酞菁和酞菁铜的三阶非线性光学性质

用INDO/SDCI方法研究了酞菁和酞菁铜的电子结构, 紫外-可见光谱, 三阶非线性光学系数及其色散效应, 发现酞菁铜中Cu^2+对γ的贡献很小, 故酞菁与酞菁铜的γ几乎相等, 我们的计算结果对此进行了合理的解释。     

Facile electrochemical growth of nanostructured copper phthalocyanine thin film via simultaneous anodic oxidation of copper and dilithium phthalocyanine for photoelectrochemical hydrogen evolution

We present a novel electrochemical approach to grow copper phthalocyanine (CuPc) thin-film photoelectrodes through anodic oxidation of copper and dilithium phthalocyanine (Li₂Pc). This circumvents the challenges associated with the electrochemical processing of unsubstituted CuPc from solution. The potentiostatic co-electrooxidation reaction at the heterogeneous interface favors the growth of CuPc thin film. The surface morphology of thin film exhibits nanorod-like features. UV-Vis, grazing angle Fourier transform infrared (FTIR), and grazing angle X-ray diffraction patterns reveal that the nanocrystalline phase corresponds only to α-CuPc and no admixture of other polymorphs. Photocurrent measurement shows a stable photoresponse in neutral medium. The photoelectrochemical hydrogen evolution on p-type CuPc coated copper photocathode shows an enhanced activity over bare copper and indium tin oxide (ITO) electrodeposited with CuPc and monolithium phthalocyanine radical (LiPc) thin films.     

Role of coordinated metal ions on the orientation of phthalocyanine based coatings

In the present work, we have investigated the molecular orientation of phthalocyanine films deposited on polycrystalline gold. Three films built from the following molecules are investigated: phthalocyanine (H(2)Pc), cobalt phthalocyanine (CoPc) and copper phthalocyanine (CuPc). The films are prepared by spin coating and drop casting methods. Orientation analysis has been performed using polarization dependent Fourier transform infrared (FTIR) spectroscopy using transmission and grazing angle reflectance mode. The FTIR study suggests that each phthalocyanine film contains both alpha- and beta-phases. H(2)Pc based films demonstrate deposition method dependence on the molecular orientation, while the CuPc and CoPc films preserve their molecular orientation independent of deposition method. Grazing angle analysis also suggests that CoPc films show negligible preferred orientation irrespective of film deposition methods. In literature, the band at 878cm(-1) in CuPc has been assigned to out-of-plane bending of C-H. Our grazing angle experiments suggest that this band cannot be assigned to out-of-plane bending vibrations of C-H. Accurate band assignments are also described here for the phthalocyanine system.     

PREPARATION AND CATALYTIC ACTIVITY OF BIOACTIVE FIBERS

Two kinds of water-soluble metallophthalocyanines, binuclear cobalt phthalocyanine （Co2Pc2） and binuclear ferric phthalocyanine （Fe2Pc2）, were synthesized through phenylanhydride-urea route and characterized by elemental analysis and FT-IR spectra. Binuclear metallophthalocyanine derivatives （Mt2Pc2） were immobilized on silk fibers and modified viscose fibers to construct bioactive fibers of mimic enzyme. Mt2Pc2 was used as the active center of bioactive fibers, viscose and silk fibers as the microenvironments. The catalytic oxidation ability of bioactive fibers on the malodors of methanthiol and hydrogen sulfide was investigated at room temperature. The experimental results indicated that the catalytic activity of such bioactive fibers was closely correlative to the types ofbioactive fibers and substrates.     

STUDY ON THE CATALYTIC ABILITY OF BIOACTIVE FIBERS

1. INTRODUCTIONEnzyme as a biologic catalyst plays an important role in all kinds of chemical reactions inside living creatures. Comparing to chemical catalysts, the natural enzyme has many advantages such as high speed, specificity, sensitivity and mild …     

STUDY ON THE CATALYTIC ABILITY OF BIOACTIVE FIBERS

Two kinds of water-soluble metallophthalocyanines (Mt2Pc2), binuclear cobalt phthalocyanine (Co2Pc2) and binuclear ferric phthalocyanine (Fe2Pc2), were supported on silk fibers and modified viscose fibers to construct bioactive fibers of mimic enzyme, Mt2Pc2 used as the active center of bioactive fibers, viscose and silk fibers as the microenvironments. The catalytic oxidation ability of bioactive fibers on the malodors of methanthiol and hydrogen sulfide was investigated at room temperature. The experimental results demonstrated that the catalytic activity of such bioactive fibers was tightly correlative to the types of bioactive fibers and substrates.     

