Copper Phthalocyanine Tetrasulfonic Acid Research Articles

Copper Phthalocyanine Tetrasulfonic Acid, a Recyclable Solid Acid Catalyst for the Synthesis of Aryl Iodides and Azides from Aryl Amines via Diazotization

Copper Phthalocyanine Tetrasulfonic Acid, a Recyclable Solid Acid Catalyst for the Synthesis of Aryl Iodides and Azides from Aryl Amines via Diazotization

Copper phthalocyanine tetrasulfonic acid (CuPcS) as an efficient recyclable catalyst for aromatic nitration using sodium nitrate

Nitration of aromatic compounds is an important transformation in synthetic organic chemistry. It becomes imperative to design a highly efficient and environmentally friendly protocol for the synthesis of nitro compounds. Towards this goal, we have developed copper phthalocyanine tetrasulfonic acid as a biodegradable and recyclable solid acid catalyst for aromatic nitration. As a result of the reaction performed, it was observed that copper phthalocyanine tetrasulfonic acid has excellent catalytic activity and can also be recycled after completion of the reaction. So this method of aromatic nitration would be more efficient, greener, and safer than the conventional method. This catalyst has been used to nitrate both activated and deactivated aromatic rings under mild conditions, and it has the ability to synthesize nitro compounds sustainably.

Fabrication of a novel solar cell using copper phthalocyanine tetrasulfonic acid tetrasodium salt / graphene oxide

Fabrication of a novel solar cell using copper phthalocyanine tetrasulfonic acid tetrasodium salt / graphene oxide

Novel composite Nafion membranes modified with copper phthalocyanine tetrasulfonic acid tetrasodium salt for fuel cell application

In this paper, Nafion membrane was firstly modified by copper phthalocyanine tetrasulfonic acid tetrasodium salt (CuTSPc) to prepare the Nafion/CuTSPc-x composite membranes. FTIR, XRD and SEM results revealed the successful incorporation of CuTSPc into Nafion and good compatibility between the two composites. The proton conductivities of the Nafion/CuTSPc-x composite membranes were evidently higher than pure cast Nafion membrane, and increased with CuTSPc contents. Among them, the Nafion/CuTSPc-6% membrane with the highest ion exchange capacity (1.14 mequiv•g−1) exhibited the highest proton conductivity of 0.084 S cm−1 at 30 °C and 0.131 S cm−1 at 80 °C, respectively. When fabricated of a membrane electrode assembly (MEA), the Nafion/CuTSPc-4.5% membrane displayed an initial fuel cell performance with a power density of 43.3 mW cm−2 at room temperature, close to that for pure cast Nafion membrane. Benefiting from the compact structure, high proton conductivity and outstanding stability, the Nafion/CuTSPc-x composite membranes show promising potentials for fuel cell applications.

Effect of annealing and chemical treatment on structural and optical properties of CuPcTs/PEDOT:PSS (BHJ Blend) thin films

In this work, The effect of annealing treatment at different temperatures (373, 423 and 473) K and chemical treatment with talwen at different immersion time (40, 60 and 80) min on structural and optical properties of the bulk heterojunction (BHJ) blend copper phthalocyanine tetrasulfonic acid tetrasodium salt/poly dioxyethylenethienylene doped with polystyrenesulphonic acid (CuPcTs/PEDOT:PSS) thin films were investigated. The films were fabricated using spin coating technique. X-ray diffraction (XRD) measurements displayed only one peak at 2θ =4.5o corresponding to (001) direction which has dhkl larger than for standard CuPcTs. The dhkl increase then decrease with increasing annealing temperature andthe time of chemical treatment with talwen. FTIR measurements show that, the peaks for O-H, in general, decrease with increasing annealing temperature, while the peaks corresponding to C=C aromatic bond and C-N bond decrease at 373 K then increase at 423 and 473 K. The peaks for O-H, in general, decrease with increasing immersing time, while the peaks corresponding to C=C aromatic bond and C-N bond decrease at 40 min then increase at more immersing time. From UV-visible measurements, the absorption spectra peaks for B and Q-bands increase at 373K and at 40 min immersing time with talwen and decrease at more annealing or chemical treated time.

