酞菁铜溶解性研究及其电沉积薄膜的制备

通过测定α-酞菁铜(α-CuPc)在4种不同的有机溶剂中的紫外可见光吸收光谱,研究了不同溶剂以及加入不同量的三氟乙酸(TFAA)对酞菁铜溶解性和质子化的影响.以溶解性研究为基础,探讨了在电化学沉积法制备酞菁铜薄膜时不同工艺条件对其形貌的影响.实验结果表明:加入TFAA后,酞菁铜在硝基甲烷和氯仿中溶解良好,而且在氯仿中更容易质子化;使用扫描电镜(SEM)表征,结果表明TFAA及酞菁铜摩尔含量对薄膜制备的影响最为明显.     

八羧基铜酞菁修饰海藻酸钠阳膜层制备CuPc(COOH)8-SA/mCS双极膜及其表征

在海藻酸钠(SA)中添加八羧基铜酞菁(CuPc(COOH)₈),并分别用Fe³⁺离子和戊二醛作为交联剂对海藻酸钠-八羧基铜酞菁阳膜层和壳聚糖(CS)阴膜层进行改性,制备了八羧基铜酞菁-海藻酸钠/改性壳聚糖双极膜(CuPc(COOH)₈-SA/mCS BPM)。在海藻酸钠中添加八羧基铜酞菁以促进中间层中水的解离。用FTIR、SEM等对制备的CuPc(COOH)₈-SA/mCS双极膜进行了表征。作为比对,制备了Fe³⁺离子改性的Fe-SA/mCS双极膜和二茂铁(Fc)离子改性的Fc-SA/mCS双极膜。实验结果表明,CuPc(COOH)₈-SA阳离子交换膜的离子交换容量、H⁺离子透过率均获得提高。与Fe³⁺离子改性或二茂铁离子改性的mSA/mCS双极膜相比,CuPc(COOH)₈-SA/mCS双极膜的阻抗、电阻压降(IR降)和溶胀度降低,在H+离子浓度低于8 mol·L^-1的酸溶液中具有稳定的工作性能。     

Dissolution of copper phthalocyanine and fabrication of its nano-structure film

The mono-protonated and di-protonated forms of copper phthalocyanine (CuPc) were obtained by increasing concentrations of trifluoroacetic acid (TFA) solution to a fixed concentration of CuPc solutions. UV-Vis spectrum shows that the Q bands of these two derivatives split and shift to the red, which means successive protonation happened and caused the two derivatives to lose their symmetry. After the protonation step, the solubility of protonated CuPc in organic solvent increased 60 times. The CuPc film was fabricated by the electrophoretic deposition (EPD) method from the protonated CuPc dissolved in nitromethane containing TFA. Scanning electron microscopy (SEM) showed that the deposited CuPc film on the indium tin oxide (ITO) substrate is composed of thread-like nanobelts with diameters between 100 nm and 200 nm. Furthermore, the CuPc film is in α phase with stacking direction (b-axis) parallel to the substrate, which was detected by X-ray diffraction.     

Adsorption and assembly of copper phthalocyanine on cross-linked TiO2(110)-(1 x 2) and TiO2(210)

Copper phthalocyanine (CuPc) on reconstructed rutile TiO(2) was studied with ultrahigh vacuum variable temperature scanning tunneling microscopy. On cross-linked TiO(2)(110)-(1 x 2), the CuPc molecules at low coverages sparsely lay flat at the link sites and tilted in troughs between [001] rows. Increase of the CuPc coverage led to the trapping of the CuPc molecules by the rectangular surface cells fenced by the oxygen columns along the [001] direction and the cross-link rows. Each cell could trap one CuPc molecule at intermediate coverages and two CuPc molecules at higher coverages. On TiO(2)(210), the CuPc molecules tilted in defect-free areas and lay at defect sites with their molecular planes parallel to the substrate surface. Further increase of the CuPc coverage induced the formation of one- and two-dimensional assemblies on TiO(2)(210).     

Vibronic spectra of solutions and sols of copper phthalocyanine

Optical spectra of solutions and sols prepared from finely dispersed crystalline copper phthalocyanine (CuPc) were studied. The CuPc preparation was demonstrated to contain an admixture of an amorphous phase. The amorphous phase proved to be soluble in dioxane and heptane with the formation of a true molecular solution of CuPc. It was found that CuPc molecules are absorbed by polyethylene, polypropylene, polycaproamide, and cellulose triacetate films. The optical spectrum of individual CuPc molecules was demonstrated to differ substantially from those of particles of the pigment. It featured intense vibronic bands belonging to three π → π* transitions typical of aromatic structures and a series of bands characteristics of n → π* transitions involving nitrogen atoms (<29000 cm^?1) but showed no absorption bands characteristic of dispersions of the pigment in the visible spectrum (400–800 cm^?1). It was revealed that the Q-band (λ = 670 nm), assigned in the literature to individual CuPc molecule, in reality belongs to CuPc associates.     

