酞菁铜衍生物LB膜／N－Si光伏电池的反常二极管整流效应

从表面态和材料电阻率的角度分析了酞菁铜衍生物ＬＢ膜光伏电池的反常整流效应，讨论了该效应与光生电流的关系，并介绍了消除反常现象提高光生电流的实验方法。     

无机杂化倍半硅氧烷／磺化杂萘联苯聚醚酮质子导电复合膜

通过磺化反应制备了一系列不同磺化程度的磺化杂萘联苯聚醚酮（SPPEK）,采用共混法将无机杂化倍半硅氧烷（POSS）掺杂到IEC值为1．60的SPPEK中,通过溶液浇铸制得复合膜。对SPPEK／POSS复合膜进行了FTIR、TGA分析和SEM表观形貌观察。研究了SPPEK／POSS复合膜的吸水性、溶胀度和质子导电性,并与Nation 117进行对比。随着POSS的加入,复合膜的吸水性、溶胀度和氧化稳定性提高。SPPEK／POSS复合膜的室温电导率达到0．75×10^-2S·cm^-1,接近Nafion 117膜相同条件下的电导率（1．08×10^-2S·cm^-1）。随着温度升高,SPPEK／POSS复合膜的电导率逐渐增大。采用不同测试方法分别对复合膜的膜平面方向和厚度方向上的电导率进行了测试,表明在两个方向上的电导率相差较大,SPPEK／POSS复合膜室温下膜平面方向上的电导率达到2．1×10^-2S·cm^-1。     

Robust proton exchange membrane for vanadium redox flow batteries reinforced by silica-encapsulated nanocellulose

High ion selectivity and mechanical strength are critical properties for proton exchange membranes in vanadium redox flow batteries. In this work, a novel sulfonated poly(ether sulfone) hybrid membrane reinforced by core-shell structured nanocellulose (CNC-SPES) is prepared to obtain a robust and high-performance proton exchange membrane for vanadium redox flow batteries. Membrane morphology, proton conductivity, vanadium permeability and tensile strength are investigated. Single cell tests at a range of 40–140 mA cm⁻² are carried out. The performance of the sulfonated poly(ether sulfone) membrane reinforced by pristine nanocellulose (NC-SPES) and Nafion® 212 membranes are also studied for comparison. The results show that, with the incorporation of silica-encapsulated nanocellulose, the membrane exhibits outstanding mechanical strength of 54.5 MPa and high energy efficiency above 82% at 100 mA cm⁻², which is stable during 200 charge-discharge cycles.     

十六氯酞菁锌有机半导体材料的合成及其气敏性研究

Due to the difficulty in synthesizing perhalogenated metallophthalocyanine, the method of ammonium molybdate solid phase catalysis was introduced, and by using tetrachlorophthalic anhydride and urea as the raw materials, hexadecachloro zinc phthalocyanine （ZnPcCl16） was synthesized. Components of the composite were analyzed by energy spectrum, and its functional group structures and absorption peaks were characterized by IR and UV-vis spectroscopy. The thin films of gas sensors were prepared in a vacuum evaporation system and evaporated onto SiO2 substrates, where sensing electrodes were made by MEMS micromachining. The optimal conditions for the films are： substrate temperature of 150 ℃ evaporation current of 95 A and film thickness of 50 nm. The result showed that the sensors were ideally sensitive to Cl2 gas and could detect the minimum concentration of 0.3 ppm.     

Environmentally friendly phthalocyanine catalysts for water decontamination—Non-photocatalytic systems

Macrocyclic porphyrin-like compounds known as phthalocyanines (Pcs) have been shown to produce singlet oxygen species upon illumination with light of an appropriate wavelength. Singlet oxygen is an effective agent for complete oxidation of common water-soluble pollutants including chlorinated phenols. The most active are, in this respect, phthalocyanines bearing Al, Zn and Si central atoms. Although these compounds were proofed to be virtually non-toxic, the presence of the Al³⁺ and Zn²⁺ ions may contradict this. On the other hand e.g. iron phthalocyanine (FePc) does not represent any danger from this point of view. However, due to the specific coordination of its central metal ion and also because of the number of electrons occupying its valence orbitals, the FePc cannot be effectively activated by the photon flux. Here we report on an alternative system in the dark. It is based on the initial catalytic decomposition of various peroxo substances by metal Pc, producing oxidising species which can decompose chlorinated phenols. A series of Pcs and peroxo substances were compared and the reaction system optimised. It was shown that the highest activity was revealed for the system comprising of FePc and tert-butylhydroperoxide. Iron phthalocyanine was also successfully immobilised on an Al₂O₃ solid matrix, and this heterogeneous system was tested analogously to the homogeneous one. Virtually zero leaching of the anchored complex was detected and the activity was found to be comfortably high.     