Effect of asymmetrical peripheral substitution of sulfonic acid group on the geometric and electronic structures and vibrations of copper phthalocyanine studied by computational and experimental techniques

The optimized geometry and vibrational frequencies of an organic compound copper phthalocyanine tetrasulfonic acid tetra sodium salt (CuPcTS) have been investigated using density functional theory. We have also optimized the structures of copper phthalocyanine (CuPc) and its substituted complex and simulated their vibrational spectra to study the substitution effects of sulfonic acid group at the peripheral sites of copper phthalocyanine. Experimentally, vibrational frequencies of these molecules have been studied using infrared absorption, Raman spectroscopic techniques. It has been found that the vibrational frequencies obtained from the theoretical studies generally agree with the experiment. Most of the bands show red shift in CuPcTS due to decrease of stretching force constant of CC and reduction in the contribution from in-plane CH bending vibrations. New bands have been observed due to SO vibrations. Degeneracy of IR bands is removed because of change of symmetry from D4h in CuPc to C1 in substituted CuPc. Effect of substitution on the structural parameters and mode compositions of the vibrational bands have also been studied. The electronic absorption spectra of the substituted copper phthalocyanine in different solvents have been studied using UV–Vis spectroscopy. It has been found that the substituted copper phthalocyanine shows aggregation effect in water because of greater extent of hydrogen bonding. The direct optical band gap energy and refractive index of CuPcTS have also been calculated in the different solvents. We have also plotted the IV characteristic for both the molecules and it has been found that electrical and photoconductivity of CuPcTS is more as compared to CuPc. The intermolecular charge transfer interactions have been studied by HOMO-LUMO and natural bonding orbital (NBO) analysis. The values of first order hyperpolaizability for both the molecules indicate that substituted copper phthalocyanine acquires excellent non-linear optical (NLO) properties. The interaction sites of the both the molecules have been studied by the molecular electrostatic potential (MEP) and solvent accessible surface area (SASA) analysis.

The Effect of Heat Treatment on Optical Properties of Copper (II) Phthalocyanine Tetrasulfonic Acid Tetrasodium Salt (CuPcTs) Organic Thin Films

Copper (II) phthalocyanine Tetrasulfonic Acid Tetrasodium Salt (CuPcTs) thin films have been prepared using a simple spin coating method on glass substrates. Thin films (100 ± 5 nm thickness) annealed at temperatures of (100, 150 and 200) ∘C for one hour. The optical properties of thin CuPcTs films have been investigated in the spectral range of (300-900) nm by using the (UV-Vis) spectrophotometer. The annealed film at 100 ∘C shows the highest absorbance whereas, the lowest was at the room temperature. All films have identical absorption coefficient patterns, α in the absorption region revealed direct transition. Analysis of α as well as the dielectric constants ei and er reveal two absorption peaks in mentioned spectral region. The results showed that the optical band gaps depended on the temperature. The film annealed at 100 ∘C has the lowest optical energy gap. FTIR measurements were tested in the infrared range of (400-4000) cm− 1to evaluate the position and bonds of CuPcTs as a comparison with H2Pc as a reference. Photoluminescence spectroscopy was applied to improve the results of (UV-Vis) measurements and get more exact value of optical energy gap. The energy band gaps have been estimated as (1.83 ± 0.05) and (3.18 ± 0.04) eV for Q and B bands respectively. In this work, the Capacitive-Resistive temperature sensor has been fabricated. The sensor shows response to variation of temperature in the range of (RT-200) ∘C and the response time of ≈ 20 ± 5 Sec. For two electrodes (Aluminum and silver), our results have shown that the aluminum electrode has a higher capacitance and resistance than silver electrode depending on the different frequency values. While the silver electrode has the shortest response time.

Sulfonated Copper Phthalocyanine/Sulfonated Polysulfone Composite Membrane for Ionic Polymer Actuators with High Power Density and Fast Response Time.

Ionic polymer composite membranes based on sulfonated poly(arylene ether sulfone) (SPAES) and copper(II) phthalocyanine tetrasulfonic acid (CuPCSA) are assembled into bending ionic polymer actuators. CuPCSA is an organic filler with very high sulfonation degree (IEC = 4.5 mmol H+/g) that can be homogeneously dispersed on the molecular scale into the SPAES membrane, probably due to its good dispersibility in SPAES-containing solutions. SPAES/CuPCSA actuators exhibit larger ion conductivity (102 mS cm-1), tensile modulus (208 MPa), strength (101 MPa), and strain (1.21%), exceptionally faster response to electrical stimuli, and larger mechanical power density (3028 W m-3) than ever reported for ion-conducting polymer actuators. This outstanding actuation performance of SPAES/CuPCSA composite membrane actuators makes them attractive for next-generation transducers with high power density, which are currently developed, e.g., for underwater propulsion and endoscopic surgery.

