金属酞菁可见光催化降解水中污染物研究进展

对金属酞菁可见光催化降解水中污染物研究现状进行了综述,从金属酞菁本身的性质、活性氧性质、金属酞菁在水中的分散性、金属酞菁的负载方式及载体性质等方面分析了影响金属酞菁可见光催化效率的关键因素,并在此基础上提出了增强金属酞菁可见光催化效率的途径。     

金属酞菁及其取代衍生物的结构与光电性能研究进展

由于取代方式的不同,使得金属酞菁衍生物数目庞大,结构各异。晶体结构的不同,造成配合物光电性能等多种性质的改变。酞菁类光敏材料研究方法有溶剂调节法,相转移法、溶胶-凝胶法、气相沉积法和真空热蒸发等,这些技术调变了酞菁衍生物的光电导性能,在光动力疗法等领域意义重大。酞菁类气敏材料对某些气体具有选择性高、响应灵敏等特点,可用于气体传感器的制作。建议进一步探讨取代金属酞菁衍生物的光敏、气敏机理,以便在分子层次上优化设计分子的结构,改善材料性能,拓宽应用范围。     

Self-Assembly and Molecular Electrical Switching Property of Phthalocyanine-Based Liquid-Crystalline Poly(Styrene Sulfonic Acid) Compounds

A series of phthalocyanine-based liquid-crystalline poly(styrene sulfonic acid) compounds (LCPCs) are synthesized using cholesterol, dicarboxylic acid, amino- zinc phthalocyanine, and polystyrene sulfonic acid. The chemical structure, thermal property, liquid-crystalline behavior, direct current conductivity, and temperature-controlled molecular electronic switch property are investigated by use of various techniques. The LCPCs show both columnar phase (Col_h) induced by the phthalocyanine moieties and nematic discotic (N_d) phase formed by the collapse of the columnar phase structure. The temperature-dependent conductivity of the LCPCs is associated with the activation energy evaluated by Broido's graphical procedure according to the thermogravimetric analytical curves. The LCPCs show low conductivity derived from 1D charge migration through phthalocyanine cores in the col_h phase, but exhibit high conductivity due to 3D ionic charge transport in the N_d phase. A temperature-controlled molecular electronic switch is fabricated on the basis of the temperature-dependent conductivity property, which can be useful for some potential applications.     

Synthesis and characterization of melt-polymerizable aminophthalocyanine monomers

The strategy, synthesis, and characterization of a soluble amine-functionalized phthalocyanine monomer and two examples of its polymerization into optically transparent glasses are reported. A simple, fast, and versatile method for incorporating metal ions into the metal-free phthalocyanine is demonstrated. Measurements of the nonlinear optical properties associated with a lead-substituted phthalocyanine/urethane copolymer are also reported. © 1995 John Wiley & Sons, Inc.

1 This article is a US Government work and, as such, is in the public domain in the United States of America.

     

酞菁衍生物的组装改性技术及应用研究进展

酞菁及金属酞菁的改性组装可以调变其结构和特性,进而开发出多种先进的功能材料。酞菁改性的理化方法包括聚合、取代、负载等手段,技术工艺包括气相沉积法、真空镀膜法、旋涂法、电化学聚合法、相转移法、溶胶-凝胶法、LB膜技术等。除用于染料和颜料外,酞菁衍生物的应用领域主要有新型功能材料(光敏材料、气敏材料等),新型仿酶催化剂(新型脱硫催化剂、有机反应的催化剂、新型水质处理剂等)。     

酞菁系类产品生产废水处理工艺设计及运行

酞菁系类颜料生产废水氨氮高、Cu2+含量高、盐分高,并含有大量SO42-及苯胺类等难处理物质,处理难度大。设计采用"分流预处理+混合生化"工艺对河北某酞菁系类颜料生产厂废水进行处理,处理后废水达到国家《污水综合排放标准》(GB 8978—1996)一级排放标准。     

负载化/固载化酞菁金属催化剂研究进展

作为新材料及催化剂,酞菁金属化合物得到了广泛深入研究。综述了酞菁金属催化剂负载化/固载化的研究进展。以共价键或配位键将酞菁金属与高分子载体连接,使得酞菁金属催化剂固载化,从而减少催化剂活性组分的流失,提高催化剂性能,是目前该领域的重要研究方向。而在酞菁金属原子上引入种类不同、数目不同的轴向配体,则能够大大改善酞菁金属化合物的催化及光学性能,为酞菁金属材料新的应用奠定了基础。     

