The phthalonitrile derivative chosen for the synthesis of substituted phthalocyanines [M: 2H, Zn(II), Co(II)] with four chloro and four phenyloxyacetic acid substituents on the periphery is 4-chloro-5-(4-phenyloxyacetic acid)phthalonitrile. The sodium salt of carboxyl substituted zinc phthalocyanine is good soluble in water. Further reactions of zinc and cobalt phthalocyanines bearing phenyloxyacetic acid with thionylchloride gave the corresponding acylchlorides. This functional group reacted with hydroxymethylferrocene in dry DMF to obtain ferrocenyl substituted phthalocyanines. Also chloro substituent in new phthalonitrile was substituted with hexylsulfanyl substituent and its cyclotetramerization in the presence of Zn(AcO)2·2H2O and 2-(dimethylamino)ethanol resulted with zinc phthalocyanine. The compounds have been characterized by elemental analysis, MALDI-TOF mass, FT-IR, 1H NMR, UV-Vis and fluorescence data. Aggregations properties of phthalocyanines were investigated at different concentrations in tetrahydrofuran, dimethylformamide, dimethylsulfoxide, water, and water/ethanol mixture. Also fluorescence spectral properties are reported. 相似文献
The catalytic activity of a binuclear complex of a macroheterocyclic compound (MHCC) containing cobalt(II) and having an enlarged coordination cavity is studied by cyclic voltammetry. Basic features of the electrochemical behavior of MHCC Co2O2 in alkaline solution are found. The complex has a higher catalytic activity as compared to cobalt phthalocyanine. 相似文献
Cobalt(II) phthalocyanine (CoPc), cobalt(II) tetrachloro phthalocyanine (CoPcCl4), cobalt(II) octachloro phthalocyanine (CoPcCl8) and cobalt(II) hexadecachloro phthalocyanine (CoPcCl16) are synthesized pure and characterized using elemental analysis, UV-visible, IR-spectroscopy, magnetic susceptibility, X-ray crystallography, and thermogravimetry. All four complexes have monoclinic structure with different crystal lattice constants. Broido's, Coats-Redfern and Horowitz-Metzger relations were employed to calculate the kinetic and activation parameters associated with thermal decomposition of the above complexes. The compounds are analyzed for kinetic parameters, activation energies for decomposition and the Arrhenious pre-exponential factors, in their pyrolysis. Using these factors and standard equations, thermodynamic parameters such as enthalpy, entropy and free energies are calculated. The activation energies are evaluated based on their electrical conductivity conducted over the temperature range 30–200°C. The electrical conductivities observed at 30°C are in the order CoPcCl16?>?CoPcCl4?>?CoPcCl8?>?CoPc. The relevant electrical conductivity data are reported. 相似文献
The integration of molecular catalysts with low‐cost, solid light absorbers presents a promising strategy to construct catalysts for the generation of solar fuels. Here, we report a photocatalyst for CO2 reduction that consists of a polymeric cobalt phthalocyanine catalyst (CoPPc) coupled with mesoporous carbon nitride (mpg‐CNx) as the photosensitizer. This precious‐metal‐free hybrid catalyst selectively converts CO2 to CO in organic solvents under UV/Vis light (AM 1.5G, 100 mW cm?2, λ>300 nm) with a cobalt‐based turnover number of 90 for CO after 60 h. Notably, the photocatalyst retains 60 % CO evolution activity under visible light irradiation (λ>400 nm) and displays moderate water tolerance. The in situ polymerization of the phthalocyanine allows control of catalyst loading and is key for achieving photocatalytic CO2 conversion. 相似文献
The present investigation describes synthesis of a good range of henna‐based compounds in the presence of novel nano cobalt phthalocyanine like molten salt (tetra‐2,3‐pyridiniumporphyrazinato cobalt tribromomethanide) [Co (TPPABr)]CBr3 as an efficient, recyclable and thermally stable heterogeneous catalyst. 相似文献
The catalytic and photocatalytic activities of supported cobalt or zinc phthalocyanine complexes, bulk MoS2, MoS2 deposited on Al2O3, potassium intercalated MoS2 (K0.33 H2O0.66 MoS2), CdS and polycrystalline nickel phosphorus trisulfide (NiPS3) have been investigated in the oxidation of sodium sulfide and Na2S2O3. The phthalocyanine complexes and the metal chalcogenides do not catalyze, in the absence of light, the complete oxidation of the sulfide ion to sulfate ion. The final product of the catalytic oxidation is the formed thiosulfate. No oxidation of Na2S2O3 has been registered in the dark in the presence of any of the catalytic samples. Their activity was enhanced upon irradiation with visible light. Thiosulfate appears to be the final product also of the photooxidation of the sulfide ion catalyzed by metal chalcogenides. They do not catalyze the further photooxidation of Na2S2O3. The only photocatalysts which favour with their presence the oxidation of the sulfide and thiosulfate ions to sulfate ion, are the zinc phthalocyanine complexes. In this case, the photooxidation process involves singlet oxygen. 相似文献
