Synchronous Synthesis and Immobilization of Metal Phthalocyanine for Aerobic Oxidation of Styrene

In this study,the precursor 4-(4-carboxy-phenoxy)phthalonitrile(CPPN)was first bonded onto the silica gel surface modified with poly(glycidyl methacrylate)(PGMA)(PGMA/SiO2)to prepare CPPN-PGMA/SiO2,and metal phthalocyanine(MPc;M=Co,Fe,Cu,Mn)was supported on the PGMA/SiO2 surface to prepare MPc-PGMA/SiO2 by synchronous synthesis and immobilization with phthalonitrile and metal salt in the solution.The chemical composition and surface morphology were characterized by the Fourier transform infrared(FTIR)spectroscopy,UV-Vis spectroscopy,scanning electron microscopy(SEM),X-ray photoelectron spectroscopy(XPS),and thermogravimetry analysis(TGA).The catalytic performance of MPc-PGMA/SiO2 in epoxidation of styrene was also investigated with molecular oxygen acting as the oxidant.The results show that MPc-PGMA/SiO2 can efficiently and selectively catalyze molecular oxygen for oxidation of styrene to styrene oxide under mild conditions.However,the catalytic activity differs substantially depending on the central metal,and a highest catalytic activity is achieved by CoPc-PGMA/SiO2.The CoPc-PGMA/SiO2 amount and temperature can also affect the catalytic oxidation of styrene,and at normal atmospheric pressure,a maximum conversion rate of styrene(99%)and selectivity of styrene oxide(53%)are obtained using 0.1 g of CoPc-PGMA/SiO2(22.61μmol of CoPc)at 100℃ for 6 h.CoPc-PGMA/SiO2 also has excellent reusability,and the conversion rate of styrene is still over 90%after 5 cycles.

Synthesis and Spectroscopic Properties of a Series of New tetra-Substituted Metal Phthalocyanines

A new class of metal phthalocyanines（MPcs） containing four 8-quinolinol（8-QH） derivative moieties were successfully synthesized and characterized by mass spectroscopy, IR, UV-Vis and element analysis, the results of which were consistent with the proposed structures. All of them can dissolve in common organic solvents, such as dichloromethane, chloroform, and acetone. The effect of metal ion on the absorption of Q band was studied with UV-Vis spectra. The fluorescent properties for those complexes were also investigated.

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.

Theory-Driven Design of Electrocatalysts for the Two-Electron Oxygen Reduction Reaction Based on Dispersed Metal Phthalocyanines

The two-electron electrochemical reduction of oxygen is an appealing approach to produce hydrogen peroxide.Metal and heteroatom-doped carbon(M–X/C)materials have recently been recognized as compelling catalysts for this process,but their performance improvement is generally hindered by the ill-defined structures of active sites.Herein,we demonstrate a theory-driven design of catalysts for oxygen reduction reactions based on molecularly dispersed electrocatalysts(MDEs)with metal phthalocyanines on carbon nanotubes.Density functional theory calculations suggest that nickel phthalocyanine(NiPc)favors the formation of*H_(2)O_(2) over*O,thus acting as a selective catalyst for peroxide production.NiPc MDE shows high peroxide yields of∼83%,superior to the aggregated NiPc and pyrolyzed Ni–N/C catalysts.The performance is further enhanced by the introduction of the cyano group(CN).NiPc–CN MDE exhibits∼92%peroxide yields and good stability.Our studies provide a new perspective for the development of heterogeneous electrocatalysts for hydrogen peroxide production from metal macrocyclic complexes.

Quantum Spin Exchange Interactions to Accelerate the Redox Kinetics in Li–S Batteries

Spin-engineering with electrocatalysts have been exploited to suppress the“shuttle effect”in Li–S batteries.Spin selec-tion,spin-dependent electron mobility and spin potentials in activation barriers can be optimized as quantum spin exchange interactions lead-ing to a significant reduction of the electronic repulsions in the orbitals of catalysts.Herein,we anchor the MgPc molecules on fluorinated carbon nanotubes(MgPc@FCNT),which exhibits the single active Mg sites with axial displacement.According to the density functional theory calculations,the electronic spin polarization in MgPc@FCNT not only increases the adsorption energy toward LiPSs intermediates but also facilitates the tunneling process of electron in Li–S batter-ies.As a result,the MgPc@FCNT provides an initial capacity of 6.1 mAh cm^(-2) even when the high sulfur loading is 4.5 mg cm^(-2),and still maintains 5.1 mAh cm^(-2) after 100 cycles.This work provides a new perspective to extend the main group single-atom catalysts enabling high-performance Li–S batteries.

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.