P-CuPcTS/n-SnO2 organic-inorganic hybrid film for ppb-level NO2 gas sensing at low operating temperature

Design and fabrication of organic-inorganic hybrid sensing materials is a promising strategy to combine the advantages of good stability of inorganic species and high sensitivity, selectivity and low operating temperature of organic ones. In this work, CuPcTS(Copper (II) Phthalocyanine Tetrasulfonic Acid Tetrasodium Salt)/SnO2 organic-inorganic hybrid film was prepared through a simple soak-assembling process. The p-type CuPcTS molecules were homogenously adsorbed on the surfaces of n-type SnO2 film to form p-n heterojunctions. Due to the low adsorption energy of NO2 on CuPcTS at low temperature, the CuPcTS/SnO2 hybrid film exhibits significantly improved sensing performance towards ppb-level NO2 with high sensitivity (Rg/Ra=2400 up to 1ppm NO2), ultra-low theoretical detection limit (∼40ppb when signal-to-noise ratio is 3) and excellent selectivity. The ultrahigh sensitivity and selectivity upon ppb-level NO2 indicate the promising capability of CuPcTS/SnO2 hybrid film for environmental monitoring of NO2 concentrations.

Study of the surface mass changes during the redox transformations of copper(II) phthalocyanine-tetrasulfonic acid on gold in acidic media

An electrochemical quartz crystal nanobalance (EQCN) has been used to study the deposition (adsorption) and dissolution (desorption) during the redox transformations of the water-soluble copper phthalocyanine-tetrasulfonic acid (CuPcTS) on a gold electrode in contact with aqueous acid solutions. The anomalous cyclic voltammetric responses that had been observed invoked the application of the EQCN technique. Indeed, it became evident that during the electroreduction in certain potential ranges, deposition/dissolution processes take place on the gold surface. Surprisingly, complex changes have been observed even when the cyclic voltammetric curves seem to be regular, i.e., characteristic to the responses of soluble redox pairs. Beside the cyclic voltammetry, EQCN was combined with galvanostatic measurements detecting the chronopotentiometric curves with the simultaneous mass changes. A reaction sequence has been suggested for the elucidation of the events occurring during the reduction and reoxidation of CuPcTS.

Marine sponge skeleton photosensitized by copper phthalocyanine: A catalyst for Rhodamine B degradation

AbstractWe present a combined approach to photo-assisted degradation processes, in which a catalyst, H2O2 and UV irradiation are used together to enhance the oxidation of Rhodamine B (RB). The heterogeneous photocatalyst was made by the process of adsorption of copper phthalocyanine tetrasulfonic acid (CuPC) onto purified spongin-based Hippospongia communis marine sponge skeleton (HcS). The product obtained, CuPC-HcS, was investigated by a variety of spectroscopic (carbon-13 nuclear magnetic resonance 13C NMR, Fourier transform infrared spectroscopy FTIR, energy-dispersive X-ray spectroscopy EDS) and microscopic techniques (scanning electron microscopy SEM, fluorescent and optical microscopy), as well as thermal analysis. The study confirms the stable combination of the adsorbent and adsorbate. For a 10 mg/L RB solution, the percentage degradation reached 95% using CuPC-HcS as a heterocatalyst. The mechanism of RB removal involves adsorption and photodegradation simultaneously.

Blue membranes: Sulfonated copper(II) phthalocyanine tetrasulfonic acid based composite membranes for DMFC and low relative humidity PEMFC

Polymer electrolyte membranes (PEMs) consisting of copper(II)phthalocyanine tetrasulfonic acid tetrasodium salt (CuPCSA) and disulfonated poly(arylene ether sulfone) (SES0005) are prepared. The TEM analysis results prove the incorporation of CuPCSA as nanoparticles into the composite membranes. Catalytic activity of CuPCSA towards peroxide degradation is shown by CV. Addition of CuPCSA increases the dimensional stability in contact with water (18% vs. 43% linear swelling for pristine SES0005). Addition of 10wt% CuPCSA (SES0005-IM10) increases the proton conductivity four fold to 16.8mScm−1 at 120°C and 50% relative humidity (rh). Activation energy decreases with CuPCSA content, reducing the conductivity's temperature dependence. Membranes were tested in low and medium temperature PEM fuel cells at 65 and 120°C, respectively, at 50% rh. In the LT-PEMFC, 40µm thick SES0005-IM10 and Nafion 212 based MEAs exhibited current densities of 470 and 454mAcm−2 at 0.7V, respectively. In the MT-PEMFC, SES0005-IM10 based MEAs demonstrated a current density of 405mAcm−2 at 0.5V, 2.4 folds more than pristine membrane based MEAs. In the DMFC, SES0005-IM10 enabled a peak power density of 153mWcm−2 at 70°C and 1M methanol feed, 20% higher than Nafion 212, 38% higher than mPES60.

