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...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.展开更多
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-substitu...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.展开更多
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...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.展开更多
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...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)).展开更多
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 ...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.展开更多
Phthalocyanines-related compounds, subphthalocyanines, are the homologues consisting of three isoindole units with boron as the center. The absorption maximum of subphthalocyanines, called the Q band, appears around 5...Phthalocyanines-related compounds, subphthalocyanines, are the homologues consisting of three isoindole units with boron as the center. The absorption maximum of subphthalocyanines, called the Q band, appears around 560 - 630 nm, which is shifted by approximately 100 nm to shorter wavelengths compared to phthalocyanines. Subphthalocyanines are used as precursors to prepare unsymmetric phthalocyanines for ring enlargement reaction. In this decade, phthalocyanines are used for dye-sensitized solar cells (DSSCs), which require strong absorption of far-red light between 700 and 850 nm because of their highly efficiency. Non-peripheral thioaryl-substituted phthalocyanines have been synthesized. They show near-infrared absorption around 780 - 870 nm and have excellent electron transfer properties. However, their lack of affinity to basal plats inhibits their use as DSSC photosensitizer. Therefore, to synthesize unsymmetrical non-peripheral thioaryl-substituted phthalocyanines possessing good affinity to basal plates, the authors prepared subphthalocyanines having thioaryl substituents as precursors. Spectroscopic properties and electron transfer abilities to synthesize non-peripheral thioaryl-substituted subphthalocyanines were estimated using cyclic voltammetry. The Q band of non-peripheral thioaryl-substituted subphthalocyanines shows around 650 nm shifted to longer wavelength by 86 nm in comparison to subphthalocyanine. The compounds show many reduction potentials. They are acceptable electrons in the subphthalocyanine ring, meaning that the compounds have good electron transfer properties.展开更多
The quantitative understanding of how atomic-level catalyst structural changes affect the reactivity of the electrochemical CO_(2)reduction reaction is challenging.Due to the complexity of catalytic systems,convention...The quantitative understanding of how atomic-level catalyst structural changes affect the reactivity of the electrochemical CO_(2)reduction reaction is challenging.Due to the complexity of catalytic systems,conventional in situ X-ray spectroscopy plays a limited role in tracing the underlying dynamic structural changes in catalysts active sites.Herein,operando high-energy resolution fluorescence-detected X-ray absorption spectroscopy was used to precisely identify the dynamic structural transformation of well-defined active sites of a representative model copper(Ⅱ)phthalocyanine catalyst which is of guiding significance in studying single-atom catalysis system.Comprehensive X-ray spectroscopy analyses,including surface sensitive△μspectra which isolates the surface changes by subtracting the disturb of bulk base and X-ray absorption near-edge structure spectroscopy simulation,were used to discover that Cu species aggregated with increasing applied potential,which is responsible for the observed evolution of C_(2)H_(4).The approach developed in this work,characterizing the active-site geometry and dynamic structural change,is a novel and powerful technique to elucidate complex catalytic mechanisms and is expected to con tribute to the rational design of highly effective catalysts.展开更多
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 elementa...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.展开更多
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 ...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.展开更多
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 t...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.展开更多
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 an...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.展开更多
Graphene-modified asphalt(GMA)for road application was prepared via using metal-free phthalocyanine-dispersed to modify an SK-70#base asphalt with graphene.The preparation parameters are as follows:the content of grap...Graphene-modified asphalt(GMA)for road application was prepared via using metal-free phthalocyanine-dispersed to modify an SK-70#base asphalt with graphene.The preparation parameters are as follows:the content of graphene is 0.26%based on the mass percentage of absolute ethanol,the content of nonmetal phthalocyanine is 190%based on the mass percentage of graphene,and then the GMA is prepared via unique high-speed shearing with continuing to ventilate nitrogen,which can prevent the aging of modified asphalt in the high-speed shearing process,and effectively evaluate the modifier.The penetration,softening point,force ductility,and fracture energy of GMA were significantly improved based on the base asphalt.Thus,the incorporation of graphene could enhance the base asphalt’s high-and low-temperature stability.The modification mechanism was researched via metallographic microscopy,computed tomography(CT),Fourier transform infrared spectroscopy(FTIR),and atomic force microscopy(AFM).Adsorption and physical dispersion of the asphaltenes and resins in the phthalocyanine-graphene system were confirmed.展开更多
