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.

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.

Structural Characterizations for Glass Ionomer Cement Doped with Transition Metal Phthalocyanines

Glass and Glass iomomer cement (GICs) based on a specific composition of cerium phosphate glass (40 CeO2-60P2O5) have been prepared. Effect of the doping type at a fixed doping concentration from metal-phthalocyanines (M-PCs) on material structure and morphologies has been carefully studied. The corresponding changes in the material structure were widely followed up by?31P MAS NMR, X-Ray diffraction and FTIR spectroscopy. The network structure of both base glass and GIC which all free from metal phthalocyanines has been confirmed to be amorphous. GIC doped with M-PCs has shown a more ordered structure. There were clear changes in the position and intensities of?31P NMR spectral peaks of glasses upon changing the dopant type. In all cases, a little concentration from M-Phthalocyanine (0.8 mol%) leads to changing the network structure from amorphous to a more ordered structure. Phosphate structural phases are evidenced to be formed upon addition of a fixed amount of M-PCs (Ga, Co, Fe). The morphologies of some selected samples were characterized by SEM. The micrographs have revealed that formulating of cerium phosphate powder of the amorphous glass with a polymeric acid successfully led to the formation of CePO4-H2O bundles phases. But formulation with GIC containing Co or Fe or Ga Phthalocyanine can simply form co-aligned linear slaps and elongated nanofibers which are consisted of hydrated and carbonated CePO4?a GaPO4, FePO4?or CoPO4?crystals. The structure of all doped materials has a lower crack length than that of base glass. This was discussed on bases of formation of more aligned and elongated tough-fibers in matrix of all doped materials. Such tough fibers have ability to withstand breaking stress via suppressing crack propagation.

Controlling Metalation Reaction of Phthalocyanine with Cobalt at Single-Molecule Level on Au(111)Surfac

Metalation reac-tion of metal-free phthalocyanine molecule with Co atom adsorbed on Au(111)surface has been studied in situ at single atom/molecule scale by low-temperature scanning tunneling microscopy(STM)experiment combined with simulations based on density function theory calculations.Through manipulations using STM tip,we showed a controlled manner to have a single metal-free phthalocyanine molecule react with a Co atom to form Co phthalocyanine molecule.In this reaction process,an intermediate state originating from π-d interaction between the metal-free phthalocyanine molecule and Co atom has been identi ed.Moreover,we also revealed that the redox reaction represented as bond breaking and bond forming relative to the Co and pyrrolic N atoms,not pyrrolic H atoms,is a key process for dehydrogenation and metalation reaction.Our DFT calculations provided theoretical supporting for the above conclusions,and further understanding of the related mechanisms.

Interfacial electronic structure at a metal–phthalocyanine/graphene interface:Copper–phthalocyanine versus iron–phthalocyanine

The energy level alignment of CuPc and FePc on single-layer graphene/Ni（111） （SLG/Ni） substrate was investigated by using ultraviolet and X-ray photoelectron spectroscopy （UPS and XPS）. The highest occupied molecular orbitals （HO- MOs） in a thick layer of CuPc and FePc lie at 1.04 eV and 0.90 eV, respectively, below the Fermi level of the SLG/Ni substrate. Weak adsorbate-substrate interaction leads to negligible interfacial dipole at the CuPc/SLG/Ni interface, while a large interracial dipole （0.20 eV） was observed in the case of FePc/SLG/Ni interface, due to strong adsorbate-substrate coupling. In addition, a new interfacial electronic feature was observed for the first time in the case of FePc on SLG/Ni substrate. This interfacial state can be attributed to a charge transfer from the SLG/Ni substrate to unoccupied orbitals of FePc.

固载化金属酞菁(MPc)催化性能的研究——Ⅱ.MPc通过配位连接在硅胶上及其对O_2的活化作用

用有机合成的方法在硅胶表面连接上可与MPc配位的有机基团——(CH_2)_3N(C_2H_5)_2,MPc与之配位从而固载在硅胶上。UV-Vis漫反射光谱表明硅胶表面存在MPc。用ESR研究固载化MPc与O_2的作用,证明固载化CoPc、FePc可以与O_2作用产生O_2^-,CuPc则不能。

硅胶键联MPc的制备及其在氧活化中的作用

The metal phthalocyanines (MPc, M=Fe, Co, Cu) were supported on the surface of silica gel by chemical linking. They could not be washed out with organic solvents such as Py. UV-Vis diffuse reflectance spectra indicated that MPc’s were supported on silica gel. ESR result showed that the supported CoPc and FePc could react with O2 to produce O2, but the supported CuPc could not.

纳米金属酞菁MPc(M=Fe,Co,Ni,Cu和Zn)的合成与表征

采用溶剂热方法以邻苯二甲腈为原料、乙二醇为溶剂在反应釜中合成了各种形貌的Fe,Co,Ni,Cu和Zn纳米金属酞菁化合物,并对它们进行了电子扫描电镜、XRD、红外光谱及紫外-可见光谱表征.结果表明,产品纯度高,产率大,形貌独特.