This work reports an in situ cobalt(II) phthalocyanine (CoPc) synthesis on a SiO2/SnO2 (SiSn) matrix surface obtained by the sol‐gel method and its electrocatalytic activity for oxidation of nitrite. A rigid disk electrode with SiSn/CoPc was used to study the electrooxidation of nitrite by the cyclic voltammetric, chronoamperometric techniques and differential pulse voltammetry (DPV). The adsorbed phthalocyanine electrocatalyzed nitrite oxidation at 0.73 V (versus SCE) using the DPV technique. The anodic peak current intensities, plotted from differential pulse voltammograms in 1 mol L?1 KCl for the concentration range 0.002 to 3.85 mmol L?1 of nitrite were linear, with a correlation coefficient of 0.998 and a detection limit of 0.95 μmol L?1. 相似文献
BiVO4‐Silica composites were prepared and grafted with sulfonated cobalt phthalocyanine. The structural and chemical properties including crystalline phase, specific surface area, UV–Visible diffuse reflectance behavior, morphology and photocatalytic activity were investigated. Depending on the silica content and subsequently amounts of loaded phthalocyanine, various catalytic activities were observed. The sample containing nominal 15% silica and grafted with phthalocyanine showed less aggregated form of this organic dye, smaller and nanometric particles, and higher photocatalytic activity in degradation of 2,4,6‐trichlorophenol. 相似文献
A novel alcohol-soluble ionophore ligand and its non-peripherally tetrasubstituted functional 1,8,15,22-tetrakis(6-hydroxyhexylsulfanyl) metallophthalocyanines M[Pc(α-SC6H12OH)4] (M = Cu(II), Zn(II), Co(II); Pc = phthalocyanine) are reported. The aggregation and cation binding behaviors of the phthalocyanine compounds in the presence of soft AgI and PdII metal ions were investigated by using UV–Vis spectroscopy. The new compounds have been characterized by elemental analysis, IR, 1H, 13C NMR, UV/Vis spectroscopy, ESI and MALDI–TOF–MS mass spectra. Voltammetric and in-situ spectroelectrochemical studies show that while copper and zinc phthalocyanine complexes give well-defined ring-based reduction and oxidation processes, the cobalt phthalocyanine gives both metal-based and ring-based redox processes which have reversible and diffusion controlled character. 相似文献
The interaction of chitosan with copper(II) and cobalt(II) tetrasulfophthalocyanines is studied by spectral methods. The main parameters of binding of chitosan to anionic metal phthalocyanines are determined by Scatchard analysis. It is found that the formation of the polymer complex is considerably contributed by donor?acceptor interactions between the coordinately unsaturated metal phthalocyanine and chitosan amino groups. Сhitosan reacts with a monomeric cobalt(II) tetrasulfophthalocyanine, whereas copper(II) tetrasulfophthalocyanine in its complex with chitosan remains in the dimeric state. The reaction centers responsible for the Cu(SO3H)4Pc)2–chitosan and Co(SO3H)4Pc–chitosan complexes are revealed by means of IR spectroscopy. 相似文献
The electrochemical properties of a glassy-carbon electrode coated with a polyvinylpyridine film doped with incorporated cobalt phthalocyanine were studied in a reaction involving a benzoquinone–hydroquinone redox couple. It was found that poly-(2-vinylpyridine) film applied to the electrode and cobalt phthalocyanine deposited onto it or incorporated in the polymeric film exhibited electrocatalytic activity on the oxidation of hydroquinone. Conditions were selected for obtaining a polyvinylpyridine film doped with cobalt phthalocyanine on the electrode surface providing a maximum catalytic effect. The current of the hydroquinone oxidation peak and the current of the reverse benzoquinone reduction peak at the chemically modified electrode were linear functions of their concentrations in the range from 1 × 10–6 to 1 × 10–3 M. 相似文献
Summary: A novel class of polymer has been prepared by reaction of a copolyimide containing carboxylic acid groups, and a cobalt phthalocyanine peripherally substituted with a reactive hydroxyl group. The incorporation of the phthalocyanine ring was achieved by esterification of the carboxylic acid groups of the polyimide with the free hydroxyl group of the phthalocyanine. In this work, a limited number of phthalocyanine rings have been introduced in order to avoid extensive modification of the copolyimide properties. The extent of modification (percentage of esterified carboxylic groups) was estimated to be about 18%. The resulting material showed good thermal stability and a high glass transition temperature (above 300 °C). The incorporation of the bulky phthalocyanine ring brought about a light decrease of thermal properties, relative to those of the initial polyimide. The presence of phthalocyanine was confirmed by the absorption band at 670 nm showing in the visible region for the modified polyimide. The novel copolyimide also exhibited a remarkable emission peak at 430 nm, when excited at 350 nm, corresponding to the emission of the cobalt phthalocyanine moiety.