Effect of Acid-Leaching on the Electrochemical Performance of Carbon-Supported Copper Phthalocyanine Tetrasulfonic Acid Tetrasodium Salt (CuTSPc/C) Catalys

Since the strong O=O bond (498kJ mol-1) with very slow oxygen reduction reaction (ORR) rate at the cathode has a much larger overpotential (or polarization) than that of hydrogen oxidation reaction (HOR) at the anode, the cathodic ORR has become the most challenging step in a fuel cell1. Up to now, Pt is still the best catalyst candidate for the ORR due to its high catalytic activity. As yet, there are still two major challenges for the Pt-based catalysts, one is high cost, and the other is insufficient electrochemical durability2-3. Therefore, the major effort in fuel cell research and development have been put on reducing Pt loading by exploring more effective synthesis technologies, and/or replacing Pt metal using other non-precious metals such as Fe, Co and Cu. In this regard, carbon-based transition metal macrocycle complexes catalysts have become one of the most promising candidates to replace Pt/C catalyst, especially these catalysts synthesized after thermal treatment show high catalytic activity3,4. For revealing the mechanism of ORR and improving the ORR activity, one should know the active site in these catalysts. So far, there is a consensus that carbon, nitrogen and transition metals are all considered to be indispensable elements for the ORR activity5. However, for the transition metals, there is few report clearly point out whether it is a part of the active sites in these macrocycle complexes. In this work, with carbon-supported copper phthalocyanine tetrasulfonic acid tetrasodium salt, CuTSPc/C, as a target, the role of transition metal in macrocycle complexe was investigated by acid-leaching procedures.

Effect of acid-leaching on carbon-supported copper phthalocyanine tetrasulfonic acid tetrasodium salt (CuTSPc/C) for oxygen reduction reaction in alkaline electrolyte: active site studies

Although the non-precious metal catalysts have been extensively studied as low-cost catalyst alternatives to Pt for oxygen reduction reaction (ORR), the nature of the active ORR catalytic sites is still a subject of controversy.

Simultaneous formation of nitrogen and sulfur-doped transition metal catalysts for oxygen reduction reaction through pyrolyzing carbon-supported copper phthalocyanine tetrasulfonic acid tetrasodium salt

In this work, we report a spontaneous formation of copper (Cu–N–S/C) catalysts containing both nitrogen (N) and sulfur (S) elements using a one-step pyrolysis of carbon supported copper phthalocyanine tetrasulfonic acid tetrasodium salt (CuTSPc/C). The obtained catalysts exhibit high catalytic activities for oxygen reduction reaction (ORR) in alkaline media. Through electrochemical measurements and physical characterizations, several observations are reached as follows: (1) different pyrolysis temperatures can result in different catalyst structures and performances, and the optimum pyrolysis temperature is found to be 700 °C; (2) the electron transfer number of the ORR process catalyzed by the unpyrolyzed catalyst is about 2.5, after the pyrolysis, this number is increased to 3.5, indicating that the pyrolysis process can change the ORR pathway from a 2-electron transfer dominated process to a 4-electron transfer dominated one; (3) increasing catalyst loading from 40 μg cm−2 to 505 μg cm−2 can effectively improve the catalytic ORR activity, under which the percentage of H2O2 produced decreases sharply from 39.5% to 7.8%; and (4) the Cu ion can bond on pyridinic–N, graphite–N and C–Sn–C to form Cu–N–S/C catalyst active sites, which play the key role in the ORR activity.