固体凝胶法制备CuCl_(14)Pc/Y复合材料及其表征 (英文)

采用固体凝胶法制备了ＣｕＣｌ_（１４）Ｐｃ／Ｙ复合材料,并采用一系列物化手段对其性能进行了表征。结果表明,无定形硅铝凝胶中所含的ＣｕＣｌ_（１４）Ｐｃ经过水热晶化后被封装在Ｙ型分子筛的超笼中,且被封装的金属配合物的比率高于采用文献中所报道的制备方法。封装于Ｙ型分子筛超笼中的ＣｕＣｌ_（１４）Ｐｃ在环己烷氧化反应中的催化能力明显高于未被封装的ＣｕＣｌ_（１４）Ｐｃ。     

Weak epitaxy growth and phase behavior of planar phthalocyanines on p-sexiphenyl monolayer film

We systematically investigated the weak epitaxy growth (WEG) behavior of a series of planar phthalocyanine compounds (MPc), i.e., metal-free phthalocyanine (H2Pc), nickel phthalocyanine (NiPc), copper phthalocyanine (CuPc), zinc phthalocyanine (ZnPc), iron phthalocyanine (FePc), cobalt phthalocyanine (CoPc), grown on a p-sexiphenyl ( p-6P) monolayer film by selected area electron diffraction (SAED) and atomic force microscopy (AFM). Two types of epitaxial relations, named as incommensurate epitaxy and commensurate epitaxy, were identified between phthalocyanine compounds and the substrate of the p-6P film. The tiny variation of the lattice constant of phthalocyanine compounds can result in different crystal orientations. The change rule of incommensurate and commensurate epitaxy was extracted. The tendency of commensurate epitaxy becomes weaker as the lattice constant b increases, while it gets stronger as the substrate temperature is elevated. Large size and continuous H2Pc films can be obtained by controlling the growth conditions. The WEG method is generally applicable in the whole family of planar phthalocyanine compounds and may be used to fabricate other high-quality organic films.     

Trapping Copper Phthalocyanine in a Silica Sono-Xerogel

A copper phthalocyanine (CuPc) has been encapsulated in silica. The trapping effects were studied comparing the UV-Vis absorption spectra of some CuPc solutions and composites prepared under different conditions. The trapped organic molecules’ stability was monitored during the gelation and drying processes. Leachability test have been carried out with the aim of checking the trapping efficiency. Hydrolysis water of pH=2 and a molar ratioR _w =6 mol acid H₂O/mol TMOS leads to a higher CuPc stacking angle homogeneity. The increase of Pc induces a narrower mesopore distribution and helps the stabilization of the composite.     

新型水溶性钴酞菁的制备及其催化氧化硫醇的性能

采用丁二酸酐、顺丁烯二酸酐对四氨基钴酞菁进行改性后制得两种新型水溶性钴酞菁衍生物, 测试了这两种改性钴酞菁对巯基乙醇的催化氧化性能, 并考察了溶液pH值、温度和时间对催化氧化活性的影响, 结果表明, 在pH＝11时, 两种改性钴酞菁对巯基乙醇的催化氧化性能最好;随着温度的升高, 催化氧化性能提高.     

Spectroscopic consideration of the surface potential built across phthalocyanine thin films on a metal electrode

The nonlinear optical properties of tert-butyl phthalocyanine copper Langmuir-Blodgett (CuttbPc LB) films and vacuum-evaporated phthalocyanine copper (CuPc) films deposited on a metal surface were investigated by second-harmonic generation (SHG) spectroscopy. At the organic/metal interface, a space charge field is formed due to the presence of excess charge injected from a metal electrode to the organic layer. Since the Pc molecule has D4h symmetry, an inversion center is present and the optical SH process is not allowed under the electric-dipole approximation. However, the space charge field at the interface directly influences the symmetric structure of the electrons in the Pc molecule. We investigated the contributions of the surface potential to the SHG using Pc LB and vacuum-evaporated films deposited on aluminum (Al) and gold (Au) metal electrodes, where a distinctive difference in the spectrum for the Pc films on the Al and Au surfaces was observed. The contribution of the surface potential was revealed based on the resonant conditions of the SH process, taking into account the electric-quadrupole transition and dc-field-induced electric-dipole transition.     