Schematic representation of the PI‐CoPc molecule and the chemical structure of the repeat unit. 相似文献
Decomposition of S‐nitrosoglutathione (GSNO) in phosphate buffer solution at physiological pH 7.4 in the presence of cuprous ion as a catalyst and sodium borohydride as a reducing agent is analyzed by observing the transient apparition of reduced glutathione GSH through its electrooxidation. Transient formation of GSH, upon decomposition of 1 mM GSNO in presence of 0.025 mM Cu(NO3)2 and 1 mM NaBH4 was detected by using an ordinary pyrolytic graphite electrode modified with an adsorbed monolayer of cobalt phthalocyanine at 0 V vs. SCE. 相似文献
Electroreduction of CO2 into carbonaceous fuels or industrial chemicals using renewable energy sources is an ideal way to promote global carbon recycling. Thus, it is of great importance to develop highly selective, efficient, and stable catalysts. Herein, we prepared cobalt single atoms (Co SAs) coordinated with phthalocyanine (Co SAs-Pc). The anchoring of phthalocyanine with Co sites enabled electron transfer from Co sites to CO2 effectively via the π-conjugated system, resulting in high catalytic performance of CO2 electroreduction into CO. During the process of CO2 electroreduction, the Faradaic efficiency (FE) of Co SAs-Pc for CO was as high as 94.8 %. Meanwhile, the partial current density of Co SAs-Pc for CO was −11.3 mA cm−2 at −0.8 V versus the reversible hydrogen electrode (vs RHE), 18.83 and 2.86 times greater than those of Co SAs (−0.60 mA cm−2) and commercial Co phthalocyanine (−3.95 mA cm−2), respectively. In an H-cell system operating at −0.8 V vs RHE over 10 h, the current density and FE for CO of Co SAs-Pc dropped by 3.2 % and 2.5 %. A mechanistic study revealed that the promoted catalytic performance of Co SAs-Pc could be attributed to the accelerated reaction kinetics and facilitated CO2 activation. 相似文献
Copper and cobalt complexes of tetra[4,5]([8,9](benzo[f]quinoline-7,10-dione)phthalocyanine, tetra[4,5]-([6,7]1-acetyl-2H-naphtho[2,3-d][1,2,3]triazole-5,8-dione) phthalocyanine, and tetra[4,5]([6,7]3-methylquinoline-5,8-dione)phthalocyanine were synthesized
and their spectral properties were investigated. 相似文献
In this study, the preparation of novel 7-hydroxy-3-(2-chloro-4-fluorophenyl)coumarin (1), the ligand, 7-(3,4-dicyanophenoxy)-3-(2-chloro-4-fluorophenyl)coumarin (2), metal-free phthalocyanine 3 and metallophthalocyanine complexes 4 and 5 (MPcs, M = Co, Zn), β-substituted with 7-oxo-3-(2-chloro-4-fluorophenyl)coumarin functional group was achieved. By the reaction of 7-hydroxy-3-(2-chloro-4-fluorophenyl)coumarin (1) with 1,2-dicyano-4-nitrobenzen in dry DMF as the solvent in the presence of K2CO3 as the base, the 7-(3,4-dicyanophenoxy)-3-(2-chloro-4-fluorophenyl)coumarin (2) was synthesized. Compound 2 reacted with Co(CH3COO)2·4H2O in 2-N,N-dimethylaminoethanol to furnish a novel coumarin containing cobalt(II) phthalocyanine 4. The cyclotetramerization of 2 with Zn(CH3COO)2·2H2O in 2-N,N-dimethylaminoethanol gave the novel coumarin containing Zn(II)phthalocyanine 5; while tetramerization without any metal salts in 2-N,N-dimethylaminoethanol gave the metal-free phthalocyanine 3. The structures of obtained compounds were confirmed by elemental analysis, UV–Vis, IR, MALDI-TOF mass and 1H NMR spectra. The cyclic and differential pulse voltammetry, and in situ spectroelectrochemistry of 7-oxo-3-(2-chloro-4-fuorophenyl)coumarin substituted phthalocyanines 3, 4 and 5 allowed us to identify metal- and phthalocyanine ring-based redox processes of the complexes. 相似文献
The development of high-performance photocatalytic systems for CO2 reduction is appealing to address energy and environmental issues, while it is challenging to avoid using toxic metals and organic sacrificial reagents. We here immobilize a family of cobalt phthalocyanine catalysts on Pb-free halide perovskite Cs2AgBiBr6 nanosheets with delicate control on the anchors of the cobalt catalysts. Among them, the molecular hybrid photocatalyst assembled by carboxyl anchors achieves the optimal performance with an electron consumption rate of 300±13 μmol g−1 h−1 for visible-light-driven CO2-to-CO conversion coupled with water oxidation to O2, over 8 times of the unmodified Cs2AgBiBr6 (36±8 μmol g−1 h−1), also far surpassing the documented systems (<150 μmol g−1 h−1). Besides the improved intrinsic activity, electrochemical, computational, ex-/in situ X-ray photoelectron and X-ray absorption spectroscopic results indicate that the electrons photogenerated at the Bi atoms of Cs2AgBiBr6 can be directionally transferred to the cobalt catalyst via the carboxyl anchors which strongly bind to the Bi atoms, substantially facilitating the interfacial electron transfer kinetics and thereby the photocatalysis. 相似文献