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。     

高比表面积CuPc/TiO2纳米管复合材料的制备及其可见光光催化活性

以P25为前驱体,在碱性条件下采用水热法制备了TiO2纳米管(NT),然后通过浸渍法将敏化剂酞菁铜(CuPc)附着于TiO2NT表面,制得可见光响应的CuPc/TiO2NT复合光催化材料,并对其进行了表征,考察了它在可见光下降解罗丹明B的光催化活性.结果表明,在NaOH碱性条件下水热法制备的TiO2NT具有较大的比表面...     

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.     

Photophysical behavior of open-shell first-row transition-metal octabutoxynaphthalocyanines: CoNc(OBu)8 and CuNc(OBu)8 as case studies

Ultrafast photodynamics and density functional theory/time-dependent density functional theory (DFT/TDDFT) results for complexes of Co and Cu with 5,9,14,18,23,27,32,36-octabutoxynaphthalocyanine [CoNc(OBu)8 and CuNc(OBu)8] are reported. As a basis for this work, details concerning the syntheses of these complexes and the corresponding Zn complex (used as a reference) are given. Transient absorption spectrometry with femtosecond time resolution combined with a detailed DFT/TDDFT analysis has been employed to construct a complete picture of the excited-state dynamics after Q-band excitation of the Co and Cu complexes and to gain an understanding of the relationship between the nature of the metal center and the excited-state lifetime. The Co complex was shown to return to its ground state via two competing channels: a (2)T1(pi, pi*) state that decayed with a lifetime of 1 ps and a low-lying (2)(d, d) state that repopulated the ground-state surface with a lifetime of 15 ps. CuNc(OBu)8 showed ground-state repopulation from the (2)T1(pi, pi*) state via a lower-lying ligand-to-metal charge-transfer (LMCT) state that was completed within a few nanoseconds. The photophysical behavior of the cobalt and copper complexes was compared to that previously reported for the nickel analog in an effort to highlight the effect of the central metal on the nature and rates of the deactivation pathways. The results described in this work provide basic knowledge that is relevant to the use of these compounds as photothermal sensitizers in cancer therapy.     

Properties of copper (fluoro-)phthalocyanine layers deposited on epitaxial graphene

We investigate the atomic structure and electronic properties of monolayers of copper phthalocyanines (CuPc) deposited on epitaxial graphene substrate. We focus in particular on hexadecafluorophthalocyanine (F(16)CuPc), using both theoretical and experimental (scanning tunneling microscopy - STM) studies. For the individual CuPc and F(16)CuPc molecules, we calculated the electronic and optical properties using density functional theory (DFT) and time-dependent DFT and found a red-shift in the absorption peaks of F(16)CuPc relative to those of CuPc. In F(16)CuPc, the electronic wavefunctions are more polarized toward the electronegative fluorine atoms and away from the Cu atom at the center of the molecule. When adsorbed on graphene, the molecules lie flat and form closely packed patterns: F(16)CuPc forms a hexagonal pattern with two well-ordered alternating α and β stripes while CuPc arranges into a square lattice. The competition between molecule-substrate and intermolecular van der Waals interactions plays a crucial role in establishing the molecular patterns leading to tunable electron transfer from graphene to the molecules. This transfer is controlled by the layer thickness of, or the applied voltage on, epitaxial graphene resulting in selective F(16)CuPc adsorption, as observed in STM experiments. In addition, phthalocyanine adsorption modifies the electronic structure of the underlying graphene substrate introducing intensity smoothing in the range of 2-3 eV below the Dirac point (E(D)) and a small peak in the density of states at ～0.4 eV above E(D).     

铜酞菁同质多晶现象的研究及其超细粒子的制备

采用路易斯酸配位法溶解了铜酞菁,并对路易斯酸溶解铜酞菁的机理进行了简单讨论,同时研究了溶解过程中不同溶剂对铜酞菁晶型的影响.最后,用路易斯酸溶解配位法和微射流纳米分散技术相结合的方法成功制备了铜酞菁超细粒子,并用激光粒度仪、原子力显微镜、紫外可见分光光度计对超细粒子的粒径和吸收光谱进行了表征.     

