Solid-state Electrochemistry of Gadolinium Hexacyanoferrate Modified Electrode and Electrocatalytic Properties of Gadolinium Hexacyanoferrate

A new electroactive polynuclear inorganic compound of rare earth metal, gadolinium hexacyanoferrate (GdHCF), was prepared and characterized using the techniques of FTIR spectroscopy, thermogravimetric analysis (TG), UV-Vis spectrometry, X-ray photoelectron spectroscopy (XPS), ICP atomic emission spectroscopy, and EDX. The results of ICP atomic emission spectroscopy, EDX, and TGA indicated that the prepared GdHCF sample had a stoichiometry of NaGdFe(CN)₆·12H₂O (when GdHCF was prepared in NaCl solution). The FTIR spectrum of GdHCF showed that there were two types of water molecules in the structure of GdHCF: one was the interstitial water (5 H₂O), which resulted from the association of water due to H-bonding, and the other was water coordinated with Gd (7 H₂O). The results obtained using XPS showed that the oxidation state of Fe and Gd in the GdHCF sample was +2 and +3, respectively. GdHCF was immobilized on the surface of spectroscopically pure graphite (SG) electrode forming the GdHCF/SG electrode, and the solid-state electrochemistry of the resultant electrode was studied using cyclic voltammetry. The cyclic voltammetric results indicated that the GdHCF/SG electrode exhibited a pair of well-defined and stable redox peaks with the formal potential of E^0′=(197±3) mV. The effects of the concentration of the supporting electrolyte on the electrochemical characteristics of GdHCF were studied, and the results showed that the value of E^0′ increased linearly with the activity of the cationic ion of the supporting electrolyte (lga_Na⁺), with a slope of 54.1 mV, which may become a novel method for determining the activity of Na⁺ in solution. Further experimental results indicated that GdHCF had electrocatalytic activities toward the oxidation of dopamine (DA) and ascorbic acid (AA), and the electrocatalytic current increased linearly with the concentration of DA (or AA) in the range of 1.0–10.0 mmol·L^?1 (for DA) or 0.5–20.0 mmol·L^?1 (for AA).     

Carbon-13 NMR evidence for cocrystallization of cellulose as a mechanism for hornification of bleached kraft pulp

Solid-state ¹³C NMR spectroscopy was used to characterize a bleached softwood kraft pulp in the never-dried state and after cycles of drying and remoistening. Changes in NMR signal strengths indicated that growth of crystalline domains involved cocrystallization rather than accretion of cellulose from noncrystalline domains. A cluster of C-4 signals at 89.4 ppm, assigned to the interiors of crystalline domains, grew at the expense of C-4 signals at 84.0 and 84.9 ppm, assigned to the well-ordered surfaces of crystalline domains. Irreversible changes were not detected until the moisture content dropped below 18%. They were enhanced by a second drying/remoistening cycle, but showed little further change on subsequent cycles. The necessary conditions resembled those reported for hornification, suggesting that cocrystallization might provide a mechanism for hornification.     

Performance of a CW pumped Nd:YVO4 amplifier with kHz pulses

Until recently, simple and reliable high repetition-rate laser sources with nanosecond pulses much shorter than from conventional A-O Q-switch lasers were not available. However over the past 2 years we have developed such lasers based on proprietary fast E-O switching technology, which allows designs delivering 1 ns pulses and subnanosecond jitter for good synchronisation. The technology provides pulses with multi-kW peak power and repetition-rates to >100 kHz.Most recently, the performance of these short pulse lasers has been developed further by implementing oscillator/amplifier (master oscillator and power amplifier, MOPA) technology which increases the output to >1 W average power. Here we report on a simple model that has been used to predict the performance of the CW pumped Nd:YVO₄ amplifier used in the MOPA laser. The model is based on the well-known expressions for the saturated gain applying to laser pulses, but more usually applied to pulse-excited amplifiers. The model is shown to allow a good interpretation of the amplifier behaviour for kHz pulses and to be a useful tool for predicting the performance of the MOPA laser.     

The time recovery of the spectroscopic properties of heavily irradiated CdZnTe and CdTe detectors

The time recovery of the spectroscopic capabilities of CdZnTe and CdTe detectors, irradiated with increasing doses of high- and low-energy neutrons, as well as electrons, has been investigated by studying their spectroscopic behavior at different photon energies using leakage current measurements and PICTS (photo-induced current transient spectroscopy) analysis. The detectors were stored at room temperature for up to one year to study the time evolution of their spectroscopic performance and to correlate it with the presence of defective states in the material. We have observed a clear improvement in the material’s detection properties with time, though only in those detectors which have not been severely degraded by the irradiation. The recovery can be associated with a decrease in the concentration of some defective states, thus allowing the assessment of the crucial role these play in determining the charge collection processes in the material and its spectroscopic capabilities. Received: 1 August 2001 / Accepted: 3 August 2001 / Published online: 20 December 2001     