Synthesis of soluble metal phthalocyanine derivatives and their electron transfer properties

Metal phthalocyanine derivatives exhibit high electron transfer abilities, although they are insoluble in most common organic solvents, which has inhibited them from being employed in functional colorants that can take advantage of their useful electron transfer properties, Soluble metal phthalocyanine derivatives, metal octakis(hexoxymethyl)phthalocyanines, and a new type of phthalocyanine derivative, metal anthraquinocyanines, have been synthesised in this study. The electron transfer behaviour of the phthalocyanines and anthraquinocyanines, were examined with cyclic voltammetry. This showed one irreversible oxidation and one pair of reduction potentials. Cyclic voltammograms of metal anthraquinocyanines exhibited the irreversible redox behaviour. The electron transfer properties of metal phthalocyanine derivatives were influenced by the ring current of π electrons about the conjugated system. Ring currents of metal phthalocyanine derivatives consisted of five loops, whereas those for metal anthraquinocyanines were made up of a simple loop.     

The growth and morphology of copper phthalocyanine on TiO2 nanotube arrays

Nanostructured copper phthalocyanine was deposited by thermal vacuum evaporation, spin-coating, immersion, and electrochemical reactions onto titania nanotubes prepared by the anodization of titanium foil so as to attain interdigited heterojunctions between them for improved interfacial contact. The effects of the titania's crystal structure on the deposition were analyzed. A sodium salt derivative of copper phthalocyanine was used to enhance its affinity to the titania. The deposited copper phthalocyanine could be grown and transformed into diverse morphologies such as polyhedrons, nanorods, and nanowires. The factors affecting the morphology of the deposited copper phthalocyanine were analyzed by SEM and crystal structure analysis.     

Surface chemistry and electrocatalytic behaviour of tetra-carboxy substituted iron, cobalt and manganese phthalocyanine monolayers on gold electrode

Surface chemistry and electrocatalytic properties of self-assembled monolayers of metal tetra-carboxylic acid phthalocyanine complexes with cobalt (Co), iron (Fe) and manganese (Mn) as central metal ions have been studied. These phthalocyanine molecules are immobilized on gold electrode via the coupling reaction between the ring substituents and pre-formed mercaptoethanol self-assembled monolayer (Au-ME SAM). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy confirmed chemisorption of mercaptoethanol via sulfur group on gold electrode and also coupling reaction between phthalocyanines and Au-ME SAM. Electrochemical parameters of the immobilized molecules show that these molecules are densely packed with a perpendicular orientation. The potential applications of the gold modified electrodes were investigated towards l-cysteine detection and the analysis at phthalocyanine SAMs. Cobalt and iron tetra-carboxylic acid phthalocyanine monolayers showed good oxidation peak for l-cysteine at potentials where metal oxidation (M^III/M^II) takes place and this metal oxidation mediates the catalytic oxidation of l-cysteine. Manganese tetra-carboxylic acid phthalocyanine monolayer also exhibited a good catalytic oxidation peak towards l-cysteine at potentials where Mn^IV/Mn^III redox peak occurs and this redox peak mediates l-cysteine oxidation. The analysis of cysteine at phthalocyanine monolayers displayed good analytical parameters with good detection limits of the orders of 10⁻⁷ mol L⁻¹ and good linearity for a studied concentration range up to 60 μmol L⁻¹.     

Synthesis and photoconductivity study of phthalocyanine polymers. VI. Ethylenediamine bridged polymeric MnPc

A novel polymer with quasi-one-dimensional structure of ethylenediamine bridged polymeric manganese phthalocyanine [PcMn(eda)]_n was synthesized by complexing of manganese phthalocyanine (MnPc) and ethylenediamine (eda). The structure of the polymer was identified by infrared, ultraviolet–visible, and differential scanning calorimetric analysis. It was found that the polymer [PcMn(eda)]_n showed much better photoconductive property than MnPc monomer when [PcMn(eda)]_n or MnPc was used as the charge-generation material (CGM)-matched hydrazone charge-transportation material (CTM). Furthermore, the photoconductivities of [PcMn(eda)]_n and MnPc were improved if the charge-generation layers (CGLs) were made by electric field poling. All these observations are ascribed to the effects of the one-dimensional molecular structure and the ordered material structure, respectively. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 69: 2609–2613, 1998     

