A STUDY OF THE SPECTRUM PROPERTIES AND THE PHOTOVOLTAGE RESPONSE OF NANOCRYSTALLINE ND2O3

The diffuse reflectance spectra of nanocrystalline Nd2O3 were measured in the ultraviolet-visible region, It is found that the part of f-->f transition bands were widened and red-shift occurred. The absorption tail-band in the region from 300 to 550 nm was assigned to the O-2p-->Nd-4f transition. The behavior of light-induced charge transfer and photovoltaic properties of nanocrystalline Nd2O3 were studied by the surface photovoltage spectroscopy (SPS) and electric field modulating SPS techniques. The SPS response shows two peaks at 330 nm(P-1) and 380 nm(P-2) in the UV-Vis range, The spectral features observed can be explained in terms of charge transfer and interband transition.

ELECTROCATALYTIC OXIDATION OF REDUCED NICOTINAMIDE COENZYMES AT ORGANIC DYE-MODIFIED ELECTRODES

Chemically modified electrodes (CMEs) were prepared by adsorbing different dyes, including methylene blue (MB), toluidine blue (TB) and brilliant cresyl blue (BCB), onto glassy carbon electrodes (GCE) with anodic pretreatment. The electrochemical reactions of adsorbed dyes are fairly reversible at low coverages. The CMEs are more stable in acid solutions than in alkaline ones, which is mainly due to decomposition of the dyes in the latter media. They exhibit an excellent catalytic ability for the oxidation of nicotinamide coenzymes (NADH and NADPH). The formation of a charge transfer complex between the coenzyme and the adsorbed mediator has been demonstrated using a rotating disk electrode. The charge transfer complex decomposition is a slow step in the overall electrode reaction process. Some kinetic parameters are estimated. Dependence of the electrocatalytic activity of the CMEs on the solution pH is discussed.

COMPARATIVE-STUDY OF CA4Y6(SIO4)(6)O-A PHOSPHORS PREPARED BY SOL-GEL AND DRY METHODS (A=PB2+,EU3+, TB3+,DY3+)

Ca4Y6(SiO4)(6)O:A (A = Pb2+, Eu3+, Tb3+, Dy3+) phosphors have been prepared by two methods: the sol-gel method and the conventional dry method. The crystallization processes and the luminescence characteristics of the phosphors were studied, The sol-gel method features low-temperature formation of the phosphor, leading to successful preparation of Pb2+-activated phosphors which could not be prepared by the dry method at high temperature. The (4f)(8-)(4f)(7)(5d)(1) absorption band of Tb3+ and the charge-transfer (CT) band of Eu3+ have higher energies and narrower half-widths in the sol-gel-derived phosphors than in the phosphors prepared by the dry method, respectively. The Tb3+ and Dy3+ ions show stronger emission in the former than in the latter. Both the yellow-to-blue intensity ratio (Y:B) of Dy3+ and the red-to-orange intensity ratio (R:O) of Eu3+ in the sol-gel-derived phosphors are smaller than those for the phosphors derived by the dry method.

The Photovoltage Properties and the Spectrum Analyses of Nanocrystalline Er2O3

The diffuse reflectance spectra of nanocrystalline Er2O3 were measured in the UV-vis region. It was found that the f -> f transition bands become stronger with the decrease of the size of particles. The tail-band in the range of 300 similar to 550nm was assigned to the O2p -> Er4f transition. Both behavior of light-induced charge transfer and photovoltaic properties of nanocrystalline Er2O3 were investigated with surface photovoltage spectroscopy (SPS). The SPS shows that two peaks appear at 340nm (p(1)) and 385nm (p(2)). The observed spectral features can be explained in terms of charge transfer and interband transition.

