Revealing the Multifunctional Electrocatalysis of Indium-Modulated Phthalocyanine for High-Performance Lithium-Sulfur Batteries

The sluggish kinetics of complicated multiphase conversions and the severe shuttling effect of lithium polysulfides(LiPSs)significantly hinder the applications of Li-S battery,which is one of the most promising candidates for the next-generation energy storage system.Herein,a bifunctional electrocatalyst,indium phthalocyanine self-assembled with carbon nanotubes(InPc@CNT)composite material,is proposed to promote the conversion kinetics of both reduction and oxidation processes,demonstrating a bidirectional catalytic effect on both nucleation and dissolution of Li_(2)S species.The theoretical calculation shows that the unique electronic configuration of InPc@CNT is conducive to trapping soluble polysulfides in the reduction process,as well as the modulation of electron transfer dynamics also endows the dissolution of Li_(2)S in the oxidation reaction,which will accelerate the effectiveness of catalytic conversion and facilitate sulfur utilization.Moreover,the InPc@CNT modified separator displays lower overpotential for polysulfide transformation,alleviating polarization of electrode during cycling.The integrated spectroscopy analysis,HRTEM,and electrochemical study reveal that the InPc@CNT acts as an efficient multifunctional catalytic center to satisfy the requirements of accelerating charging and discharging processes.Therefore,the Li-S battery with InPc@CNT-modified separator obtains a discharge-specific capacity of 1415 mAh g^(-1)at a high rate of 0.5 C.Additionally,the 2 Ah Li-S pouch cells deliver 315 Wh kg^(-1)and achieved 80%capacity retention after 50 cycles at 0.1 C with a high sulfur loading of 10 mg cm^(-2).Our study provides a practical method to introduce bifunctional electrocatalysts for boosting the electrochemical properties of Li-S batteries.

Pyrolysis of Copper Phthalocyanine as Non-noble Metal Electrocatalysts for Oxygen Reduction Reaction

We investigated the relationship between oxygen reduction reaction(ORR)activity and the pyrolysis temperature(650-850℃)of CuPc in alkaline solution.The highly active sites were formed through the decomposition of CuPc or Cu-N_(4) structure after releasing 4-nitrophthalonitrile.Cu-Nx incorporated with carbon were the main active sites.The XPS measurement results show that,at lower temperature,the contents of pyridinic-N and pyrrolic-N account for the most of the total N.As the temperature is higher than 750℃,the content of graphitic N(26.11%)increases and pyridinic-N(58.81%)becomes the dominant specie.When the temperature is higher than 850℃,the content of graphitic N increases remarkably and becomes the dominant species.Moreover,the specific surface areas decrease with increased pyrolysis temperature.Benefiting from the synergistic effect,the pyrolysis temperature at 750℃of CuPc displays superior electrocatalytic properties.The obtained results reveal that the fabricated non-noble metal catalysts can be used as low-cost,efficient catalyst for water splitting ORR in metal-air batteries and fuel cells.

Assessing the dynamics of O_(2) desorption from cobalt phthalocyanine by in situ electrochemical scanning tunneling microscopy

We report here the in situ electrochemical scanning tunneling microscopy(ECSTM) study of cobalt phthalocyanine(CoPc)-catalyzed O_(2) evolution reaction(OER) and the dynamics of CoPc-O_(2) dissociation.The self-assembled CoPc monolayer is fabricated on Au(111) substrate and resolved by ECSTM in 0.1 M KOH electrolyte.The OH^(-)adsorption on CoPc prior to OER is observed in ECSTM images.During OER,the generated O_(2) adsorbed on Co Pc is observed in the CoPc monolayer.Potential step experiment is employed to monitor the desorption of OER-generated O_(2) from CoPc,which results in the decreasing surface coverage of CoPc-O_(2) with time.The rate constant of O_(2) desorption is evaluated through data fitting.The insights into the dynamics of Co-O_(2) dissociation at the molecular level via in situ imaging help understand the role of Co-O_(2) in oxygen reduction reaction(ORR) and OER.