Tumor lymph node(LN)metastasis seriously affects the treatment prognosis.Studies have shown that nanoparticles with size of sub-50 nm can directly penetrate into LN metastases after intravenous administration.Here,we ...Tumor lymph node(LN)metastasis seriously affects the treatment prognosis.Studies have shown that nanoparticles with size of sub-50 nm can directly penetrate into LN metastases after intravenous administration.Here,we speculate through introducing targeting capacity,the nanoparticle accumulation in LN metastases would be further enhanced for improved local treatment such as photothermal therapy.Trastuzumabtargeted micelles(<50 nm)were formulated using a unique surfactantstripping approach that yielded concentrated phthalocyanines with strong near-infrared absorption.Targeted micellar phthalocyanine(T-MP)was an effective photothermal transducer and ablated HT-29 cells in vitro.A HER2-expressing colorectal cancer cell line(HT-29)was used to establish an orthotopic mouse model that developed metastatic disease in mesenteric sentinel LN.T-MP accumulated more in the LN metastases compared to the micelles conjugated with control IgG.Following surgical resection of the primary tumor,minimally invasive photothermal treatment of the metastatic LN with T-MP,but not the control micelles,extended mouse survival.Our findings demonstrate for the first time that targeted small-sized nanoparticles have potential to enable superior paradigms for dealing with LN metastases.展开更多
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 photocondu...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.展开更多
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 ...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.展开更多
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 s...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.展开更多
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 ...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.展开更多
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 N...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.展开更多
Oxygen reduction reaction(ORR)catalysts play a critical role in energy storage and conversion devices and have been attracted enormous interests,and however,it remains challenging to develop highly active cheap cataly...Oxygen reduction reaction(ORR)catalysts play a critical role in energy storage and conversion devices and have been attracted enormous interests,and however,it remains challenging to develop highly active cheap catalysts in a simple and green route.Inspired by the heme-copper oxidases(HOCs),in which the ORR active center is originated from the incorporation of Fe-N_(4)with copper atom,we here developed a fine manganese oxide nanosheets(MnO_(x)NSs)integrated with iron phthalocyanine(FePc)anchored on highly conductive graphene(MnO_(x)/FePc-G)through a green route only involve ethanol as the reagent.The bio-inspired catalyst MnO_(x)/Fe Pc-G demonstrated high ORR activity with a half-wave potential(E_(1/2))of 0.887 V,about 57 mV more positive than that of Pt/C.And the current density(j)at 0.9 V is about 1.9 m A cm^(-2),which is three times of Pt/C and FePc-G.More importantly,the bio-inspired systems show superior stability in comparison to commercial Pt/C,showing a potential of 0.863 V to deliver a j of 3 mA cm^(-2)after 18000 s polarization,about 80 mV higher than that of 0.783 V for Pt/C.The high activity is contributed by the integration of the Fe Pc and MnO_(x)NSs that plays the role to assist the cleavage of the O_(2)bond.Our approach provides a new evidence to develop highly efficient ORR catalysts through imitate the naturally involved systems through a simple route.展开更多
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 phthalocy...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.展开更多
文摘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.
基金supported by the National Natural Science Foundation of China(Grant Nos.21975116 and 51950410598)the Major Program of Guangdong Basic and Applied Research(Grant No.2019B121205001)+2 种基金Shenzhen NSQKJJ(Grant No.K20799112)the Shenzhen Science and Technology Innovation Committee(Project No.JCYJ20170412154426330)the‘‘Climbing Program”Special Funds(Project No.pdjh2021c0027)。
文摘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.
基金financially supported by the National Natural Science Foundation of China(22172093 and 21776167)。
文摘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.
基金financial supports from the Research Grants Council of the Hong Kong Special Administrative Region(Poly U15217521)the Hong Kong Polytechnic University(Q-CDA3)Initiative for fostering University of Research and Innovation Program of the National Research Foundation(NRF)funded by the Korean government(MSIT)(No.2020M3H1A1077095)
文摘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)).
基金the financial support from the National Natural Science Foundation of China(22005099)。
文摘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.