Bipolar membrane modified by cation/anion exchange nanofibers containing copper phthalocyanine derivatives with different substituents

Carboxymethyl cellulose (CMC)-polyvinyl alcohol (PVA) and chitosan (CS)-polyvinyl alcohol were cross-linked by Fe3+ and glutaraldehyde respectively to prepare the cation exchange membrane layer and the anion exchange membrane layer, polyvinyl alcohol-sodium alginate (SA)-copper phthalocyanine tetrasulfonic acid (CuTsPc, or copper tetracarboxy phthalocyanine: CuTcPc) cation exchange nanofibers or polyvinyl alcohol-chitosan-copper tetraaminophthalocyanine (CuTAPc) anion exchange nanofibers prepared by electrospinning technique were introduced into the interlayer to obtain the modified bipolar membrane (BPM). The experimental results showed that in comparison with the BPM without the cation/anion exchange nanofibers interlayer, the water splitting efficiency of the modified BPM was obviously increased, and its membrane impedance decreased. When the concentration of CuTsPc in the PVA-SA-CuTsPc nanofibers was 3.0 %, the transmembrane voltage drop (IR drop) of the CMC-PVA/PVA-SA-CuTsPc/CS-PVA BPM was as low as 0.5 V at a high current density of 90 mA·cm−2.

The Oxygen Reduction Reaction Catalyzed By Carbon-Supported Copper Phthalocyanine Tetrasulfonic Acid (CuPcTSA/C) By High Temperature Treatment

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The Oxygen Reduction Reaction Catalyzed by Carbon-Supported Copper Phthalocyanine Tetrasulfonic Acid (CuPcTSA/C) by High Temperature Treatment

This work reports the preparation and electrochemical property of carbon-supported copper phthaloctyanine tetrasulfonic acid (CuPcTSA/C) for oxygen reduction reaction (ORR) in alkaline media. The catalyst was synthesized via a combined solvent-impregnation. For optimizing the electrocatalytic activity, the catalyst obtained at room temperature was further treated at high temperature ranged from 600 to 800oC. The catalytic activity was found to be strongly dependent on the heat-treated temperature. Results of electrochemical characterization, which was performed using a rotating disc electrode (RDE) by cyclic voltammetry (CV) and liner sweep voltammetry (LSV), with emphasis on the activity of the catalyst were presented. The resulting CuPcTSA/C-700 of 40/60 mass ratio showed the best catalytic activity in terms of ORR among the overall prepared catalysts, where the onset potential at 0.11V and a half-wave potential at 0.03V were achieved.

Photocatalytic degradation of rhodamine B by dye-sensitized TiO2 under visible-light irradiation

Perylene tetracarboxylic diimide (PTCDI), widely used in organic photovoltaic devices, is an n-type semiconductor with strong absorption in the visible-light spectrum. There has been almost no study of the PTCDI-sensitized TiO2 composite used to photocatalytically degrade pollutants. In this study, PTCDI- and copper phthalocyanine tetrasulfonic acid (CuPcTs)-sensitized TiO2 composites were prepared using a hydrothermal method. The morphologies and structures of the two composites were characterized by X-ray diffraction, transmission electron microscopy, ultraviolet-visible spectroscopy, and fluorescence spectroscopy. The visible-light photocatalytic activities of the composites were evaluated using the degradation of rhodamine B as a model reaction. Results showed that dye-sensitized TiO2 samples had a wider absorption spectrum range and higher visible-light photocatalytic activity compared to TiO2 samples. The double dye-sensitized (or co-sensitized) TiO2 composite with efficient electron collection exhibited higher photocatalytic activity than did the single dye-sensitized TiO2 composite. The electron transfer processes of single and double dye-sensitized TiO2 composites were illustrated according to band theory.

Molecular level studies on binding modes of labeling molecules with polyalanine peptides

In this work, the binding modes of typical labeling molecules (thioflavin T (ThT), Congo red (CR) and copper(II) phthalocyanine tetrasulfonic acid tetrasodium salt (PcCu(SO(3)Na)(4))) on pentaalanine, which is a model peptide segment of amyloid peptides, have been resolved at the molecular level by using scanning tunneling microscopy (STM). In the STM images, ThT molecules are predominantly adsorbed parallel to the peptide strands and two binding modes could be identified. It was found that ThT molecules are preferentially binding on top of the peptide strand, and the mode of intercalated between neighboring peptides also exists. The parallel binding mode of CR molecules can be observed with pentaalanine peptides. Besides the binding modes of labeling molecules, the CR and PcCu(SO(3)Na)(4) display different adsorption affinity with the pentaalanine peptides. The results could be beneficial for obtaining molecular level insight of the interactions between labeling molecules and peptides.