TiO<Subscript>2</Subscript>@MgO core-shell film: Fabrication and application to dye-sensitized solar cells

In this study,TiO2@MgO core-shell film was obtained by using a simple chemical bath deposition method to coat a thin MgO film around TiO2 nanoparticles. The core-shell configuration was characterized by X-ray diffractometer (XRD),scanning elec-tron microscopy (SEM),energy dispersive X-ray spectroscopy (EDX),and high-resolution transmission electron microscopy (HRTEM). Lattice fringes were observed for the TiO2 particles,and the MgO shell showed an amorphous structure,revealing a clear distinction between the core and shell materials. Applying the core-shell film as photoanode to the dye-sensitized solar cells (DSSCs),it shows a superior performance compared to the pure TiO2 electrode. Under the illumination of simulated sunlight (75 mW-cm-2),the short circuit photocurrent (Jsc),the open circuit photovoltage (Voc),and the fill factor (fF) are 8.80 mA-cm-2,646 mV,and 0.69,respectively,and the conversion efficiency (η) in-creased by 21.8% (from 4.32% to 5.26%) when dipping for opti-mum condition.     

An effective novel reaction system for the photo-degradation of aqueous organic pollutants

A novel reaction system consisted of a supported TiO₂ film electrode, a Ru−Ti oxide film electrode and air (oxygen) electrode is reported. The air (oxygen) electrode can provide H₂O₂ continuously for homogeneous photochemical oxidation reaction on the spot. In this reactor, degradation reaction of aniline occur from interface of TiO₂ film to all solution which is irradiated by ultraviolet ray. The degradation rate of aniline was characterized by measuring the change of chemical oxygen demand (COD) in solution under different conditions. It was found that the degradation rate of aniline in the novel system increased apparently as compared with single heterogeneous photocatalysis and homogeneous photochemistry system. It can be explained in terms of combining acts of heterogeneous photocatalysis and homogeneous photochemistry. Foundation item: Supported by the National Natural Science Foundation of China (10791033) Biography: CAI Nai-cai (1946-), male, Associate professor, Research direction: electrochemical catalysis and photocatalysis.     

I-V andC-V properties of TiO2 thin film by pulsed-laser reactive deposition

TiO-2 thin films have bee deposited on p-Si(111) substrates by pulsed-laser ablation of metallic Ti target in the O-3 ambient. The current-voltage and capacitance-voltage of the Al/TiO-2/Si capacitors are measured. The results show that the dielectric constant of thin film after being annealed at 700℃ is found to be 46, and the border trap density and the interface state density at the TiO-2/p-Si interface are 1.8×10 12 cm -2 and 2×10 12 eV -1·cm -2, respectively. The conduction mechanisms of as-deposited films are also discussed.     

Crystal structure and negative thermal expansion of solid solution Lu<Subscript>2</Subscript>W<Subscript>3−<Emphasis Type="Italic">x</Emphasis></Subscript>Mo<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>12</Subscript>

A new series of solid solutions Lu₂W_3−x Mo _x O₁₂ (0.5≤x≤2.5) were successfully synthesized by the solid-state method. Their crystal structure and negative thermal expansion properties were studied using high-temperature X-ray powder diffraction and the Rietveld method. All samples of rare-earth tungstates and molybdates are found to crystallize in the same orthorhombic structure with space group Pnca and show the negative thermal expansion phenomena related to transverse vibration of bridging oxygen atoms in the structure. Thermal expansion coefficients (TEC) of Lu₂W_3−x Mo _x O₁₂ are determined as −20.0×10⁻⁶ K⁻¹ for x=0.5 and −16.1×10⁻⁶ K⁻¹ for x=2.5 but -18.6×10⁻⁶ and −16.9×10⁻⁶ K⁻¹ for unsubstituted Lu₂W₃O₁₂ and Lu₂Mo₃O₁₂ in the identical temperature range of 200 to 800°C. High-temperature X-ray diffraction (XRD) data and bond length analysis suggest that the difference between W-O and Mo-O bond is responsible for the change of TECs after the element substitution in this series of solid solutions.     

