Preparation and Characterization of Mixed‐Valent Nickel Oxide/Nickel Hexacyanoferrate Hybrid Films and Their Electrocatalytic Properties

Polynuclear mixed‐valent nickel oxide and nickel hexacyanoferrate hybrid film was prepared on glassy carbon electrode by multiple scan cyclic voltammetry. The film growth was monitored using electrochemical quartz crystal microbalance (EQCM). The cyclic voltammogram of the nickel hexacyanoferrate film is characterized by single redox couple whereas nickel oxide/nickel hexacyanoferrate hybrid film exhibits two redox couples. Cyclic voltammetric features suggest that the charge transfer process in both films resembles that of surface‐confined redox species. In stronger basic solution (pH ≥9), nickel hexacyanoferrate film was gradually converted into nickel oxide film during potentiodynamic cycling. The peak potential of nickel oxide redox couple moved into more negative side with increasing pH of contacting solution whereas the peak potential of nickel hexacyanoferrate redox couple remains the same. Electrocatalytic behavior of hybrid film coated electrodes toward ascorbic acid, hydrazine and hydroxylamine was investigated using cyclic voltammetry technique. Analytical application of nickel oxide/nickel hexacyanoferrate hybrid film electrode was tested in amperometry and flow injection analysis.     

Electron Probe Microanalysis of HfO2 Thin Films on Conductive and Insulating Substrates

Quantitative electron probe microanalysis of highly insulating materials is a complicated problem, partially solved by coating samples with grounded thin conductive layers or using novel scanning electron microscopy (SEM) techniques, such as low-voltage and/or variable pressure SEM. In this work, some problems of quantitative X-ray microanalysis of thin HfO₂ films, in particular the possibility to determine mass thickness correlated to the density of the layer material, are discussed. For comparison, Al₂O₃, Ta₂O₅ and TiO₂ films grown onto both semiconductive Si and insulating quartz substrates were also analysed. All the films studied were synthesized by atomic layer deposition method.     

Effect of monomer concentration on characteristics of methacrylic acid-grafted polyethylene film prepared by photografting

The effect of monomer concentration on photografting of methacrylic acid (MAA) onto linear low-density polyethylene (PE) film (thickness=30 μm) was investigated at 60 °C in water solvent together with the location of MAA-grafted chains. Xanthone was used as a photoinitiator which was coated on the film sample earlier. The higher percentage of grafting and graft efficiency were afforded for the system with the higher monomer concentration. The resultant MAA-grafted films were subjected to measurements of pH-responsive character and ability to adsorb cupric ion in order to understand the characteristics of function introduced. The grafted samples exhibited the pH-responsive character, where they shrank and swelled in acidic and alkaline media, respectively. The pH-responsive character of the grafted films was higher for the samples prepared in the system with a higher monomer concentration. Moreover, the grafted samples exhibited the ability to adsorb cupric ion, and the ability was reduced when the sample was prepared in the system with a higher monomer concentration. The different extents of the pH-responsive character and ability to adsorb cupric ion of the resulting grafted PE films were discussed in terms of location of grafted chains in the film substrate, which was determined by a scanning electron microscope and an attenuated total reflection infrared spectroscopy.     

Heterometallic lead-titanium oxyalkoxide precursors to lead titanate thin films

Two lead titanium oxyalkoxides with composition Pb₂Ti₄O₂(O₂CCH₃)₂(OC₂H₅)₁₄ and Pb₂Ti₂O₂(O₂CCH₃)₂(OCH(CH₃)₂)₈ have been isolated and characterised by elemental analysis, IR, ²⁰⁷Pb NMR and molecular weight measurements. X-ray structural analysis of the 1:2 complex confirmed the presence of two Pb₂Ti₂O units which are linked by a common Pb···Pb edge and are held together by alkoxide and acetate bridges. The acetate groups have migrated from the Pb to the Ti centres during the reaction. Hydrolysis of the 1:1 Pb/Ti complex produced clear gels providing the H₂O/complex ratio was less than 4. Heat treatment of the gel results in loss of residual organics below 400°C. The XRD pattern indicates the presence of the pyrochlore and perovskite phases after heating at 500°C but the sample is poorly crystalline. Complete conversion to the perovskite phase of lead titanate occurs on heating to 600°C for 1 hour. Thin films of lead titanate were deposited by dip-coating a solution of this complex in isopropanol. Analyses of the films, carried out using electron microprobe, Scanning Auger Spectroscopy and Rutherford Backscattering, indicated that they were of excellent quality, crystalline after heating at 600°C and with relatively sharp substrate-coating interface.     