Indirect Electroanalysis of 3-Methyl-4-Nitrophenol in Water Using Carbon Fiber Microelectrode Modified with Nickel Tetrasulfonated Phthalocyanine Complex

Electrochemical detection of 3-methyl-4-nitrophenol (MNP) in direct phenol oxidation occurs at high potentials and generally leads to progressive passivation of the electrochemical sensor. This study describes the use of a carbon fiber microelectrode modified with a tetrasulfonated nickel phthalocyanine complex for the detection of MNP at a lower potential than that of direct phenol oxidation. The MNP voltammogram showed the presence of an anodic peak at -0.11 V vs SCE, corresponding to the oxidation of the hydroxylamine group generated after the reduction of the nitro group. The effect of buffer pH on the peak current and SWV parameters such as frequency, scan increment, and pulse amplitude were studied and optimized to have better electrochemical response of the proposed sensor. With these optimal parameters, the calibration curve shows that the peak current varied linearly as a function of MNP concentration, leading to a limit of detection (LoD) of 1.1 μg/L. These results show an appreciable sensitivity of the sensor for detecting the MNP at relatively low potentials, making it possible to avoid passivation phenomena.

Iron(Ⅲ) phthalocyanine chloride-catalyzed oxidation–aromatization of α,β-unsaturated ketones with hydrazine hydrate: Synthesis of 3,5-disubstituted 1H-pyrazoles

We have developed an iron（III） phthalocyanine chloride‐catalyzed oxidation–aromatization ofα,β‐unsaturated ketones with hydrazine hydrate. Various 3,5‐disubstituted 1H‐pyrazoles were obtained in good to excellent yields. This method offers several advantages, including room‐tem‐perature conditions, short reaction time, high yields, simple work‐up procedure, and use of air as an oxidant. The catalyst can be recovered and reused five times without loss of activity.

Influence of dye molecular structure on electron transfer in 2,9,16,23-tetracarboxy zinc phthalocyanine sensitized solar cell

2, 9, 16, 23-tetracarboxy zinc phthalocyanine （ZnTCPc） is synthesized and characterized by physicochemical and theoretical methods and it is used as a photosensitizer in dye-sensitized solar cells （DSSC）. The excited lifetime, band gap and frontier orbital distribution of ZnTCPc are investigated by fluorescence spectra, cyclic voltammetry and quantum calculation. The results show that the excited lifetime and band gap are 0. 1 ns and 1.81 eV, respectively. Moreover, it is found that the highest occupied molecular orbital （HOMO） location is not shared by both the zinc metal and the isoindoline ligands, and the lowest unoccupied molecular orbital（LUMO） location does not strengthen the interaction coupling between ZnTCPc and TiO：. As a result, the ZnTCPc-DSSC gains a short-circuit current density of 0. 147 mA/cm2, an open-circuit photovoltage of 277 mV, a fill factor of 0. 51 and an overall conversion efficiency of 0. 021%.

Study on the Synthesis and in vitro Photodynamic Anti-cancer Activity of Tetra(trifluoroethoxy) Germanium Phthalocyanine

The synthesis and in vitro photodynamic anticancer activity of a new photosen- sitizer, tetra（trifluoroethoxy） germanium phthalocyanine （GePcF）, were studied. GePcF was characterized by UV-Vis, IR, MS and elemental analysis. The in vitro photodynamic activity of GePcF was studied by MTT. IC50 of GePcF for SW480 cells of human colonic adenocarcinoma and HeLa cells of cervical cancer were 36.53 and 45.78 μmol/L, respectively. GePcF as a photosensitizer may be used to treat cancers due to its photodyrmmic anticancer activity.

Calculation of Visible Absorption Maxima of Phthalocyanine Compounds by Quantum Theory

Based on HYPERCHEM, the structures of five phthalocyanie compounds were optimized with PM3 and their visible absorption maxima were calculated with ZINDO/S method by selecting appropriate p-p overlap weighting factor (OWFp-p), the agreement with experiment was excellent. The relationship between OWF- and molecular structure parameters was obtained by the method of stepwise regression and was explained in terms of quantum theory. OWF-=0.58126+0.04562ANC1+0.03839X. Where, ANC1 and X are the symbols of average net charges on coordinated bonded nitrogens and electronegativity of central atom, respectively.

