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.

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.

Peripheral octamethyl-substituted nickel(Ⅱ)-phthalocyanine-decorated carbon-nanotube electrodes for high-performance all-solid-state flexible symmetric supercapacitors

Construction of advanced electrode materials with unique performance for supercapacitors(SCs)is essential to achieving high implementation in the commercial market.Here,we report a novel peripheral octamethyl-substituted nickel(Ⅱ)phthalocyanine(Ni Me_(2)Pc)-based nanocomposite as the electrode material of all-solid-state SCs.The highly redox-active NiMe_(2)Pc/carboxylated carbon nanotube(CNTCOOH)dendritic nanocomposite provides rapid electron/electrolyte ion-transport pathways and exhibits excellent structural stability,resulting in high-capacity activity and impressive cycling stability.The composite prepared with the optimized weight ratio of Ni Me_(2)Pc:CNT-COOH(6:10)showed the highest specific capacitance of 330.5 F g^(-1)at 0.25 A g^(-1).The constructed NiMe_(2)Pc/CNT-COOH-based all-solid-state symmetric SC device showed excellent performance with a maximum energy density of 22.8 Wh kg^(-1)and outstanding cycling stability(111.6%retained after 35,000 cycles).Moreover,flexible carbon cloth significantly enhanced the energy density of the NiMe_(2)Pc/CNT-COOH all-solid-state symmetric device to 52.1 Wh kg^(-1)with 95.4%capacitance retention after 35,000 cycles,and it could be applied to highperformance flexible electronics applications.These findings provide a novel strategy to design phthalocyanine-based electrode materials for next-generation flexible SC devices.

Sodium-Coordinated Polymeric Phthalocyanines as Stable High-Capacity Organic Anodes for Sodium-Ion Batteries

Sodium-ion batteries(SIBs)have attracted considerable interest as an alternative to lithium-ion batteries owing to their similar electrochemical performance and superior long-term cycle stability.Organic materials are regarded as promising anode materials for constructing SIBs with high capacity and good retention.However,utilization of organic materials is rather limited by their low energy density and poor stability at high current densities.To overcome these limitations,we utilized a novel polymeric disodium phthalocyanines(pNaPc)as SIB anodes to provide stable coordination sites for Na ions as well as to enhance the stability at high current density.By varying the linker type during a one-pot cyclization and polymerization process,two pNaPc anodes with O-(O-pNaPc)and S-linkers(S-pNaPc)were prepared,and their structural and electrochemical properties were investigated.The O-pNaPc binds Na ions with a lower binding energy compared with S-pNaPc,which leads to more facile Na-ion coordination/dissociation when engaged as SIB anode.The use of O-pNaPc significantly improves the redox kinetics and cycle stability and allows the fabrication of a full cell against Na_(3)V_(2)(PO_(4))_(2)F_(3)/C cathode,which demonstrates its practical application with high energy density(288 Wh kg^(-1))and high power density(149 W kg^(-1)).

Conjugated polymerized bimetallic phthalocyanine based electrocatalyst with Fe-N_(4)/Co-N_(4) dual-sites synergistic effect for zinc-air battery

The bifunctional oxygen catalyst is essential for zinc-air batteries(ZABs).Here,an efficient bifunctional oxygen catalyst,PPcFeCo/3D-G,is obtained throughπ-πinteraction between the conjugated polymerized iron-cobalt phthalocyanine(PPcFeCo)with excellent thermal stability and three-dimensional graphene(3D-G).The bimetallic synergistic effect of PPcFeCo,verified by DFT(Density functional theory)calculation,andπ-πinteractions enhances the catalytic activity and durability of the PPcFeCo/3D-G.Regarding electrochemical performance,the PPcFeCo/3D-G with a high electron transfer number(3.98,@0.768 V vs.RHE)has excellent half-wave potential(E_(1/2)=0.890 V vs.RHE)and exhibits outstanding reversibility(ΔE=0.700 V,ΔE=Ej=10-E_(1/2)).The liquid ZAB(LZAB)employed PPcFeCo/3D-G displays a high power density(222 m W cm^(-2)),a specific capacity(792 m A h g-1),and excellent durability(120 h).This work has guiding significance for the preparation of high-efficiency bifunctional catalysts.

Cobalt phthalocyanine-based conjugated polymer as efficient and exclusive electrocatalyst for CO_(2) reduction to ethanol

Electrocatalytic conversion of carbon dioxide to high value-added chemicals is a promising method for solving the energy crisis and global warming.Electrochemical active metal-containing conjugated polymers have been widely studied for heterogeneous carbon dioxide reduction.In the present contribution,we designed and synthesized a stable cobalt phthalocyanine-based conjugated polymer,named CoPPc-TFPPy-CP,and also explored its electro-catalytic application in carbon dioxide reduction to liquid products in an aqueous solution.In the catalyst,cobalt phthalocyanine acts as building blocks connected with 1,3,6,8-tetrakis(4-formyl phenyl)pyrenes via imine-linkages,leading to mesoporous formation polymers with the pore size centered at 4.1nm.And the central co-balt atoms shifted to a higher oxidation state after condensation.With these chemical and structural natures,the catalyst displayed a remarkable electrocatalytic CO_(2) reduction performance with an ethanol Faradaic efficiency of 43.25%at-1.0V vs RHE.While at the same time,the electrochemical reduction process catalyzed by cobalt phthalocyanine produced only carbon monoxide and hydrogen.To the best of our knowledge,CoPPc-TFPPy-CP is the first example among organic polymers and metal-organic frameworks that produces ethanol from CO_(2) with a remarkable selectivity.

Structure of Cu-Phthalocyanine Vacuum Deposited on Inclined Glass Substrates

Cu-phthalocyanine is widely studied as a hole-transport layer in organic electronic devices. Since Cu-phthalocyanine is a molecular solid, the crystal structure depends on a circumstance to a great extent. Vacuum deposited layers were known to consist of two consecutive layers. In this article, Cu-phthalocyanine was deposited on the glass substrate inclined at several angles. The thickness of the first layer was found to be dependent on the substrate angle.

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.