Modeling the interactions of phthalocyanines in water: from the Cu(II)-tetrasulphonate to the metal-free phthalocyanine

A quantum and statistical study on the effects of the ions Cu(2+) and SO(3)(-) in the solvent structure around the metal-free phthalocyanine (H(2)Pc) is presented. We developed an ab initio interaction potential for the system CuPc-H(2)O based on quantum chemical calculations and studied its transferability to the H(2)Pc-H(2)O and [CuPc(SO(3))(4)](4-)-H(2)O interactions. The use of the molecular dynamics technique allows the determination of energetic and structural properties of CuPc, H(2)Pc, and [CuPc(SO(3))(4)](4-) in water and the understanding of the keys for the different behaviors of the three phthalocyanine (Pc) derivatives in water. The inclusion of the Cu(2+) cation in the Pc structure reinforces the appearance of two axial water molecules and second-shell water molecules in the solvent structure, whereas the presence of SO(3)(-) anions implies a well defined hydration shell of about eight water molecules around them making the macrocycle soluble in water. Debye-Waller factors for axial water molecules have been obtained in order to examine the potential sensitivity of the extended x-ray absorption fine structure technique to detect the axial water molecules.     

醋酸溶液中Pd-CuPc/Y催化甲烷选择氧化制甲醇

以氯化铜、钼酸铵、苯酐、氯化铵、尿素和NaY分子筛为原料,采用苯酐-尿素法制备了酞菁铜/分子筛复合物CuPc/Y.采用等体积浸渍法将金属钯担载在CuPc/Y上制备了Pd-CuPc/Y催化剂,并在醋酸水溶液中考察了其催化甲烷选择氧化合成甲醇反应的性能,结果表明,催化性能与反应温度、溶剂中CH₃COOH与H₂O的混合比例、对苯醌用量、反应时间等因素有关,在0.5%Pd-0.5%CuPc/Y添加量0.5 g、CH₃COOH与H₂O体积比4∶1、对苯醌用量1 000 μmol、反应时间3 h、反应温度150 ℃的条件下,甲醇的最佳生成量为1 840 μmol.Pd-CuPc/Y催化剂可以多次循环使用,但由于催化剂流失和催化剂表面的钯粒子聚集的原因,循环使用后的催化剂催化活性有所下降.Pd-CuPc/Y在醋酸溶液中催化甲烷选择氧化合成甲醇是亲电取代反应和活性氧物种氧化共同作用的结果.     

In-situ Synthesis of Copper Phthalocyanine in Silica Xerogel Matrix

Using a newly developed in-situ syntheses technique during sol-gel process, copper phthalocyanine (CuPc) is synthesized in-situ in silica xerogel matrix homogeneously. It has been confirmed by UV-Vis and IR spectroscopies that the copper ions which existed in the form of complex-ions [Cu(H₂O)₄]²⁺ and [CuCl₄]^2– in the stages of sol and wet gel were destroyed in the heat treatment process, meanwhile the copper phthalocyanine molecules were synthesized in-situ gradually during the wet gel to xerogel transition. The dimerization phenomenon of CuPc in the composite is suppressed greatly because the in-situ synthesized CuPc molecules were well isolated in the micro-pores of the xerogel matrix. The doping concentration of Copper phthalocyanine in sol-gel derived matrix can be enhanced also by this in-situ synthesis method.     

Investigated aerobic oxidation of aminochlorophenol catalyzed by phthalocyanine complexes

The synthesis of 9-Octadecenamide substituted Fe(II) phthalocyanine (ODAFePc) and Ni(II) phthalocyanine (ODANiPc) complexes from Fe(II) tetracarboxylic acid phthalocyanine (FeTcPc) and Ni(II) tetracarboxylic acid phthalocyanine (NiTcPc) with 9-Octadecenamide. These complexes have high molecular weight and soluble in organic solvents. The complexes have been confirmed by FTIR, Mass spectroscopy, UV–Visible X-ray diffraction, and thermogravimetric analysis. The synthesized complexes exhibit excellent stability and are catalytically active in 2-amino-4-chlorophenol (ACP) oxidation. The new method was used for the determination of the oxidation of phenol by applying different experimental parameters like concentration, catalytic quantity, temperature, and pH to get a good yield and catalytic activity of ODAFePc and ODANiPc were studied. ACP was oxidized by dissolved oxygen with ODAFePc and ODANiPc as a catalyst and immediately combined with 4-aminoantipyrine (4-AAP) to form a pink dye and was determined by appearance of absorption intensity at 580 ​nm. All the experimental results show that ODAFePc and ODANiPc complexes exhibit good catalytic behavior on oxidation of 2-amino-4-chlorophenol.     