Synthesis and Photoconductivity of Nanosized Phthalocyanine

Functional phthalocyanine （Pc） compounds of H2Pc, TiOPc, FePc and CIAIPc were synthesized with a yield of 46.7%, 91.2%, 37.4% and 34.0%, respectively. Nanosized TiOPc was synthesized via a one-step sol-gel method and effects of surfactant doses, nucleation temperature on TiOPc particle size and photoconductivity were investigated. When re（PEG）： m（TiOPc） was 0.1 and nucleation temperature was 0℃, the as-obtained TiOPc had the smallest particle size and largest specific surface area, which were 60 nm and 83m^2/g, respectively. TiOPc synthesized under these conditions also exhibits excellent photoconductivity with charging potential V0, dark decay speed Rd and energy for half-discharging of potential E1/2 being 1160 V, 30 V/s and 0.6 1x.s, respectively.

First-Principles Study of Two Dimensional Transition Metal Phthalocyanine-Based Metal-Organic Frameworks in Kagome Lattice

Transition metal phthalocyanines (TMPc) and relevant derivatives can act as pervasive molecules for their electronic, magnetic, and optical applications. Numerous researches based on TMPc are carried out, attempting to synthesize novel two-dimensional (2D) metal-organic frameworks. Recently, some 2D poly-TMPc frameworks including FePc [J. Am. Chem. Soc. 133, 1203 (2011)], CoPc [Chem. Commun. 51, 2836 (2015)], and Ni-NiPc [J. Mater. Chem. A 6, 1188 (2018)] frameworks have been successfully synthesized experimentally. Meanwhile, potential applications in catalysis, gas storage, and spintronics were predicted by theoretical studies. Here, we propose a new kind of 2D poly-TMPc frameworks with kagome lattice (denoted as kag-TMPc) and systematically investigate their electronic and magnetic properties by employing first-principles calculations. We have demonstrated that the 2D kag-MnPc framework displays quite stable ferromagnetic ordering with Curie temperature about 125 K as indicated by Monte Carlo simulations based on Heisenberg model and prefers out-of-plane easy-magnetization axis. The 2D kag-CrPc framework is an ideal candidate for S=2 kagome antiferromagnet with RT3 magnetic order. Particularly, the investigations on optical absorption suggest that when the TMPc molecules are self-assembled into 2D kag- TMPc frameworks, their absorption wave bands are broadened, especially in visible region.

Studies on Metal Phthalocyanine as a Dual Functional Mimic Enzyme

Four phthalocyanines (iron tetracarboxylphthalocyanine, copper tetracarboxylphthalocyanine, manganese tetracarboxylphthalocyanine, cobalt tetracarboxylphthalocyanine) were used as dual functional mimic enzymes of superoxide dismutase (SOD) and catalase (CAT). The first function, eliminating O 2 -, was proved by using riboflavine methionine photoreduction method in the concentration range of 10 -5 to 10 -6 mol/L. The second function, clearing out H 2O 2, was demonstrated by means of spectrophotometry with the decomposing percentage being increased with the increase of the concentration of the imitating compounds. Measurements of metal phthalocyanines, SOD and CAT by the liver homogenate technique of mice showed that they had obvious action of decreasing the lipid peroxidation.

Covalent Functionalization of Carbon Nanotube by Tetrasubtituted Amino Manganese Phthalocyanine

The multiwall carbon nanotube (MWCNT) bonded to 2, 9, 16, 23-tetraamino manganese phthalocyanine (TAMnPc) was obtained by covalent functionalization, and its chemical structure was characterized by TEM. The photoconductivity of single-layered photoreceptors, where MWCNT bonded by TAMnPc (MWCNT-b-TAMnPc) served as the charge generation material (CGM), was also studied.