X-RAY PHOTOELECTRON-SPECTRA OF SOME BIOINORGANIC COMPLEXES OF THE RARE-EARTHS WITH N-ACETYLALANINE

X-Ray photoelectron spectra of some bioinorganic complexes of La, Ce, PT, Nd, Sm and Eu with N-acetylalanine have been measured and the 3d5/2 and 3d3/2 main peaks and their satellites have also been assigned. ne spin-orbit splitting between the 3d5/2 and 3d3/2 core-level of the rare earth ion in these complexes becomes slightly larger than that of the free rare earth atom due to the effect of the crystal field. The satellite for the 3d main peaks of La in the solid state complex are in higher binding energy region and may be attributable to the L --> 4f charge-transfer shake-up process. The satellites for the 3d main peaks of Ce, Pr, Nd, Sm and Eu are in the lower binding energy region and may be attributable to the 4f --> L charge-transfer shake-down process.

HIGH-TEMPERATURE SUPERCONDUCTOR, YBA2CU3O7-X AS ALL-SOLID-STATE LITHIUM CELL

The utility of the high-temperature superconductor, YBa2Cu3O7-x as the cathode material for an all-solid-state lithium cell has been examined. The capacity of YBa2Cu3O7-x is 223 mA h g-1 and the discharge efficiency is > 92%. Measurements of a.c. impedance show that the charge-transfer resistance at the interface of the electrolyte/cathode is very low and increases with the depth-of-discharge of the battery. Studies using X-ray photoelectron spectroscopy (XPS) reveal that the cathode becomes doped with Li+ ions as the cell discharges.

INVESTIGATIONS OF HYDROLYSIS KINETICS OF ATROPINE SULFATE BY ELECTROANALYSIS AT THE WATER NITROBENZENE INTERFACE

The hydrolysis kinetics of atropine sulphate has been investigated by cyclic voltammetry at the water/nitrobenzene interface. The transfer process is diffusion controlled and the transfer species is a 1:1 proton-atropine complex. Two main factors, pH and temperature, which have notable effects on the hydrolysis rate, are illustrated. The most suitable pH for atropine to be preserved in aqueous solution and related parameters were estimated.

STRUCTURE OF HEXAMETHYLENETETRATELLURAFULVALENE DIIODIDE

C12H12I2Te4, M(r) = 920.44, monoclinic, P2(1)/n, a = 10.942 (2), b = 14.924 (2), c = 11.415 (2) angstrom, beta = 104.32 (1)-degrees, V = 1806.0 (5) angstrom 3, Z = 4, D(x) = 3.38 g cm-3, lambda(Mo K-alpha) = 0.71069 angstrom, mu = 100.7 cm-1, F(000) = 1592, T = 294 K, R = 0.033 for 1828 observed reflections. One of the Te atoms is bonded to the two I atoms, which are on either side of the molecular plane. The Te-I distances are 2.963 (1) and 2.961 (1) angstrom, which means oxidation at the Te atom instead of at the C = C bonds.

INVESTIGATION ON THE LUMINESCENCE PROPERTIES OF DY3+ AND EU3+ IN M3LN2(BO3)4 (M=CA, SR, BA, LN= LA, GD, Y)

In this paper, the luminescence properties of Dy3+ and Eu3+ in M3Ln2 (BO3)4 (M = Ca,Sr,Ba; Ln = La, Gd, Y) were systematically studied. The hypersensitive transitions of Dy3+ and Eu3+ were investigated in relation to the host compositions; the relationship between the energy of Eu3+ charge-transfer band and M2+ ion was discussed, and the concentration quenching of Dy3+ luminescence was reported.

STUDY ON STRUCTURE-PROPERTY RELATIONSHIP OF POLYIMIDE BLENDS .1. A DYNAMIC MECHANICAL STUDY OF THE MISCIBILITY OF POLYIMIDE POLYIMIDE BLENDS

Three pairs of polyimide/polyimide blends (50/50 wt%) with different molecular structures were prepared by two ways, i.e. mixing of the polyamic acid precursors with subsequent imidization, and direct solution mixing of the polyimides. The blends were studied with DMA technique. The results obtained show that all the blends prepared with these two different ways are miscible, as there existed only one glass transition temperature(Tg) for all the blends. It is suggested that the miscibility of these polyimide/polyimide blends is a result of the strong inter-molecular charge-transfer interaction between the chains of their components.