文摘Phthalocyanines-related compounds, subphthalocyanines, are the homologues consisting of three isoindole units with boron as the center. The absorption maximum of subphthalocyanines, called the Q band, appears around 560 - 630 nm, which is shifted by approximately 100 nm to shorter wavelengths compared to phthalocyanines. Subphthalocyanines are used as precursors to prepare unsymmetric phthalocyanines for ring enlargement reaction. In this decade, phthalocyanines are used for dye-sensitized solar cells (DSSCs), which require strong absorption of far-red light between 700 and 850 nm because of their highly efficiency. Non-peripheral thioaryl-substituted phthalocyanines have been synthesized. They show near-infrared absorption around 780 - 870 nm and have excellent electron transfer properties. However, their lack of affinity to basal plats inhibits their use as DSSC photosensitizer. Therefore, to synthesize unsymmetrical non-peripheral thioaryl-substituted phthalocyanines possessing good affinity to basal plates, the authors prepared subphthalocyanines having thioaryl substituents as precursors. Spectroscopic properties and electron transfer abilities to synthesize non-peripheral thioaryl-substituted subphthalocyanines were estimated using cyclic voltammetry. The Q band of non-peripheral thioaryl-substituted subphthalocyanines shows around 650 nm shifted to longer wavelength by 86 nm in comparison to subphthalocyanine. The compounds show many reduction potentials. They are acceptable electrons in the subphthalocyanine ring, meaning that the compounds have good electron transfer properties.
基金supported by the National Natural Science Foundation of China,grant number:U1732267.
文摘The quantitative understanding of how atomic-level catalyst structural changes affect the reactivity of the electrochemical CO_(2)reduction reaction is challenging.Due to the complexity of catalytic systems,conventional in situ X-ray spectroscopy plays a limited role in tracing the underlying dynamic structural changes in catalysts active sites.Herein,operando high-energy resolution fluorescence-detected X-ray absorption spectroscopy was used to precisely identify the dynamic structural transformation of well-defined active sites of a representative model copper(Ⅱ)phthalocyanine catalyst which is of guiding significance in studying single-atom catalysis system.Comprehensive X-ray spectroscopy analyses,including surface sensitive△μspectra which isolates the surface changes by subtracting the disturb of bulk base and X-ray absorption near-edge structure spectroscopy simulation,were used to discover that Cu species aggregated with increasing applied potential,which is responsible for the observed evolution of C_(2)H_(4).The approach developed in this work,characterizing the active-site geometry and dynamic structural change,is a novel and powerful technique to elucidate complex catalytic mechanisms and is expected to con tribute to the rational design of highly effective catalysts.
基金Supported by the Natural Science Foundation of Fujian Province(2012J01368)
文摘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.
文摘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.
基金the National Key Research Development Program of China (No.2016YFA0200604 and No.2017YFA0204904)the National Natural Science Foundation of China (No.21473174)+1 种基金the Fundamental Research Funds for the Central Universities (No.WK2340000074 and No.WK2060190084)The computational resources of Super-computing Center of University of Science and Technology of China, Supercomputing Center of Chinese Academy of Sciences, Tianjing, and Shanghai Supercomputer Centers are also acknowledged.
文摘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.
基金This work was financially supported by the National High-Tech Research and Development Pogram of China ("863" Program, Nos. 2002AA325050 and 2004AA302010) the Key Project of Chinese Ministry of Education.(No. 305002)the National Natural Science Foundation of China (Nos. 20325621 and 20236020).
文摘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.
基金Funded by National Natural Science Foundation of China(No.51778096)Natural Scienceof CQ CSTC(No.cstc2016jcyjA0119)
文摘Graphene-modified asphalt(GMA)for road application was prepared via using metal-free phthalocyanine-dispersed to modify an SK-70#base asphalt with graphene.The preparation parameters are as follows:the content of graphene is 0.26%based on the mass percentage of absolute ethanol,the content of nonmetal phthalocyanine is 190%based on the mass percentage of graphene,and then the GMA is prepared via unique high-speed shearing with continuing to ventilate nitrogen,which can prevent the aging of modified asphalt in the high-speed shearing process,and effectively evaluate the modifier.The penetration,softening point,force ductility,and fracture energy of GMA were significantly improved based on the base asphalt.Thus,the incorporation of graphene could enhance the base asphalt’s high-and low-temperature stability.The modification mechanism was researched via metallographic microscopy,computed tomography(CT),Fourier transform infrared spectroscopy(FTIR),and atomic force microscopy(AFM).Adsorption and physical dispersion of the asphaltenes and resins in the phthalocyanine-graphene system were confirmed.