Enhancing Heterogeneous Catalytic Activity of Iron(II) Phthalocyanine by Ethanol and Its Application in 2,4-dichlorophenol Detection

A chemical system for facile and accurate detection of 2,4-dichlorophenol （DCP） via iron （Ⅱ） phthalocyanine （Fe（Ⅱ）Pc） catalyzed chromogenic reaction is reported for the first time. In this system, DCP could be oxidized by dioxygen with the catalysis of Fe（Ⅱ）Pc and then coupled with 4-aminoantipyrine （4-AAP） to generate pink antipyrilquinoneimine dye. Control experiments showed that the addition of ethanol could obviously enhance the catalytic activity of heterogeneous Fe（Ⅱ）Pc catalysts because of the partial dissolution of Fe（II）Pc nanocubes, which was confirmed by the SEM analysis. On the basis of the detection results of DCP in the range from 2×10^-5 to 9×10^-4 mol/L, we obtained a regression equation （A = 0.187 5 ＋ 0.01 209C （R2=-0.995 6）） with the detection limit （3σ） of 3.26×10^-6 mol/L, which could be successfully used in detecting the real samples.

Polymeric complex micelle loaded with axially substituted silicon(Ⅳ) phthalocyanine

A novel axially substituted silicon（IV） phthalocyanine, namely di-pyridyloxy axially substituted silicon（IV） phthalocyanine 2 was synthesized and characterized by UV/vis, IR, elemental analysis, MS as well as IH NMR spectroscopy. Hydrophobic 2 was encapsulated by amphiphilic triblock copolymer poly[N^e-（benzyloxycarbonyl-lysine]-poly（ethylene glycol）-poly [N^e-（benzyl oxycarbonyl） （PLL（Z）-b-PEG-b-PLL（Z）） to form hydrophobic 2-loaded polymeric complex micelle （PIC） （2-loaded P/C）. Atom force microscopy （AFM） image showed that 2-loaded PIC formed a spherical nanocarrier with approximately 35-50 nm in diameter. The fluorescence intensity and lifetime of 2-loaded PIC was significantly enhanced bv the incorporation 2 into PIC nanocarrier.

Tetraalkyl-substituted zinc phthalocyanines used as anode buffer layers for organic light-emitting diodes

Two soluble tetraalkyl-substituted zinc phthalocyanines(ZnPcs)for use as anode buffer layer materials in tris(8-hydroxyquinoline)aluminum(Alq3)-based organic light-emitting diodes(OLEDs)are presented in this work.The holeblocking properties of these Zn Pc layers slowed the hole injection process into the Alq3 emissive layer greatly and thus reduced the production of unstable cationic Alq3(Alq3^+)species.This led to the enhanced brightness and efficiency when compared with the corresponding properties of OLEDs based on the popular poly-(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)buffer layer.Furthermore,because of the high thermal and chemical stabilities of these Zn Pcs,a nonaqueous film fabrication process was realized together with improved charge balance in the OLEDs and enhanced OLED lifetimes.

Synthesis and photophysical properties of metal anthraquinone phthalocyanine

A novel anthraquinone phthalocyanine AI（Ⅲ） 4 and Co（Ⅱ） 5 were synthesized and characterized by elemental analysis, IR UV/ vis, ^1H NMlL HPLC and MS. The photophysical properties of the two metal complexes were studied and compared by fluorescence spectrum method.

A Fiber Optic Sensor for Determination of 2,4-dichlorophenol based on Iron(Ⅱ) Phthalocyanine Catalysis

A new fi ber optic sensor based on the oxidation of 2,4-dichlorophenol（DCP） catalyzed by iron（II） phthalocyanine（Fe（II）Pc） was developed for the determination of DCP. The optical oxygen sensing fi lm containing fl uorescence indicator Ru（bpy）3Cl2 was used to detect the consumption of oxygen in solution. Moreover, a lock-in amplifier was used to determine the lifetime of the sensor head by detecting its phase delay change. The results reveal that the sensor has a linear detection range of 1.0×10^-6- 9.0×10^-5 mol/L and a response time of 5 min. The sensor also has high selectivity, good repeatability and stability. It can be used effectively to determine DCP concentration in real samples.