Photocatalytic activity and biodegradation of polyhydroxybutyrate films containing titanium dioxide

This study aims to evaluate the photocatalytic activity and biodegradation of polyhydroxybutyrate (PHB) films containing titanium dioxide (TiO₂). Nanosized TiO₂ photocatalysts were immobilized onto PHB film to overcome the difficulty of the recovery process. PHB is a suitable base material as it is naturally biodegradable and is produced from renewable resources. The photocatalytic degradation of organic compounds, photocatalytic sterilization activity and biodegradation rate in garden soil of PHB-TiO₂ composite films were investigated. After an hour under solar illumination, 96% of methylene blue solution was decolorized. The antibacterial activity against Escherichia coli (E. coli) using PHB-TiO₂ composite film exhibited enhanced photocatalytic sterilization activity over time. As for the ability to biodegrade, PHB-TiO₂ composite films placed on soil surface with no direct solar illumination showed slower degradation rate compared to those receiving direct solar illumination. Interestingly, the latter composite films showed faster degradation rates compared to pure PHB films indicating that the degradation is mainly due to photocatalytic activity. PHB-TiO₂ composite films buried in soil generally showed slower degradation rates compared to pure PHB films and were dependent on the soil microbial activity.     

Linked crystallites in the conducting topmost layer of polymer bilayer films controlled by temperature: from micro- to nanocrystallites.

Temperature has great impact on the structure and size of the linked crystallites of the conducting topmost layer formed at the surface of a polycarbonate film via the reaction BEDT-TTF+IBr [BEDT-TTF=bis(ethylenedithio)tetrathiafulvalene]. We show that fine temperature control permits formation of a semiconducting topmost layer of alpha'-(BEDT-TTF)(2)(I(x)Br(1-x))(3) crystallites with either micro- or nanometre size, a result that opens a route to miniaturized conducting plastic materials.     

Selective Formation of Spinel Iron Oxide in Thin Films by Complexing Agent-Assisted Sol-Gel Processing

The structure of iron oxide was controlled by regulating the hydrolytic polymerization of aquo iron complexes with organic polydentate ligands such as diols. Iron oxides were prepared by calcining the precursor polymers obtained from iron nitrate nonahydrate and diols. When the diols were 1,2-pentanediol, 1,2-hexanediol and 1,2-octanediol, α-Fe₂O₃ with corundum structure appeared exclusively or as the main crystalline phase, in spite of the amount of diol used and the calcination temperature. In the case of 1,2-decanediol and 1,2-dodecanediol, when five moles of the diols were used to one mole of iron nitrate and the calcination temperatures were below 400°C, ψ-Fe₂O₃ with spinel structure appeared as the main phase and, when less than five moles of the diols were used, α-Fe₂O₃ appeared exclusively or as the main phase, irrespective of the calcination temperature. This tendency was also observed in thin films. Thus, a transparent magnetic film composed of γ-Fe₂O₃ could be prepared by applying a benzene solution of the iron polymer, obtained with 5 equivalents of 1,2-decanediol, on quartz and calcining the gel film at 350°C.     

IONIC CONDUCTIVITY OF METHYLSILOXANE TERMINATED POLYETHYLENE OXIDE WITH LITHIUM PERCHLORATE NETWORK FILMS

Complex films of crosslinked poly(methylsiloxane-co-ethylene oxide) and lithium perchlorate were prepared. These solid state polymeric electrolytes show a markedly higher ionic conductivity, and excellent flexibility. The ionic conductivity of the network films closed to 10~(-5) Scm~(-1) at room temperature. The effects of Li~+ content, species and contents of crosslinking agents, molecular weight of poly(ethylene oxide) and temperature on the ionic conductivity of the network films were also investigated.     

铁氰化锰修饰玻碳电极的制备及其电化学性能

A thin film of manganese hexacyanoferrate （MnHCF） was electrochemically formed on a glassy carbon （GC） electrode to prepare a chemically modified electrode （CME）. The mechanism of film formation of MnHCF and its growth process were investigated in detail by cyclic voltammetry. The results show that the stoichiometric composition of MnHCF is Mn^ⅢFe^Ⅲ（CN）6, an analogue of prussian yellow. There exist three clear-cut stages in the whole modification process and the last stage is indispensable to the fabrication of homogenized, stable MnHCF film and must last for an appropriate time. The surface morphology of MnHCF/GC electrode was characterized by scanning electron microscopy （SEM）, which further verified the effective deposition of MnHCF film on GC. The kinetic constants of MnHCF/GC electrode process were also evaluated. The resulting MnHCF film modified electrode presented good stability and high electrocatalytic activity toward the oxidation of H2O2, indicating that MnHCF film possesses function of catalase and can be expected for analytical purposes.     

超高感彩卷乳剂微晶体电镜研究

应用物理和化学相结合的方法，将超高感彩卷分层剥离，离心沉降，水洗除胶，电镜观测各层乳剂的微晶体结构。揭示了超高感彩卷各乳剂层的结构情况，披露了超高感彩剂制造技术。