非手性的酞菁铜分子在Bi(111)表面上的手性特征

利用低温扫描隧道显微镜（LT-STM）研究了酞菁铜（CuPc）分子在Bi（111）表面上的吸附和手性自组装结构。由于较弱的分子-衬底相互作用,我们发现在液氮温度（78 K）下吸附在Bi（111）表面上的单个CuPc分子围绕着分子中心发生旋转,直到遇到其他分子形成团簇为止。随着分子覆盖度的增加,CuPc分子形成了自组装分子单层。高分辨STM图表明,非手性的CuPc分子出现了手性特征：两个相对的酞菁基团发生了弯曲。当覆盖度超过一个分子层,酞菁铜分子的吸附取向由“平躺”转变到“站立”姿态。我们认为,酞菁铜分子的手性起源是由两种因素共同导致的结果：一种是分子-衬底之间的非对称电荷转移,另一种是相邻分子间的非对称性的范德华力作用。     

Circuit simulation for the dielectric responses of the composites of copper phthalocyanine oligomers and sulfonated polyurethanes by separating the structural elements

The copper phthalocyanine (CuPc) oligomer with high dielectric constant was synthesized by the solution method. The FT‐IR and X‐ray diffraction results revealed its chemical structure. The high dielectric constant of CuPc was proved to result from the free movement of charge carriers along the conjugated orbitals. The composites of CuPc and sulfonated polyurethane (PUI) were prepared and the contents of CuPc in the composites were varied from 10 to 50 wt %. The dielectric performance was greatly enhanced for the composite compared with that of average polymers. Different from the behaviors appeared in a common composite with conductive fillers, there is no percolation phenomenon observed in the CuPc/PUI composite, and the dielectric constants of CuPc/PUI composites decreased with the increase in the CuPc content, which is assumed to due to the strong electrostatic interactions between CuPc and PUI. Considering the many‐body interactions within the bulk sample and the contact effect between the bulk sample and the metallic electrode, an equivalent circuit was established to simulate the dielectric behaviors of the composites and computational curve fitting was done. The results were in good agreement, indicating that the dielectric responses of the composites come from both the extrinsic and the intrinsic contributions. The extrinsic was associated with the Maxwell‐Wagner relaxation at the interface between the electrode and the bulk sample, and the intrinsic was associated with the huge dipoles provided by the mobile charges within the CuPc grains and the interaction among them in the bulk composites. A circuit model concerning the universal dielectric response was proposed in describing the intrinsic contribution, which quantitatively verified the strong interaction among the dipoles with the relaxation time, representing the aggregated structure of CuPc when its content was high in the composites. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1146–1155, 2009     

CuPc(COOH)8-SA/CuTAPc-CS双极膜的制备及表征

分别用八羧基铜酞菁[CuPc(COOH)₈]和四氨基铜酞菁(CuTAPc)改性海藻酸钠(SA)阳膜层和壳聚糖(CS)阴膜层, 制备了CuPc(COOH)₈-SA/CuTAPc-CS双极膜. 实验结果表明, 经八羧基铜酞菁和四氨基铜酞菁改性后, 促进了双极膜中间层水的解离, 增大了阳离子交换膜层和阴离子交换膜层的离子交换容量及H⁺和OH^-的透过率. 与Fe³⁺改性的Fe-SA/mCS双极膜相比, CuPc(COOH)₈-SA/CuTAPc-CS双极膜的阻抗、电阻压降(即IR降)和溶胀度降低. 当电流密度高达120 mA/cm²时, CuPc(COOH)₈-SA/CuTAPc-CS双极膜的IR降仅为0.9 V.     

酞菁铜与四氰代二甲基苯醌电荷转移反应的测定

用红外光谱、紫外可见光谱、循环伏安法等研究了三．（２，４－二特戊基苯氧基）－８－喹淋氧基酞菁铜（简称酞菁铜）和２－十八烷基－７，７，８，８－四氰二甲基苯醌（简称Ｃ１８－ＴＣＮＱ）在Ｌａｎｇ－ｍｕｉｒ－Ｂｌｏｄｇｅｔｔ（ＬＢ）膜中的电荷转移。实验结果表明，在交替和混合ＬＢ膜中，酞菁铜和Ｃ１８－ＴＣ－ＮＱ分子之间均发生了电荷转移，其中酞菁铜为给体分子，ＴＣＮＱ为受体分子。在混合ＬＢ膜中，电荷转移程度较大。电导率测量表明荷移反应使ＬＢ膜的电导率较纯酞菁铜ＬＢ膜提高了３个数量级。     

Electrophoretic deposition of phthalocyanine in organic solutions containing trifluoroacetic acid