Spectroscopic and photoelectric investigations of resonance effects in selected sulfonated phthalocyanines

Zinc phthalocyanine dyes, which had been symmetrically and asymmetrically substituted with sulfonate groups were investigated using absorption, fluorescence and photoacoustic spectroscopic methods, supported by light-induced optoacoustic spectroscopy and photoelectric measurements; unsubstituted zinc phthalocyanine was employed as reference. Fluorescence quantum yields were determined on the basis of absorption and fluorescence spectra, whereas thermal parameters as well as the yield of triplet state population and the kinetics of thermal relaxation at microsecond intervals were determined using with photoacoustic methods. The effect of the sulfonate groups on photocurrent generation was discussed in terms of the dye's molecular structure and resonance (mesomeric, inductive, steric) effects. Sulfonation of zinc phthalocyanine changed markedly its absorption and fluorescence properties owing to redistribution of the electron density within the molecule as a result of both mesomeric and inductive effects, although other effects cannot be excluded. The enhanced light-generated photocurrent observed for phthalocyanine with two sulfonate groups is explained in terms of mesomeric effects, whereas in phthalocyanine with three and four sulfonate groups, inductive effects are essential and lead to photocurrent decline.     

Molecular structure and transport dynamics in Nafion and sulfonated poly(ether ether ketone ketone) membranes

An atomistic simulation technique is performed to investigate the molecular structure and transport dynamics inside a hydrated Nafion membrane and a hydrated sulfonated poly(ether ether ketone ketone) (SPEEKK) membrane. The simulation system consists of the representative fragments of the polymer electrolytes, hydronium ions and solvent molecules, such as water plus methanol molecules. Simulation results show that the hydrated SPEEKK has less phase separation among hydrophobic and hydrophilic regions in comparison with the Nafion. Those water channels formed in the SPEEKK are much narrower compared to those in the Nafion. These characteristics lead to a lower mobility of hydronium ions and water molecules and hence relatively lower diffusion coefficient of methanol in the SPEEKK. It results in the reduction of the methanol permeation problem in direct methanol fuel cells.     

Synthesis of Cyclic Carbonates from Olefins and CO2 over Zeolite-Based Catalysts

Metal phthalocyanine complexes (MPc; M = Cu²⁺, Co²⁺, Ni²⁺ and Al³⁺) encapsulated in zeolite-Y exhibit high catalytic activity for the cycloaddition of CO₂ to epichlorohydrin and propylene oxide yielding the corresponding cyclic carbonates. The catalysts could be separated easily from the reaction mixture and reused with little loss in activity. These environmentally benign catalysts are also more efficient than either the neat complexes or those obtained by supporting them on solids like silica.     

Influence of heat treatment on indium-tin-oxide anodes and copper phthalocyanine hole injection layers in organic light-emitting diodes

Modifications of indium-tin-oxide (ITO) and copper phthalocyanine (CuPc) layers by heat treatment aimed at lowering driving voltage in organic light-emitting diodes (OLEDs) are examined. Significant changes were observed in the surface morphology and carrier injection properties of ITO and CuPc layers after annealing at T = 250 °C for 0-60 min in a glove box. In the case of ITO annealing, although the ITO work function gradually decreased and the surface of the ITO layer became smoother than that of an unannealed ITO layer, we observed an appreciable decrease in the driving voltage with an increase in annealing time. In the case of CuPc annealing, on the other hand, we observed deterioration of the OLED's characteristics. All devices demonstrated an increase in driving voltage due to the pronounced crystallization of the CuPc layer.