenebutyrate-intercalated layered double hydroxide (FcLDH) was prepared by the coprecipitation method and characterized by PXRD, FTIR, TEM and elemental analysis. FcLDH nanoparticles in deionized water were deposited onto the surface of graphite powder to yield graphite powder-supported FcLDH, which was subsequently dispersed into methyltrimethoxysilane-derived gels to fabricate surface-renewable, stable, rigid carbon ceramic electrodes containing the electroactive ferrocenyl group. Cyclic voltammetric study revealed that peak currents of the FcLDH-modified electrode were diffusion-con trolled in 0.1 mol l(-1) KCl aqueous solution. In addition, the formal potential of the modified electrode is related to the activity of chloride ion with a Nernst slope of 56 mV per decade.

Electrochemiluminescent determination of glucose with a sol-gel derived ceramic-carbon composite electrode as a renewable optical fiber biosensor

A sol-gel derived ceramic-carbon composite electrode is used for fabrication of a new type of optical fiber biosensor based on luminol electrochemiluminescence (ECL). The electrode consists of graphite powder impregnated with glucose oxidase in a silicate network. In this configuration, the immobilized enzyme oxidizes glucose to liberate hydrogen peroxide and graphite powder provides percolation conductivity for triggering the ECL between luminol and the liberated hydrogen peroxide. Both of the reactions occur simultaneously on the surface of the composite electrode, thereby the response of the biosensor is very fast. The peak intensity was achieved within only 20 s after glucose injection. In addition, the electrode could be renewed by a simple mechanical polishing step in case of contamination or fouling. The linear range extends from 0.01 to 10 mM for glucose and the detection limit is about 8.16 muM. The renewal repeatability and stability of the biosensor are also investigated in detail.

Sol-gel derived carbon ceramic electrode containing methylene blue-intercalted alpha-zirconium phosphate micro particles

Methylene blue-intercalated a-zirconium phosphate (MBZrP) micro particles in deionized water were deposited onto the surface of graphite powder to prepare graphite powder-supported MBZrP, which was subsequently dispersed into methyltrimethoxysilane-derived gels to yield a conductive composite. The composite was used as electrode material to fabricate a surface-renewable, rigid, leak-free carbon ceramic composite electrode, bulk-modified with methylene blue (MB). In the configuration, alpha-zirconium phosphate was employed as a solid host for MB, which acted as a catalyst. Graphite powder ensured conductivity by percolation, the silicate provided a rigid porous backbone and the methyl groups endowed hydrophobicity and thus limited the wetting section of the modified electrode. Peak currents of the MBZrP-modified electrode were surface-confined at low scan rates but diffusion-controlled at high scan rates. Square-wave voltammetric study revealed that MBZrP immobilized in carbon ceramic matrix presented a two-electron, three-proton redox process in acidic aqueous solution with pH ranged from 0.44 to 2.94. In addition, the chemically modified electrode showed an electrocatalytic activity toward nitrite reduction at +0.15 V (vs. Ag/AgCl) in acidic aqueous solution (pH=0.44). The linear range and detection limit are 1 x 10(-6)-4 x 10(-3) mol L-1 and 1.5 x 10(-7) mol L-1, respectively.

Cupric hexacyanoferrate nanoparticle modified carbon ceramic composite electrodes

Graphite powder-supported cupric hexacyanoferrate (CuHCF) nanoparticles were dispersed into methyltrimethoxysilane based gels to produce a conducting carbon ceramic Composite, which was used as electrode material to fabricate surface- renewable CuHCF-modified electrodes. Electrochemical behavior of the CuHCF-modifled carbon ceramic composite electrodes was characterized using cyclic and square-wave voltammetry. Cyclic voltammograms at various scan rates indicated that peak currents were surface-confined at low scan rates. In the presence of glutathione, a clear electrocatalytic response was observed at the CuHCF-modified composite electrodes. In addition, the electrodes exhibited a distinct advantage of reproducible surface-renewal by simple mechanical polishing on emery paper, as well as ease of preparation, and good chemical and mechanical stability in a flowing stream.

Carbon ceramic electrodes modified with sub-micron particles of new methylene blue (NMB) intercalated alpha-zirconium phosphate

New methylene blue-intercalated a-zirconium phosphate (NMBZrP) was synthesized in the presence of n-butylamine and characterized by powder XRD, FTIR, TEM and elemental analysis. Sub-micron particles of NMBZrP in deionized water were apt to deposit onto the surface of graphite powder to yield graphite powder-supported NMBZrP, which was subsequently dispersed into methyltrimethoxysilane-derived gels to fabricate surface-renewable, stable, rigid carbon ceramic electrodes containing new methylene blue. Cyclic voltammetric studies revealed that peak currents of the NMBZrP-modified electrode were surface-confined at low scan rates but diffusion-controlled. at high scan rates. In addition, NMBZrP immobilized in a carbon ceramic matrix presented a two-electron, three-proton redox process in acidic aqueous solution in the pH range from 0.52 to 3.95.

Sol-gel derived carbon ceramic electrode bulk-modified with tris(1,10-phenanthroline-5,6-dione)iron(II) hexafluorophosphate and its use as an amperometric iodate sensor

A surface-renewable tris (1,10-phenanthroline-5, 6-dione) iron (II) hexafluorophosphate (FePD) modified carbon ceramic electrode was constructed by dispersing FePD and graphite powder in methyltrimethoxysilane (MTMOS) based gels. The FePD-modified electrode presented pH dependent voltammetric behavior, and its peak currents were diffusion-controlled in 0.1 mol/L Na2SO4 + H2SO4 solution (pH = 0. 4). In the, presence of iodate, clear electrocatalytic reduction waves were observed and thus the chemically modified electrode was used as an amperometric sensor for iodate in common salt. The linear range, sensitivity, detection limit and response time of the iodate sensor were 5 x 10(-6)-1 x 10(-2) mol/L, 7.448 muA.L/mmol, 1.2 x 10(-6) mol/L and 5 s, respectively. A distinct advantage of this sensor is its good reproducibility of surface-renewal by simple mechanical polishing.

Bienzymatic amperometric biosensor for glucose based on polypyrrole/ceramic carbon as electrode material

A novel amperometric biosensor utilizing two enzymes, glucose oxidase (GOD) and horseradish peroxidase (HRP), was developed for the cathodic detection of glucose. The glucose biosensor was constructed by electrochemical formation of a polypyrrole (PPy) membrane in the presence of GOD on the surface of a HRP-modified sol-gel derived-mediated ceramic carbon electrode. Ferrocenecarboxylic acid (FCA) was used as mediator to transfer electron between enzyme and electrode. In the hetero-bilayer configuration of electrode, all enzymes were well immobilized in electrode matrices and showed favorable enzymatic activities. The amperometric detection of glucose was carried out at +0.16 V (versus saturated calomel reference electrode (SCE)) in 0.1 M phosphate buffer solution (pH 6.9) with a linear response range between 8.0 x 10(-5) and 1.3 x 10(-3) M glucose. The biosensor showed a good suppression of interference in the amperometric detection.