Laser printing of nanocomposite solid-state electrolyte membranes for Li micro-batteries

The electrochemical and mechanical properties of nanocomposite solid-state electrolyte membranes deposited using a laser direct-write technique from a suspended solution comprised of an ionic liquid (1,2-dimethyl-3-n-butylimidazolium-bis-trifluoromethanesulfonylimide)-polymer (poly(vinylidene fluoride-co-hexafluoropropylene)) matrix with dispersed nano-particles (TiO₂) are reported and discussed. These laser printed nanocomposite solid-state membranes are shown to exhibit the proper electrochemical behavior for ionic liquids while maintaining the strength and flexibility of the polymer matrix. This combination of physical properties and deposition technique makes these deposited nanocomposite membranes ideally suited for use as an electrolyte/separator in Li micro-batteries. Sample Li micro-batteries using these laser printed nanocomposite membranes have been fabricated and their charge/discharge behavior tested, demonstrating the feasibility of using these nanocomposite membranes in Li micro-battery applications.     

LD泵浦固体激光器基模振荡光的场分布噪音

通过调整泵浦光直径,使得LD端面泵浦固体激光器的振荡光工作于基模.在排除高阶横模的条件下,测量了由于热透镜的不稳定引起的光场场分布的噪音.实验发现,基模振荡光的高斯半径、光束指向角都在波动,而且光斑存在畸变波动.对一个未采取抑制措施的2W连续LD端面泵浦Nd:YAG固体激光器进行了测量.结果表明,在总功率不变的情况下,激光束峰值点附近的光强波动达到6.3%;激光的高斯半径波动达到5.8%;激光的指向角波动达到0.3mrad.     

Structural characterization and ferromagnetic behavior of Fe-doped TiO2 powder by high-energy ball milling

Fe-doped TiO₂ powder was prepared by high-energy ball milling, using TiO₂ Degussa P-25 and α-Fe powders as the starting materials. The structure and magnetic properties of the Fe-doped TiO₂ powder were studied by X-ray diffraction, ⁵⁷Fe Mossbauer spectroscopy and vibrating sample magnetometer. The Reitveld refinement of XRD revealed that ball milling not only triggered incorporation of Fe in TiO₂ lattice but also induced the phase transformation from anatase to rutile in TiO₂ and consequently the milled Fe-doped TiO₂ powder contained only rutile.⁵⁷Fe Mössbauer effect measure showed that Fe atoms existed in Fe²⁺ and Fe³⁺ state, which were assigned to the solid solution Fe_xTi_1−xO₂. The magnetization measurements indicated that the milled Fe-doped TiO₂ powder was ferromagnetic above room temperature. The ferromagnetism in our milled Fe-doped TiO₂ powder seemingly does not come from Fe and iron oxides particles/clusters but from the Fe-doped TiO₂ powder matrices.     

Influence of fluoride on f-f transitions of Eu in LiEuM2O8 (M=Mo, W)

The influence of fluoride on the luminescence of LiEuM₂O₈ (M=Mo, W) was studied. LiEuMo₂O₈ and LiEuW₂O₈ formed the whole range of solid solutions, which emitted intense red luminescence under the excitations by 395, 465 and 535 nm wavelengths. When doped with fluoride, the materials also formed solid solutions and the luminescent intensity was remarkably enhanced. The phosphor with optimized compositions in this system would be a promising red component for solid-state lighting devices based on GaN light-emitting diodes.     

The synthesis mechanism of Ca3Al2O6 from soft mechanochemically activated precursors studied by time-resolved neutron diffraction up to 1000°C

The reaction pathway for the Ca₃Al₂O₆ formation up to 1300°C, from mechanochemically treated mixtures of amorphous aluminum hydroxide and CaCO₃, was studied in situ by differential thermal analysis, constant heating rate dilatometry and time-resolved neutron powder diffraction. The experiment was carried out, in an open system, on a sample with the nominal Ca₃Al₂O₆ stoichiometry. The results obtained by neutron diffractometry and thermal analysis were in good agreement with the data obtained by scanning electron microscopy and X-ray diffraction on heat-treated and-quenched samples. The synthesis path implied the formation of cryptocrystalline Al₂O₃, crystalline CaO, CaAl₂O₄ and Ca₁₂Al₁₄O₃₃ as transitory phases. Finally the nucleation and growth of the single phase Ca₃Al₂O₆ took place at 1300°C and exhibited porous structure due to CO₂ and H₂O release.     

固体CD光谱研究及其应用于手性席夫碱M(II)配合物

结合课题组近期的相关研究,对固体CD光谱在手性配合物研究中的应用,特别是手性样品固体CD光谱的测试方法进行了概述,通过对四对手性席夫碱M(II)(M=Ni、Cu)配合物的固体和溶液CD光谱进行比较研究,发现配合物的手性构型在固液相中保持一致,但其固液CD光谱之间存在不同程度的差异,可能是由于相应配合物在固体和溶液相中的四面体扭曲或构象的微妙不同所致.