2种萘氧基MPc/TiO_2复合材料的制备及其表征

合成了萘氧基酞菁的前体化合物3-(2-萘氧基)邻苯二腈,通过1H NMR和熔点测定对其结构进行了表征,采用原位合成法合成了3-(2-萘氧基)CoPc/TiO_2和3-(2-萘氧基)CuPc/TiO_2复合材料,并利用IR、UV-Vis、XRD对产物进行表征,讨论了中心金属离子和负载TiO_2后对酞菁Q带最大吸收波长的影响,以及负载酞菁后对TiO_2晶型的影响.结果表明:复合材料Q带吸收发生一定程度红移,酞菁的负载使TiO_2的晶粒变小,但晶型没有改变.

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.

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%).

Efficient Carbon-Based CsPbBr_3 Inorganic Perovskite Solar Cells by Using Cu-Phthalocyanine as Hole Transport Material

Metal halide perovskite solar cells(PSCs) have attracted extensive research interest for next-generation solution-processed photovoltaic devices because of their high solar-to-electric power conversion efficiency(PCE)and low fabrication cost. Although the world's best PSC successfully achieves a considerable PCE of over 20% within a very limited timeframe after intensive efforts, the stability, high cost, and up-scaling of PSCs still remain issues. Recently, inorganic perovskite material, CsPbBr_3, is emerging as a promising photo-sensitizer with excellent durability and thermal stability, but the efficiency is still embarrassing. In this work, we intend to address these issues by exploiting CsPbBr_3 as light absorber, accompanied by using Cu-phthalocyanine(CuPc) as hole transport material(HTM) and carbon as counter electrode. The optimal device acquires a decent PCE of 6.21%, over 60% higher than those of the HTM-free devices. The systematic characterization and analysis reveal a more effective charge transfer process and a suppressed charge recombination in PSCs after introducing CuPc as hole transfer layer. More importantly, our devices exhibit an outstanding durability and a promising thermal stability, making it rather meaningful in future fabrication and application of PSCs.

MPc-Pt/C复合催化剂的甲醇氧化催化活性研究

介绍了用浸渍法制各金属酞菁(MPc,M=Fe、Co、Ni、Cu)掺杂Pt/C抗甲醇中毒复合催化剂。TEM图显示,Pt在复合催化剂中分散性良好,没有发生大的团聚。运用循环伏安法系统评价了这几种复合催化剂的甲醇氧化参数,甲醇氧化峰电流(If)与中间产物氧化峰电流(Ib)的比值If/Ib以及甲醇氧化单位质量峰电流密度Im,得到催化活性强弱顺序:CuPc-Pt/C>NiPc-Pt/C>CoPc-Pt/C>FePc-Pt/C,即促进甲醇氧化的催化活性随金属酞菁中心金属离子3d轨道电子数增加而递增。MPc-Pt/C复合催化剂基本都要在40次循环以后If/Ib比值趋于稳定,其中CuPc-Pt/C稳定性最好。

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.

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.

Reversion of Bioluminescent Bacteria (Mutatox^(TM)) toTheir Luminescent State upon Exposure to OrganicCompounds, Munitions, and Metal Salts

Mutatox is a new genotoxicity bioassay which uses as the endpoint the bioluminescence produced on reversion of a dark strain of the marine bacterium Vibrio fischeri ±S9.Reversion can occur by several mechanisms, including base substitution, frame-shift, SOS induction, and DNA intercalation. For screening, Mutatox provides many advantages over the Salmonella trphimurium (Ames) assay: it requires minimal sterility, employs a shorter incubation period, and does not require culture maintenance. Eighteen organic chemicals (phenol, polynuclear aromatic hydrocarbons, nitrotoluenes, others), Na3PO4, and 4 genotoxic metals (Cu2+, Ni2+, As3+, Cd2+) were tested. Most of the organic compounds positive in S. typhimurium assays were positive in Mutatox. None of the metals was genotoxic in V. fischeri, possibly due to poor uptake from the saline medium

酞菁敏化MIL-53(Al)光催化氧化脱硫性能

采用水热法将羧基取代金属酞菁(MTc Pc,M=Mn、Fe、Co、Ni、Cu、Zn)负载在金属有机框架MIL-53(Al)表面上,制备了复合材料MTcPc/MIL-53(Al)。通过SEM、XRD、FTIR、UV-Vis吸收光谱和XPS对MTcPc/MIL-53(Al)进行了表征,在常温常压、空气中氧气为氧化剂的条件下,测试其对噻吩/正辛烷为模拟燃油的光催化氧化脱硫性能。结果表明,MTcPc分子以有序晶态形式较均匀地分散在MIL-53(Al)表面上,其平面共轭结构对MIL-53(Al)晶体特定方向的生长具有明显诱导作用。与MTcPc相比,MTcPc/MIL-53(Al)的Q带存在一定程度的红移,扩展了光响应范围。MnTcPc/MIL-53(Al)表现出最佳的光催化脱硫性能,催化反应150 min,噻吩转化率100%,经4次循环后,噻吩转化率为93.01%。MTcPc与MIL-53(Al)之间的π-π堆积作用提高了MTcPc的分散,MIL-53(Al)的呼吸效应促进了噻吩分子和氧分子在MTcPc/MIL-53(Al)表面的强吸附富集作用,有利于活性中间体MIL-53(Al)/MTcPc–^(1)O_(2)的形成,从而提高了氧化脱硫的活性;MTcPc的共轭结构和中心离子的构型也是影响氧化脱硫效率的重要因素。

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.