INVESTIGATION ON THE LUMINESCENCE PROPERTIES OF DY-3+ AND EU-3+ IN ALKALINE-EARTH BORATES

In this paper, the yellow-to-blue intensity ratio of Dy3+ (Y/B) and the red-to-orange intensity ratio of Eu3+ (R/O) were studied in relation to the compositions and structures of alkaline-earth borates. The dependence of the energy of the Eu3+ charge-transfer band (CTB) and of the emission intensity of Dy3+ on the alkaline-earth ions and the boron content of the hosts is discussed.

XPS STUDY ON RARE-EARTH PHTHALOCYANINE COMPLEXES

The rare earth monophthalocyanine complexes, LnPcCl and LnPc(OAc)2 (Ln = Tb, Ho, Tm, Lu, Pc=Phthalocyanine, OAc = Acetate), were synthesized. The electronic structures of the complexes have been studied by means of XPS. The experimental results of binding energies for the complexes indicate that the bonds of the complexes have a certain covalent character depending on L-->Ln charge transfer. This L-->Ln charge transfer process of phythalocyanine complexes differs from that of crown ether complexes. Both coordination and substitution are included in the former case, but only coordination in the latter. Phthalocyanine ring is an electrophilic group and its electronegativity is large. So, the O1s binding energies of coordinating oxygen atoms of acetate in LnPc(OAc)2 are larger than those of Ln(OAc)3. The magnitude of valent charge delocalized from ligand onto metal atom is dependent on electronegativity, coordination number, valence state and so on. Because coordination number of Ln in LnPc(OAc)2 is larger than that in LnPcCl and electronegativity of Clin LnPcCl is larger than that of O in LnPc(OAc)2, the Ln4d5/2 binding energies of LnPc (OAc)2 are less than those of LnPcCl.

ELECTROCATALYSIS OF POLYPYRROLE-METHYLENE BLUE FILM MODIFIED ELECTRODE FOR DIRECT REDOX REACTION OF CYTOCHROME-C

The electron transfer process of hemeproteins on the electrode surface is considered a promising subject in the area of bioelectrochemistry. Electrochemists believe that electron transfer between electroactive proteins and electrode surface might be expected to simulate the electron transfer between proteins. This research provides information about the electron transfer mechanism in biological system. Cytochrome c is a typical electron transferring protein,

ELECTRONIC-STRUCTURE AND CHEMICAL BONDING OF EUROPIUM NITRATE COMPLEX WITH AZACROWN (2, 2)

The electronic structure and bond character of europium nitrate complex with azacrown (2, 2)(1, 7, 10, 16-tetraoxa-4, 13-diazacyclooctadecane), [Eu(NO_3)_2(2, 2)] NO_3, have been studied by means of XPS and INDO method. The data of electronic binding energies and charge distribution of atoms in the complex showed that chemical shift of less electronegative nitrogen N1s binding energy was larger than that of more electronegative oxygen O1s binding energy in coordinating atoms, and that charge transfer from N...

THE ELECTROCATALYTIC OXIDATION OF ASCORBIC-ACID ON PRUSSIAN BLUE FILM MODIFIED ELECTRODES

The kinetics of prussian blue (PB) film itself during the redox process and of the catalytic oxidation of ascorbic acid (AH_2) on it have been studied in detail. The charge transfer diffusion coefficient D_(ct) in PB film is determined as 2.62×10~(-10)cm~2·s~(-1), using potential-step chronoamperometry, chronocoulometry and constant-current chronopotentialmetry, respectively. The rate constant of the cross-exchange reaction between AH_2 in solution and the active centers in PB film is measured in rotating d...