Performances improvement of eosin Y sensitized solar cells by modifying TiO2 electrode with silane-coupling reagent

Chemical fixing of xanthene dye （eosin Y） on the surface of TiO2 electrode was carried out by modifying the electrode with silane-coupling reagent to obtain stable dye-sensitized TiO2 electrode. Such silane modification can not only evidently enhance the stability of dye-sensitized TiO2 electrode but also improve the energy conversion efficiency of the assembled cells by increasing short-circuit photocurrent （Jsc） and open-circuit photovoltage （Voc）. It was found that the improvements of cell performances differ depending on the composition of the electrolyte. The optimum cell of the cell performance was achieved in the electrolyte with 0.5 mol/L TBAI/0.05 mol/L 12/EC：PC（3：1 w/w）, yielding Jsc of 4.69 mA. cm-2, Voc of 0,595 V, fill factor （FF） of 0.64 and ηof 1,78%, Different spectroscopic techniques including UV-Vis spectra, fluorescence spectra, EIS and dark current measurements were employed to derive reasonable analysis and explanations.     

Magnetoelectric and converse magnetoelectric res ponses in TbxDy1-xFe2-y alloy ＆ Pb（Mg1/3Nb2/3）（1-x）TixO3 crystal laminated composites

Measured results of magnetoelectric （ME） and converse magnetoelectric （CME） effects of TbxDy1-xFe2-y/ Pb（Mg1/3Nb2/3）（1-x）TixO3/TbxDy1-xFe2-y （TD/PMNT/TD） and PMNT/TD/PMNT laminated composites are presented. ME effect was determined by measuring laminate voltage output under a Helmholtz-generated AC field biased by a DC field （0-1 kOe） （1Oe = 79.58 A/m）. The CME effect was measured by recording the voltage induced in a solenoid encompassing the ME sample while exposed to a DC bias field and PMNT layer driven by a 10 V AC source. The ME and CME responses in the two laminated structure are linear. The highest values of ME coefficients in TD/PMNT/TD and PMNT/TD/PMNT composites are 384 mV/Oe and 158 mV/Oe, respectively, while the highest values of CME coefficients in the two composites are 118 mG/V and 162 mG/V （1 G=10^-4 T）, respectively.     

Synthesis and electrochemical properties of LiNi0.8Al0.2−xTixO2 cathode materials by an ultrasonic-assisted co-precipitation method

A new co-precipitation route was proposed to synthesize LiNi_0.8Al_0.2−xTi_xO₂ (x=0.0-0.20) cathode materials for lithium ion batteries, with Ni(NO₃)₂, Al(NO₃)₃, LiOH·H₂O, and TiO₂ as the starting materials. Ultrasonic vibration was used during preparing the precursors, and the precursors were protected by absolute ethanol before calcination in the air. The influences of doped-Ti content, calcination temperature and time, additional Li content, and ultrasonic vibration on the structure and properties of LiNi_0.8Al_0.2−xTi_xO₂ were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and charge-discharge tests, respectively. The results show that the optimal molar fraction of Ti, calcination temperature and time, and additional molar fraction of Li for LiNi_0.8Al_0.2−xTi_xO₂ cathode materials are 0.1, 700°C, 20 h, and 0.05, respectively. Ti doping facilitates the formation of the α-NaFeO₂ layered structure, and ultrasonic vibration improves the electrochemical performance of LiNi_0.8Al_0.2−xTi_xO₂.     

Photo-induced degradation of Ru（Ⅱ） complex absorbed on anatase TiO2 thin film electrode

Photo-induced degradation of a monolayer of Ru（Ⅱ） complex absorbed on anatase TiO2 thin film was studied by using resonant micro-Raman spectroscopy. Under intense light radiation of a laser and in the absence of a reducing agent, the dye decomposed quickly. When the dye-sensitized TiO2 thin film electrode was covered by a reducing agent, namely the I^-/I3^- redox couple, the photo-induced decomposing rate was slowed by a factor of -10^6. In both cases, the dye decomposed with time under an exponential law.     