基金Hai-Yi Feng and Yihang Yuan contributed equally to this work.We thank Prof.Gang Zheng(University of Toronto)for valuable discussion.We also thank the Core Facility of Basic Medical Sciences(SJTU-SM)for frozen section making and scanningThis work was supported by National Natural Science Foundation of China(81572998,81773274,82073379)+1 种基金Shanghai Municipal Science and Technology Commission(20ZR1451700,16520710700)Shanghai Collaborative Innovation Center for Translational Medicine(TM201731).
文摘Tumor lymph node(LN)metastasis seriously affects the treatment prognosis.Studies have shown that nanoparticles with size of sub-50 nm can directly penetrate into LN metastases after intravenous administration.Here,we speculate through introducing targeting capacity,the nanoparticle accumulation in LN metastases would be further enhanced for improved local treatment such as photothermal therapy.Trastuzumabtargeted micelles(<50 nm)were formulated using a unique surfactantstripping approach that yielded concentrated phthalocyanines with strong near-infrared absorption.Targeted micellar phthalocyanine(T-MP)was an effective photothermal transducer and ablated HT-29 cells in vitro.A HER2-expressing colorectal cancer cell line(HT-29)was used to establish an orthotopic mouse model that developed metastatic disease in mesenteric sentinel LN.T-MP accumulated more in the LN metastases compared to the micelles conjugated with control IgG.Following surgical resection of the primary tumor,minimally invasive photothermal treatment of the metastatic LN with T-MP,but not the control micelles,extended mouse survival.Our findings demonstrate for the first time that targeted small-sized nanoparticles have potential to enable superior paradigms for dealing with LN metastases.
文摘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.
基金Funded by the National Natural Science Foundation of China(No.61377092)
文摘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.
基金This study was supported by the National Natural Science Foundation of China (No. 20604007);Natural Science Foundation of Fujian (No. C0510007);Key Foundation for Ministry of Education (No. 206071);Key Foundation for Education 0ffice of Fujian (No. JA05195);Key Laboratory for Structure Chemistry (No. 040083).
文摘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.
基金Project supported by the Shenzhen Personal Maker Project,China(Grant No.GRCK2017082316173208)the Shenzhen Overseas High-level Talents Innovation Plan of Technical Innovation,China(Grant No.KQJSCX20180323140712012)the Special Funds for the Development of Strategic Emerging Industries in Shenzhen,China(Grant No.JCJY20170818154457845)
文摘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.
基金supported by the National Natural Science Foundation of China(No.20604007)Natural Science Foundation of Fujian(No.2008J0078)+1 种基金Key Foundation for Ministry of Education,China(No.206071)Project WKJ2008-2-61 supported by science research foundation of Ministry of Health & United Fujian Provincial Health and Education Project for Tackling the Key Research,China.
文摘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.
基金funded by an Australian Research Council LIEF grant(LE120100026)supported by the National Natural Science Foundation of China(U19A2017)
文摘Oxygen reduction reaction(ORR)catalysts play a critical role in energy storage and conversion devices and have been attracted enormous interests,and however,it remains challenging to develop highly active cheap catalysts in a simple and green route.Inspired by the heme-copper oxidases(HOCs),in which the ORR active center is originated from the incorporation of Fe-N_(4)with copper atom,we here developed a fine manganese oxide nanosheets(MnO_(x)NSs)integrated with iron phthalocyanine(FePc)anchored on highly conductive graphene(MnO_(x)/FePc-G)through a green route only involve ethanol as the reagent.The bio-inspired catalyst MnO_(x)/Fe Pc-G demonstrated high ORR activity with a half-wave potential(E_(1/2))of 0.887 V,about 57 mV more positive than that of Pt/C.And the current density(j)at 0.9 V is about 1.9 m A cm^(-2),which is three times of Pt/C and FePc-G.More importantly,the bio-inspired systems show superior stability in comparison to commercial Pt/C,showing a potential of 0.863 V to deliver a j of 3 mA cm^(-2)after 18000 s polarization,about 80 mV higher than that of 0.783 V for Pt/C.The high activity is contributed by the integration of the Fe Pc and MnO_(x)NSs that plays the role to assist the cleavage of the O_(2)bond.Our approach provides a new evidence to develop highly efficient ORR catalysts through imitate the naturally involved systems through a simple route.
基金This work was supported by the Natural Science Foundation of the Shanxi Province of China(No.201801D121069).
文摘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.