Synthesis,characterization, pyrolysis kinetics and conductivity studies of chloro substituted cobalt phthalocyanines

Cobalt(II) phthalocyanine (CoPc), cobalt(II) tetrachloro phthalocyanine (CoPcCl₄), cobalt(II) octachloro phthalocyanine (CoPcCl₈) and cobalt(II) hexadecachloro phthalocyanine (CoPcCl₁₆) are synthesized pure and characterized using elemental analysis, UV-visible, IR-spectroscopy, magnetic susceptibility, X-ray crystallography, and thermogravimetry. All four complexes have monoclinic structure with different crystal lattice constants. Broido's, Coats-Redfern and Horowitz-Metzger relations were employed to calculate the kinetic and activation parameters associated with thermal decomposition of the above complexes. The compounds are analyzed for kinetic parameters, activation energies for decomposition and the Arrhenious pre-exponential factors, in their pyrolysis. Using these factors and standard equations, thermodynamic parameters such as enthalpy, entropy and free energies are calculated. The activation energies are evaluated based on their electrical conductivity conducted over the temperature range 30–200°C. The electrical conductivities observed at 30°C are in the order CoPcCl₁₆?>?CoPcCl₄?>?CoPcCl₈?>?CoPc. The relevant electrical conductivity data are reported.     

The Microwave-assisted syntheses and a conductivity study of a platinum phthalocyanine and its derivatives

The parent platinum phthalocyanine (PtPc) and its derivatives with tetranitro (PtTNPc) and tetramine (PtTAPc) on the peripheral benzene were synthesized in the pure state for the first time by microwave irradiation. These complexes were characterized using physico-chemical methods like elemental, electronic absorption, IR spectral, magnetic susceptibility, thermogravimetry and X-ray powder diffraction studies. Kinetic and thermodynamic parameters associated with the thermal decomposition were calculated using the thermogravimetric analytical data. Electrical conductivity studies were carried out using the two-probe technique in the temperature range 298–473 K for each complex to study the effect of the donor and acceptor substituents on the platinum phthalocyanine macrocycle. The electrical conductivities observed at room temperature are in the order PtTAPc > PtTNPc > PtPc. The improvement in the intrinsic electrical conductivity of PtTAPc is due to the electron donating amine substituents which are expected to facilitate greater intermolecular contact and increase interactions, providing a greater pathway for charge carriers.     

Synthesis and characterization of new mesomorphic octakis(alkylthio)-substituted lead phthalocyanines and their films

The syntheses of new octakis (alkylthio)-substituted phthalocyanines of Pb(II) (1a and 2a) are described. These compounds are very soluble in most common organic solvents. They have been fully characterized using elemental analysis, NMR, infrared and UV–Vis spectroscopy. The mesogenic properties of these new materials were studied by differential scanning calorimetry and optical microscopy. These phthalocyanine derivatives are liquid at room temperature and form columnar-hexagonal (Col_h) mesophases below −10 °C. It has been indicated that the addition of methylene bridges to the phthalocyanine (Pc) core increases the clearing point temperatures. Also, the coordination of Pb²⁺ with the phthalocyanine core decreases the clearing point temperatures and the liquid crystal phase transition temperatures. Thin films of octakis(alkylthio)-substituted Pb(II) phthalocyanines 1a and 2a were prepared by the method of spin-coating. To obtain films with an ordered structure the film of 1a was slowly cooled from room temperature down to −10 °C. Sandwich structures of the form Au/PbPc(1a)/Au were prepared for the investigation of their electrical properties. It was shown that a slowly cooled Au/PbPc(1a)/Au structure demonstrates repeatable and stable electrical switching behaviour for applied bias voltages between −1 V and +1 V.     

Studies on phthalocyanine sheet polymers

Cobalt, nickel and copper phthalocyanine sheet polymers are synthesized by heating their respective metal (II) phthalocyanine tetracarboxylic acids at 400 °C in nitrogen atmosphere. These polymers are characterized using UV-Visible spectra, IR spectra, magnetic susceptibility, X-ray powder diffraction and thermogravimetric analysis. Electrical conductivity studies are carried out using two-probe technique in the temperature range 25-200 °C for each polymer. These polymeric materials showed room temperature electrical conductivity 10-1000 times higher values compared to earlier reported values for this type of sheet polymers.     