MCM-41分子筛负载金属酞菁在氧化脱硫反应中的催化性能

采用浸渍法将8种金属酞菁分别负载到MCM-41分子筛上制得负载型金属酞菁,通过红外光谱进行表征。以二苯并噻吩（DBT）为反应底物,空气为氧化剂,己内酰胺四丁基溴化铵离子液体为溶剂考察了这8种催化剂在氧化脱硫反应中的催化活性,筛选出较优催化剂,并对工艺条件进行优化。结果表明,合成的8种负载型金属酞菁催化剂中,MCM-41分子筛负载钴酞菁具有较好的催化性能,最优工艺条件为：剂油比1：1,催化剂用量0.004 g·（10 ml模型油）^-1,空气流速50 ml·min^-1,反应时间1 h,室温,DBT脱硫率最高可达97.56%。DBT的氧化产物为DBT砜。又考察了此催化氧化系统对不同硫化物的催化氧化效果,发现不同硫化物的脱硫率均在90%以上。该催化剂在重复利用4次后脱硫率无明显的降低。     

Synthesis and Electric Modulus Formalism of Novel Metal-Phthalocyanine Bridged Polymers

Novel nickel and copper phthalocyanine polymers, with uniformly carboxylic end groups and carbonyl groups as bridges linking the phthalocyanine units, were successfully prepared. Structural modelling and atomic absorption spectroscopy confirmed the network polymeric structure and suggested at least nine phthalocyanine units in each polymeric network. The dielectric properties of the prepared polymers were investigated over a wide range of frequencies at room temperature. The electric modulus formalism was used to study the conductivity relaxation in the prepared polymers. The collapsing of the real part of the conductivity function, σ’, at higher frequencies for both materials was observed indicating that the local molecular dynamics is due to the polymer conjugated backbone (functional and/or terminal groups) with no clear effect of the central metal.     

Hydrophilic property of titanium oxide aiming for bio-applications

Surface functionalization of titanium metal is very attractive for bio- and environmental applications. This is because titanium metal is very stable and has a good biocompatibility. In this case, surface roughness and crystalline structure are important factors for obtaining effective characteristics. Titanium metal is usually covered with a surface passive film of thermodynamically stable rutile-TiO₂ that grows as the heat treatment temperature in air increases. On the other hand, to obtain an anatase-TiO₂ surface layer on titanium metal, we must employ specific treatments such as our previous method, which uses a silica-coexisting heat-treatment process. In this paper, the relationship between the fine structure formed on the titanium metal and the surface hydrophilic property was clarified, and the potential for the bio-application was discussed. The formed anatase-TiO₂ coexisting with silica exhibited improved biocompatibility with good apatite formation.     

Synthesis,characterisation and electrochemical investigation of phthalocyanines with pendant 4‐{2‐[2‐(4‐tert‐butylphenoxy)ethoxy]ethoxy} substituents

In this study, a novel metal‐free phthalocyanine and three metallophthalocyanines carrying four 2‐[2‐(4‐tert‐butylphenoxy)ethoxy groups on the periphery were prepared by cyclotetramerisation of a dinitrile derivative in the presence of the corresponding divalent metal salts [zinc(ii ), cobalt(ii ), copper(ii )]. These new phthalocyanine compounds have been characterised by infrared, ¹H and ¹³C nuclear magnetic resonance and electrospray mass spectroscopies and elemental analysis. The electrochemical properties of the metal‐free, zinc(ii ) and cobalt(ii ) phthalocyanines were investigated by cyclic voltammetry and differential pulse voltammetry methods. The cobalt complex showed a metal‐based reduction process, while the metal‐free and zinc(ii ) phthalocyanines showed ligand‐based electron transfer processes. It has been found that the absorption spectra substantially depend on concentration. It has been shown that these changes are attributable to the association of the phthalocyanine molecule. The number of molecules in the associates and the equilibrium constants for this association are determined.     