Matrix effects on copper(II)phthalocyanine complexes. A combined continuous wave and pulse EPR and DFT study

The effect of the electron withdrawing or donating character of groups located at the periphery of the phthalocyanine ligand, as well as the influence of polar and nonpolar solvents are of importance for the redox chemistry of metal phthalocyanines. Continuous wave and pulse electron paramagnetic resonance and pulse electron nuclear double resonance spectroscopy at X- and Q-band are applied to investigate the electronic structure of the complexes Cu(II)phthalocyanine (CuPc), copper(II) 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine (CuPc(t)), and copper(II) 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluoro-29H,31H-phthalocyanine (CuPc(F)) in various matrices. Isotope substitutions are used to determine the g values, the copper hyperfine couplings and the hyperfine interactions with the 14N, 1H and 19F nuclei of the macrocycle and the surrounding matrix molecules. Simulations and interpretations of the spectra are shown and discussed, and a qualitative analysis of the data using previous theoretical models is given. Density functional computations facilitate the interpretation of the EPR parameters. The experimental g, copper and nitrogen hyperfine and nuclear quadrupole values are found to be sensitive to changes of the solvent and the structure of the macrocycle. To elucidate the electronic, structural and bonding properties the changes in the g principal values are related to data from UV/Vis spectroscopy and to density functional theory (DFT) computations. The analysis of the EPR data indicates that the in-plane metal-ligand sigma bonding is more covalent for CuPc(t) in toluene than in sulfuric acid. Furthermore, the out-of-plane pi bonding is found to be less covalent in the case of a polar sulfuric acid environment than with nonpolar toluene or H2Pc environment, whereby the covalency of this bonding is increased upon addition of tert-butyl groups. No contribution from in-plane pi bonding is found.     

氧化铈气凝胶担载氧化铜催化剂上的一氧化碳氧化

 以一氧化碳氧化为探针反应,考察了氧化铈气凝胶担载氧化铜催化剂的催化活性,研究了催化剂中氧化铜的含量、载体及催化剂的焙烧温度对催化剂活性的影响．结果表明,氧化铈气凝胶担载的氧化铜催化剂对一氧化碳氧化反应呈现出高催化活性,适当温度下焙烧载体及催化剂有利于提高催化剂的催化活性;随着催化剂中氧化铜含量的增加,一氧化碳完全转化的温度降低,但当w（CuO）＞12％时,过量的氧化铜以体相形式而不是以高分散形式存在,对催化剂活性的影响很小．     

一价铜改性ZSM-5催化剂及其催化碳烟氧化反应性能研究

采用固态离子交换法制备了系列一价铜改性的ZSM-5催化剂,结合多种表征手段,研究了一价铜改性对碳烟氧化反应催化活性的影响。结果表明,采用固态离子交换法可以制备出高负载量的一价铜改性Cu/ZSM-5分子筛催化剂,而不会破坏ZSM-5分子筛原有微孔结构;随催化剂中一价铜比例的增加,低温还原峰和高温还原峰均向低温段移动,且低温还原峰面积增加。改性催化剂对碳烟氧化反应的催化活性随改性元素比例变化先增加后降低;当铜改性比例超过11%后,铜物种的分散性及催化剂对碳烟氧化反应的催化活性均恶化。同时研究还发现,反应气氛中通入NO可以改善催化剂对碳烟氧化反应的催化效果。     

Metal—ligand and π singlet—triplet transitions in phthalocyanine films studied by inelastic electron tunneling spectroscopy

Inelastic electron tunneling spectroscopy (IETS) on AlAl₂O₃/PcPb tunneling junctions at 4.2 K has been used to study electronic transitions involving π, π^≠ and metal-ligand orbitals of phthalocyanine (Pc) films (H₂Pc, FePc, CoPc, NiPc, CuPc, ZnPc). The results are compared with calculations for Pc molecules.     

Anthracene Substituted Co (II) and Cu (II) phthalocyanines; Preparations,Investigation of Catalytical and Electrochemical Behaviors

An approach to investigation of catalytical behaviors of Co (II) and Cu (II) phthalocyanines is reported that is based on changing any parameter to effect these behaviors. Towards this end, new anthracene substituted Co (II) and Cu (II) phthalocyanines were prepared and characterized spectroscopic methods. New cobalt (II) and copper (II) phthalocyanines were used as catalyst for oxidation of different phenolic compounds (such as 2,3‐dichlorophenol, 4‐methoxyphenol, 4‐nitrophenol, 2,3,6‐trimethylphenol) with different oxidants. Then, electrochemical characterization of cobalt (II) and copper (II) phthallocyanines were determined by using cyclic voltammetry (CV) and square wave voltammetry (SWV) techniques. Although copper (II) phthalocyanine showed similar Pc based electron transfer processes, cobalt (II) phthalocyanine showed metal and ligand based reduction reactions as expected.