TFEL of Ce3+ in zine sulpho-oxide

A new TFEL material ZnS_xO_1−x: Ce³⁺ is prepared. The EL brightness of ZnS_xO_1−x: Ce³⁺ is at least one order higher than that of ZnS: Ce³⁺ at the same doping concentration of Ce³⁺. The EL emission wavelength of ZnS_xO_1−x: Ce³⁺ (X = 0.5) ranges from 400 to 600 nm. The emission of ZnS_xO_1−x: Ce³⁺ may be used as the blue part of white TFEL.     

Surface chemical structure of titania-silica nanocomposite powder

Titania-silica （TS） nanocomposite powder with three different composite structures, containing 10-30 mol% SiO2 in each structure, have been prepared by sol-gel processes. The surface characteristics of these titania-silica samples have been investigated by X-ray photo-emission spectroscopy （XPS） and high resolution transmission electron microscopy （HRTEM）. The study for all TS oxides annealed at 773 and 1173 K showed： an abnormal surface enrichment in Si increased with increasing annealing temperature; the Ti^3＋, Ti^2＋, Si^3＋ and Si^2＋ oxides coexisted with Ti^4＋ and Si^4＋ oxides, and the contents of these Ti/Si suboxides increased with increasing SiO2 content and annealing temperature; there was a layer rich in O on the topmost surface and the excess O could be attributed to the chem-adsorption of H2O; different composite structures could lead to different contents of Ti/Si suboxides. These results indicated that the surface of TS oxide powder derived by sol-gel process was a double layer with enriched O first and then SiOx/TiOy（x, y〈2）. Ti/Si suboxides could result from the thermal diffusion of Ti^4＋ and Si^4＋, which might be induced by the strong interaction between Ti^4＋ and Si^4＋.     

Magnetic properties and giant magnetoresistance effect of nanometer Fe−In2O3 granular films

Nanometer ferromagnetic metal-semiconductor matrix Fe−In₂O₃ granular films are fabricated by the radio frequency sputtering. Magnetic properties and the giant magnetoresistance (GMR) effect of Fe_x(In₂O₃)_1−x granular film samples are studied. The result shows that the magnetoresistance (MR) ratio Δρ/ρ ₀ value of the granular film samples with Fe volume fraction x=35% is 4.5% at room temperature. The temperature dependence (T=1.5–300 K) of the MR ratio Δρ/ρ ₀ value of Fe_0.35(In₂O₃)_0.65 granular films shows that Δρ/ρ ₀ value below 10 K increases rapidly with the decrease of the temperature, and when T=2 K, Δρ/ρ ₀ value is 85%. Through the study of the dependence of low field susceptibility on temperature and the hysteresis loops at different temperatures, it has been found that, when the temperature decreases to a critical point T _p=10 K, the change of the structure in Fe_0.35)In₂O₃)_0.65 granular films results in the transformation of state from ferromagnetic to spin-glass-like. The remarkable increase of the MR ratio Δρ/ρ ₀ value of Fe_0.35(In₂O₃)_0.65 granular films below 10 K seems to arise from the peculiar conducting mechanism of the granular film samples in the spin-glass-like state.     

Effect of Ag addition on the thermal stability and glass-forming ability of Zr<Subscript>35</Subscript>Ti<Subscript>30</Subscript>Cu<Subscript>7.5</Subscript>Be<Subscript>27.5</Subscript> bulk metallic glass

The thermal stability and glass forming ability (GFA) of Zr35-xTi30Cu7.5Be27.5Agx (x = 0-10) alloys were studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and ultrasonic techniques. We found that the addition of 1 at.% Ag can considerably enhance the GFA as indicated by an increase in the critical glass dimension from 15 mm in the Zr35Ti30Cu7.5Be27.5 alloy to 20 mm in the Zr34Ti30Cu7.5Be27.5Ag1 alloy. However, with the addition of more Ag the supercooled liquid region (△Tx) and y parameter (defined as Tx/(Tg+Tl)) drastically decreased from 155 K and 0.436 to 76 K and 0.363, respectively, resulting in a decrease in the GFA. Additionally, the elastic constant (the ratio of shear modulus to bulk modulus or Poisson’s ratio) was also used as a gauge to evaluate the GFA in Zr35-xTi30Cu7.5Be27.5Agx alloys.     