Preparation & Properties Research of Two Indium Phthalocyanine Materials

Two iodo（phthalocyainato） indium complexes were synthesized and mixed with polymer solution（PMMA/chloroform）to prepare iodo（phthalocyainato）indium/PMMA compound film materials on a glass slice by the method of dipping film.Two materials have typical B-band and Q-band absorption of Phthalocyanine compounds in the UV-Vis spectrum.The reverse saturable absorption experiments show that two materials have better reverse saturable absorption properties while they have higher linear transmissivity.In addition,the highest transmittance of visible light is over 70%（tetrakis（cumylphenoxy）phthalocyainate indium/OMMA compound film material）.The initial threshold is 127.1mJ/cm^2.The dynamic range is 1.43.It can be concluded that introduction of the substituted groups having bigger steric hindrance and conjugative effect in the Phthalocyanine ring may increase the reverse saturable absorption effect of the Phthalocyanine indium material.

Non-peripherally octaalkyl-substituted nickel phthalocyanines used as non-dopant hole transport materials in perovskite solar cells

This report presents two non-perihperally octaalkyl-substituted nickel phthalocyanines(NiPcs),namely,NiEt2Pc and NiPr_(2)Pc,for use as dopant-free hole transport materials in perovskite solar cells(PSCs).The length extension of the alkyl chains from ethyl to propyl significantly tunes the NiPcs’energy levels,thus reducing charge carrier recombination at the perovskite/hole transport layer(HTL)interface and leading to higher open-circuit voltage(VOC)and short-circuit current density(JSC)observed for the NiPr_(2)Pc-based PSC.And higher charge carrier mobility,higher thin film crystallinity,and lower surface roughness of the NiPr_(2)Pc HTL compared with that of the NiEt2Pc one also lead to higher JSC and fill factor(FF)observed for the NiPr_(2)Pc-based device.Consequently,the NiPr_(2)Pc-based PSC exhibits a higher power conversion efficiency(PCE)of 14.07%than that of the NiEt2Pc-based device(8.63%).

Reformation of thiophene-functionalized phthalocyanine isomers for defect passivation to achieve stable and efficient perovskite solar cells

Lewis acid–base passivation is a significant technique to achieve structural stability of perovskite solar cells(PSCs) by overcoming the issues of wide grain boundaries, crystal defects, and the instability of PSCs. In this work, the combined effects of thiophene with phthalocyanine(Pc) as isomers(S2 and S3)on the photovoltaic performance of PSCs were studied for the first time. Through density functional theory calculations, we confirmed that the position of the S atom in the structure affects Lewis acid–base interactions with under-coordinated Pb^(2+) sites. The morphology of methylammonium lead iodide(MAPbI_(3)) for passivated devices was improved and thin dense layers with compact surface and large grain size were observed, leading to improvement of the charge extraction ability and reduction of non-radiative recombination and the trap density. A highest power conversion efficiency of 18% was achieved for the Pc S3 passivated device, which was 6.69% more than that of the controlled device.Furthermore, the Pcs passivated devices demonstrated remarkable stability under high-moisture and high-temperature conditions.

Activation of Carbon Dioxide and Synthesis of Propylene Carbonate

Cycloaddition of carbon dioxide and propylene oxide to propylene carbonate catalyzed by tetra-tert-butyl metal phthalocyanine in the presence of tributylamine (TBA) shows higher yield than catalyzed by unsubstituted metal phthalocyanine. Comparing different catalysts of diverse metals, (t-Bu)4PcMg is more active than (t-Bu)4PcFe. But (t-Bu)4PcCo and (t-Bu)4PcNi only have low catalytic activities towards the reaction. Moreover, the yield will increase as the temperature increases.

A flexible nickel phthalocyanine resistive random access memory with multi-level data storage capability

Metal phthalocyanine is considered one of the most promising candidates for the design and fabrication of flexible resistive random access memory(RRAM)devices due to its intrinsic flexibility and excellent functionality.However,performance degradation and the lack of multi-level capability,which can directly expand the storage capacity in one memory cell without sacrificing additional layout area,are the primary obstacles to the use of metal phthalocyanine RRAMs in information storage.Here,a flexible RRAM with pristine nickel phthalocyanine(Ni Pc)as the resistive layer is reported for multi-level data storage.Due to its high trap-concentration,the charge transport behavior of the device agrees well with classical space charge limited conduction controlled by traps,leading to an excellent performance,including a high on-off current ratio of 10^(7),a long-term retention of 10^(6)s,a reproducible endurance over6000 cycles,long-term flexibility at a bending strain of 0.6%,a write speed of 50 ns under sequential bias pulses and the capability of multi-level data storage with reliable retention and uniformity.