Zinc phthalocyanine as an efficient catalyst for halogen-free synthesis of formamides from amines via carbon dioxide hydrosilylation under mild conditions

The combination of a zinc phthalocyanine(ZnPc)catalyst and a stoichiometric amount of dimethyl formamide(DMF)provided a simple route to formamide derivatives from amines,CO2,and hydrosilanes under mild conditions.We deduced that formation of an active zinc‐hydrogen(Zn‐H)species promoted hydride transfer from the hydrosilane to CO2.The cooperative activation of the Lewis acidic ZnPc by strongly polar DMF,led to formation of activated amines and hydrosilanes,which promoted the chemical reduction of CO2.Consequently,the binary ZnPc/DMF catalytic system showed excellent yields and superior chemoselectivity,representing a simple and sustainable pathway for the reductive transformation of CO2into valuable chemicals as an alternative to conventional halogen‐containing process.

A bipolar metal phthalocyanine complex for sodium dual-ion battery

Dual-ion batteries(DIBs) have attracted immense interest as a new generation of energy storage device due to their low cost,environmental friendliness and high working voltage.However,developing DIBs using organic compounds as active electrode materials is in its infancy.Herein,we first report a bipolar and self-polymerized Cu phthalocyanine(CuTAPc) as an electrode material for sodium-based DIBs(SDIBs).Benefitting from the bipolar property,CuTAPc could serve as the cathode or anode material to construct metal sodium-based or metal sodium-free SDIB(cell 1 or 2) by coupling with sodium anode or graphite cathode,respectively.As a result,cell 1 displays a high discharge capacity of 195.7 mAh g^(-1) at 50 mA g^(-1) and a high reversible capacity of 57 mAh g^(-1) over 2500 cycles at 1 A g^(-1),and cell 2 shows a high energy density of 324 Wh kg^(-1) and a high power density of 7481 W kg^(-1).Subsequently,the proposed binding mechanism and the bipolar reactivity of CuTAPc have been revealed by the detailed reaction kinetic analysis and ex-situ techniques as well as the density functional theory(DFT) calculations.This work could open a pathway to develop the advanced SDIBs constructed by elemental abundant and environmentally friendly organic materials.

Evaluation of Silicon Phthalocyanine 4 Photodynamic Therapy against Human Cervical Cancer Cells in Vitro and in Mice

Background: Cervical cancer is the second most common cancer in women worldwide [1]. Photodynamic therapy has been used for cervical intraepithelial neoplasia with good responses, but few studies have used newer phototherapeutics. We evaluated the effectiveness of photodynamic therapy using Pc 4 in vitro and in vivo against human cervical cancer cells. Methods: CaSki and ME-180 cancer cells were grown as monolayers and spheroids. Cell growth and cytotoxicity were measured using a methylthiazol tetrazolium assay. Pc 4 cellular uptake and intracellular distribution were determined. For in vitro Pc 4 photodynamic therapy, cells were irradiated at 667 nm at a fluence of 2.5 J/cm2 at 48 h. SCID mice were implanted with CaSki and ME-180 cells both subcutaneously and intracervically. Forty-eight hours after Pc 4 photodynamic therapy was administered at 75 and 150 J/cm2. Results: The IC50s for Pc 4 and Pc 4 photodynamic therapy for CaSki and ME-180 cells as monolayers were, 7.6 μM and 0.016 μM and >10 μM and 0.026 μM;as spheroids, IC50s of Pc 4 photodynamic therapy were, 0.26 μM and 0.01 μM. Pc 4 was taken up within cells and widely distributed in tumors and tissues. Intracervical photodynamic therapy resulted in tumor death, however mice died due to gastrointestinal toxicity. Photodynamic therapy resulted in subcutaneous tumor death and growth delay. Conclusions: Pc 4 photodynamic therapy caused death within cervical cancer cells and xenografts, supporting development of Pc 4 photodynamic therapy for treatment of cervical cancer. Support: P30-CA47904, CTSI BaCCoR Pilot Program.