Preparation of porous nanoparticle TiO2 films for flexible dye-sensitized solar cells

A TiO2 paste was prepared by mixing commercial TiO2 (P25), ethanol, distilled water and a small amount of Ti (IV) tetrai-sopropoxide (TTIP), following by a hydrothermal treatment. Before hydrothermal treatment, a stirring for 48 h can prevent cracking TiO2 films. TTIP significantly promote the chemical connection between TiO2 particles and its adherence to the substrate, the TTIP amount of 6 mol% is suitable. UV irradiation can remove some impurities and water from the TiO2 film with an optimal time of 2 h. Transmission electron microscopy, X-ray diffraction, scanning electron microscopy and photovoltaic tests are charac- terized and measured. Shortcircuit current density, open-circuit voltage, fill factor and photoelectric conversion efficiencies for the fabricated flexible dye-sensitized solar cell are 7.20 mA cm-2, 0.769 V, 0.686 and 3.84%, respectively, under irradiation with a simulated solar light of 100 mW cm-2.     

Dielectric properties of low dielectric constant Ba0.60Sr0.40Mg0.15Ti0.85O3-Mg2TiO4 composite thin films for tunable applications

Ba0.60Sr0.40Mg0.15Ti0.85O3-xmol%Mg2TiO4 （x = 0-40 mol%） （BSTM-MT） composite thin films were fabricated by sol-gel method. The precursor solution of these composite thin films was prepared through mixing the Ba0.80Sr0.40Mg0.15Ti0.85O3 and Mg2TiO4 solution. The microstructures and dielectric tunability of composite thin films were investigated. The dielectric constant of composite thin films can be tailored from 155 to 55 by changing the concentration of Mg2TiO4. The dielectric loss of these composite thin films were still kept below 0.01 and the tunability was above 20% at a dc-applied electric field of 500 kV/cm. Suitable dielectric constant, low dielectric loss, and high tunability of this kind of composite thin films can be useful for potential microwave tunable applications.     

Preparation and performance of dye-sensitized solar cells based on ZnO-modified TiO<Subscript>2</Subscript> electrodes

The ZnO-modified TiO₂ electrode was prepared by adding Zn(CH₃COO)₂·2H₂O to the TiO₂ colloid during the sol-gel production process, and was used in dye-sensitized solar cells (DSCs). The open circuit voltage (V _OC) and fill factor (ff) of the cells were improved significantly. The performances of the ZnO-modified TiO₂ electrode such as dark current, transient photocurrent, impedance, absorption spectra, and flat band potential (V _fb) were investigated. It is found that the interface charge recombination impedance increases and V _fb shifts about 200 mV toward the cathodic potential. The effect mechanism of ZnO modification on the performance of DSCs may be that ZnO occupies the surface states of the TiO₂ film.     

Lithium intercalation mechanism for β-SnSb in Sn-Sb thin films

Based on the first-principles plane wave pseudo-potential method, the electronic structure and electrochemical performance of Li_xSn₄Sb₄ (x=2, 4, 6, and 8) and Li_xSn_1-xSb₄ (x=9, 10, 11, and 12) phases were calculated. A Sn-Sb thin film on a Cu foil was also prepared by radio frequency magnetron sputtering. The surface morphology, composition, and lithium intercalation/extraction behavior of the fabricated film were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and cyclic voltammetry (CV). Lithium atoms can easily insert into and extract out of the β-SnSb cell due to the low lithium intercalation formation energy. It is found that lithium atoms first occupy the interstitial sites, and then Sn atoms at the lattice positions are replaced by excessive lithium. The dissociative Sn atoms continue to produce different Li-Sn phases, which will affect the electrode stability and lead to the undesirable effect due to their large volume expansion ratio. The calculated lithium intercalation potential is stable at about 0.7 V, which is consistent with the experimental result.     