Development of redox resin using metal phthalocyanine derivatives

Utilisation of the reduction and oxidation properties of metal phthalocyanine derivatives was carried out for the development of new types of redox resin. The redox resins were prepared by fixing the synthesised metal phthalocyanine tetrasulfonic acids onto ion exchange resins. The adsorption properties of metal phthalocyanine tetrasulfonic acid onto an anion exchange resin was found to be the Freundlich type with the characteristics of both chemisorption and physisorption. The capabilities of the redox resins were estimated with the decomposition of hydrogen peroxide which was shown to increase with increasing reaction time. The capability was found to be dependent on the central metal in the metal phthalocyanine tetrasulfonic acid.     

金属络合染料光稳定性研究进展

综述了不同金属离子对偶氮型、甲臜型和酞菁型3种染料光稳定性的影响。在染料结构中引入Co(Ⅲ)、Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)等金属离子后,由于这些金属离子的最低激发态能量低于染料三重态能量,在染料结构中起到了能量吸收剂的作用,有效猝灭了染料三重态,从而使染料的光稳定性得到明显提高。     

Synthesis and characterization of new monomeric and polymeric phthalocyanines

Monomeric (M = 2Li or 2H) and polymeric (M = 2H, Zn, Cu, Co, or Ni), where M is metal or hydrogen, phthalocyanines were prepared by the tetramerization reaction of bisphthalonitrile monomer with appropriate materials. The electrical conductivities of the polymeric phthalocyanines, which were measured as gold sandwiches, were found to be 10⁻¹⁰–10⁻⁷ S/cm in vacuo and in air. The binding property of a Co‐containing polymeric phthalocyanine ( 10 ) toward alkali, alkaline‐earth, and some heavy cations was studied in tetrahydrofuran. The extraction affinity of 10 for K⁺ was found to be the highest in the heterogeneous phase extraction experiments. The disaggregation property of a Ni‐containing polymeric phthalocyanine ( 11 ) was investigated with K⁺, Na⁺, and NH₄⁺ cations. The intrinsic viscosities of all polymers were also measured by means of viscometry. All the novel compounds were characterized with elemental analysis, ultraviolet–visible, Fourier transform infrared, NMR, and mass spectrometry spectral data, and differential thermal analysis/thermogravimetry. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of Polymer-Metal Complexes and Their Effects on Dielectric Properties and Ageing and UV Resistance of SBR Vulcanizates

Metal free and some metal-perylene polymers as well as some metal phthalocyanine polymers were incorporated into butadiene styrene rubber (SBR) compounds as coloring agents. Ageing and UV resistance of the vulcanizates obtained were studied in terms of the mechanical properties. The dielectric properties of the vulcanizates were also discussed. The results obtained revealed that cobalt perylene and cobalt phthalocyanine polymers showed superior performance in SBR vulcanizates against thermal ageing and UV radiation. The optimum concentration of cobalt phthalocyanine polymer was found to be 1 phr (parts per hundred parts of rubber).     

Struktur-Aktivitäts/Selektivitäts-Beziehungen von Oxidationskatalysatoren

Structure-Activity/Selectivity Correlation of Oxidation Catalysts Various reactive forms of oxygen are active in the selective oxygen functionalization of olefins and aromatic compounds. These forms are different on different crystal faces of transition metal oxides as shown by their different cation-oxygen bond lengths. Therefore, face specifity of transition metal oxides as catalysts can be expected for the selective oxidation of hydrocarbons. Furthermore, the reactivity of the framework oxygen in the transition metal oxides for selective oxygen functionalization of hydrocarbons is dependent on the nature of the catalytic cycle (one- or two-electron-processes). Therefore, structure sensitivity of oxidation catalysts on the selectivity of transition metal oxides as oxidation catalysts is possible. Starting from this concept the following phenomena of the activity/selectivity relations are discussed for the most important industrial oxidation catalysts:

• —ensemble effects on the selectivity of supported Ag catalysts for the oxidation of ethylene to ethylenoxide.
• —face specifity of multicomponent Bi/Mo-oxide catalysts in the selective oxidation of propylene to acrolein and in the ammoxidation of propylene.
• —structure sensitivity of V₂O₅-containing catalysts in the oxidation of aromatic compounds.