The absorption spectra of copper phthalocyanine (CuPc) 1,2-dichloroethane (DCE) solutions containing trifluoroacetic acid (TFAA) shows that the number of protons coordinating to the CuPc molecule was 1 and 2 for the first and second proton adducts, respectively, which indicates the formations of CuPcH(+) and CuPcH(2)(2+). This CuPc molecule may act as a catalyst to dissociate TFAA into trifluoroacetate anion (A(-)) and H(+) and form the proton adducts. The electrical conductivity dependence of the solution on CuPc concentration also supports this mechanism. A dense film of CuPc was deposited on an indium tin oxide cathode plate by electrophoresis of the solution. Similar dense films of a wide variety of phthalocyanines (MPc; M = Cu, H(2), Fe, Ni, Zn, Pb, VO) were also deposited using this method. Similar films of CuPc were also formed using dichloromethane (DCM) and 1,1,1-trichloroethane (TCE) in place of DCE. Depositions are ascribed to the migration of positively charged monomers (i.e., protonated MPc). Scanning electron microscopy revealed that these films are composed of fibrous crystallites, size of which was found to increase with the electrophoresis time, the strength of the applied electrical field and the concentration of CuPc in the bath. The influence of the dielectric constant of the organic solvent on the film growth is discussed.     

Study of interface properties in CuPc based hybrid inorganic-organic solar cells

Metal-substituted phthalocyanine thin films such as copper-phthalocyanine (CuPc) are often used as photo-active and hole transporting layers (HTLs) in fully organic photovoltaic devices. In this work, CuPc is vacuum sublimated on an electron acceptor layer of mesoporous titania (TiO(2)) for the formation of hybrid TiO(2):CuPc solar cell devices. The performance of these hybrid solar cell devices was demonstrated without and with dye sensitization at the TiO(2):CuPc interface. The charge separation and photocurrent contribution at the interfaces in these multilayer hybrid devices was studied by using a variety of optoelectrical and photophysical characterization techniques. It is important to understand the fundamental interface properties of these multilayer hybrid solar cell devices for optimized performance.     

Effects of Langmuir-Blodgett Film as Hole Transport Layer on Organic Electroluminescent Device Performance

Three types of organic electroluminescence(EL) cells with organic material FY as the EL-emitting layer and a copper phthalocyanine (CuPc) as the hole transport layer which were sandwiched between indium/tinoxde(ITO) and aluminum electrode have been fabricated by vacuum-vapor and Langmuir-Blodgett (LB) deposition:(a) ITO/FY/Al;(b)ITO/CuPc/FY/Al;(c) ITO/CuPc(LB)/FY/Al. It was found for the first time that the cell with the LB film as the hole transport layer has the highest luminescent intensity at the same bias-voltage. These results are attributed to the order orientation of the CuPc molecule in the layer of LB film.     

TiO_2/CuPc/NiFe-LDH photoanode for efficient photoelectrochemical water splitting

Photoelectrochemical(PEC) water splitting is a promising approach for renewable hydrogen production.However,the practical PEC solar-to-fuel conversion efficiency is still low owing to poor light absorption and rapid recombination of charge carriers in photoelectrode.In this work,we report a ternary photoanode with simultaneously enhancement of light absorption and water oxidation efficiency by introducing copper phthalocyanine(CuPc) and nickel iron-laye red double hydroxide(NiFe-LDH) on TiO_2(denoted as TiO_2/CuPc/NiFe-LDH).An experimental study reveals that CuPc loading on TiO_2 bring strong visible light absorption;NiFe-LDH as an oxygen evolution reaction catalyst efficiently accelerates the surface water oxidation reaction.This synergistic effect of CuPc and NiFe-LDH gives enhanced photocurrent density(2.10 mA/cm2 at 0.6 V vs.SCE) and excellent stability in the ternary TiO_2/CuPc/NiFeLDH photoanode.     

Microwave-assisted synthesis and reverse saturable absorption of phthalocyanines and porphyrins

Soluble phthalocyanines, including tetrakis(2,9,16,23-cumylphenoxy) copper phthalocyanines (CuPc(β-CP)₄), tetrakis(1,8,15,22-cumylphenoxy) copper phthalocyanines (CuPc(α-CP)₄) as well as tetrakis(2,9,16,23-tert-butyl) copper phthalocyanines (CuPc(β-t-butyl)₄), and porphyrins (5,10,15,20-tetrakis(4-tert-butylphenyl)porphyrins; M(TBP), M=H₂, Zn, Cu, Mg, InCl, AlCl) have been quickly synthesized by microwave irradiation. Furthermore, their reverse saturable absorption have also been investigated by dissolving them in solvent or incorporating them in polymer-silica hybrid material with a sol-gel process with polyvinyl butyral and tetraethyl orthosilicate as precursors. A new method for the preparation process of phthalocyanines and porphyrins in the solids has been successfully used.