Direct electrochemistry and electrocatalysis of horseradish peroxidase in MnO2 nanosheet film

A novel material MnO2 nanosheet has been used as the support matrix for the immobilization of horseradish peroxidase （HRP）. HRP entrapped in MnO2 nanosheet film exhibits facile direct electron transfer with the electron transfer rate constant of 6.86 s^-1. The HRP/MnO2 nanosheet film gives a reversible redox couple with the apparent formal peak potential （E^0＇） of -0.315 V （vs. Ag/AgCl） in pH 6.5 phosphate buffer solution （PBS）. The formal potential E^0＇ of HRP shifts linearly with pH with a slope of -53.75 mV.pH^-1, denoting that an electron transfer accompanies single-proton transportation. The immobilized HRP shows an electrocatslytic activity to the reduction of H2O2. The response time of the biosensor for H2O2 is less than 3 s, and the detection limit is 0.21 μmol · L^-1 based on signal/noise = 3.     

Co-substituted ATS-type molecular sieves and films for cyclohexane oxidation

Pure CoAPO-36 crystal grains were synthesized by hydrothermal reaction. Porous α-Al₂O₃, stainless steel and K₂Ti₆O₁₃ supported CoAPO-36 films were fabricated using in situ crystallization for the first time. SEM images and XRD measurements demonstrate that a continuous CoAPO-36 film was obtained on the K₂Ti₆O₁₃ substrate. Diffuse reflectance UV-Vis spectra indicate that Co²⁺ has been incorporated into the ATS framework. Both CoAPO-36 crystal grains and the K₂Ti₆O₁₃ supported CoAPO-36 film exhibit satisfactory catalytic activities for the oxidation of cyclohexane.     

High conversion efficiency of pristine TiO<Subscript>2</Subscript> nanotube arrays based dye-sensitized solar cells

We prepared highly-ordered titanium dioxide nanotube arrays (TNAs) by anodizing Ti foils in F-containing electrolytes.The crystalline nature and morphology of the TNAs were studied using X-ray diffraction patterns and scanning electron microscopy.We found the morphology of TNAs affects the light-to-electricity conversion efficiency (η) of dye-sensitized solar cells (DSSCs).The efficiency of DSSCs reached 5.95% under the condition of light illuminated from the counter electrode.The high efficiency of TNA-based DSSCs was attributed to the neat top surface of TNAs,which allows more dye molecule loading on the surface of the TiO 2 nanotubes,and fewer electron recombination centers and a low interface resistance of integrated TNAs.     

Investigation of the electronic structure and photoluminescence properties of Eu3＋ in Sr2Mgl_xZnxSi207 （0 〈x 〈 1）

Undoped and Eu 3+-doped Sr 2 Mg 1-x Zn x Si 2 O 7 (0≤x≤1) powder crystals were obtained by conventional solid-state reaction.X-ray diffraction,inductively coupled plasma analysis,and Fourier transform infrared spectroscopy results implied that a complete solid-solution formed between Sr 2 MgSi 2 O 7 and Sr 2 ZnSi 2 O 7 as well as local structural adjustment.Excitation spectra exhibited O 2-Eu 3+ charge transfer (CT) bands centered at 250 nm for Sr 2 MgSi 2 O 7:Eu 3+ and 258 nm for Sr 2 ZnSi 2 O 7:Eu 3+.Emission spectra exhibited a major band around 616 nm,which showed the environment around Eu 3+ was non-centrosymmetric in both Sr 2 MgSi 2 O 7:Eu 3+ and Sr 2 ZnSi 2 O 7:Eu 3+.In addition,first principles calculations within the local density approximation (LDA) of density functional theory (DFT) were used to calculate the electronic structure of Sr 2 MgSi 2 O 7 and Sr 2 ZnSi 2 O 7.Calculated results were correlated with experimental UV-vis reflection spectra and the observed shift of the O 2-Eu 3+ CT band.