Studies on tetra-amine phthalocyanines

Metal(II) tetranitro phthalocyanines of cobalt, nickel and copper are synthesized in pure state by a novel modified method. The complexes are characterized using elemental, electronic and IR spectral studies. Pure metal(II) tetra-amino phthalocyanines of cobalt, nickel and copper are synthesized by reducing the nitro groups of the above complexes using sodium sulphide. These complexes are also characterized by elemental, electronic, IR spectral and magnetic susceptibility measurements. The nature of the electrical conductivities of the above three metal(II) tetra-amino phthalocyanine derivatives are studied in the temperature range 303-473 K and the data are presented. Among the effect of various substituent groups on the electrical conducting property of phthalocyanine, amine group substituent on the peripheral benzene ring of the phthalocyanine molecule has been found to increase electrical conductivity to a greatest extent. These complexes showed about 10⁵-10⁶ times higher electrical conductivities compared to their parent phthalocyanine compounds.     

Selective metal sensor phthalocyanines bearing non-peripheral functionalities: Synthesis,spectroscopy, electrochemistry and spectroelectrochemistry

A novel alcohol-soluble ionophore ligand and its non-peripherally tetrasubstituted functional 1,8,15,22-tetrakis(6-hydroxyhexylsulfanyl) metallophthalocyanines M[Pc(α-SC₆H₁₂OH)₄] (M = Cu(II), Zn(II), Co(II); Pc = phthalocyanine) are reported. The aggregation and cation binding behaviors of the phthalocyanine compounds in the presence of soft Ag^I and Pd^II metal ions were investigated by using UV–Vis spectroscopy. The new compounds have been characterized by elemental analysis, IR, ¹H, ¹³C NMR, UV/Vis spectroscopy, ESI and MALDI–TOF–MS mass spectra. Voltammetric and in-situ spectroelectrochemical studies show that while copper and zinc phthalocyanine complexes give well-defined ring-based reduction and oxidation processes, the cobalt phthalocyanine gives both metal-based and ring-based redox processes which have reversible and diffusion controlled character.     

Enhanced electrical conductivity of Ag-mercaptosuccinic acid-redoped polyaniline nanoparticles during thermal cycling above 200 °C

Ag-doped polyaniline (PANI) nanoparticles are prepared via doping-dedoping-redoping with the thiol group in mercaptosuccinic acid (MSA) providing the linkage between PANI molecules and Ag atoms. Ag-MSA-doped PANI maintains the electrical conductivity well above the room-temperature value of 3.0 S/cm up to 220 °C, reaching its maximum (9.0 S/cm) at 180 °C. In addition, Ag-MSA-doped PANI nanoparticles show remarkable stability against repeated thermal aging at 120 °C. The room-temperature conductivity, in fact, increases by a factor of ∼3 after 3 cycles of thermal aging. The enhanced stability against repeated thermal aging is attributed to the formation of uniformly distributed Ag nanoparticles within the PANI particles upon heating.     

New synthesis of nanopowders of proton conducting materials. A route to densified proton ceramics

Low temperature routes have been developed for the preparation of BaCe_0.9Y_0.1O_2.95 (BCY10) and BaZr_0.9Y_0.1O_2.95 (BZY10) in the form of nanoparticulate powders for use after densification as ceramic membranes for a proton ceramic fuel cell. These methods make use on the one hand of the chelation of metal (II), (III) and (IV) ions by acrylates (hydrogelation route) and on the other of the destabilisation and precipitation of micro-emulsions. Both routes lead to single phase yttrium doped barium cerate or zirconate perovskites, as observed by X-ray diffraction, after thermal treatment at 900 °C for 4 h for BCY10 and 800 °C for BZY10. These temperatures, lower than those usually used for preparation of barium cerate or zirconate, lead to oxide nanoparticles of size <40 nm. Dense ceramics (?95%) are obtained by sintering BCY10 pellets at 1350 °C and BZY10 pellets at 1500 °C for 10 h. The water uptake of compacted samples at 500 °C is 0.14 wt% for BCY10 and 0.26 wt% for BZY10. Total conductivities in the range 300-600 °C were determined using impedance spectroscopy in a humidified nitrogen atmosphere. The total conductivity was 1.8×10⁻² S/cm for BCY10 and 2×10⁻³ S/cm for BZY10 at 600 °C. The smallest perovskite nanoparticles and highest conductivities were obtained by hydrogelation of precursor barium, zirconium, cerium and yttrium acrylates.     

A new route to obtain PVDF/PANI conducting blends

Electrically conductive poly(vinylidene fluoride)(PVDF) - polyaniline blends of different composition were synthesized by chemical polymerization of aniline in a mixture of PVDF and dimethylformamide (DMF) and studied by electrical conductivity measurement, UV-Vis-NIR and FTIR spectroscopy. The samples were obtained as flexible films by pressing the powder at 180 °C for 5 min. The electrical conductivity showed a great dependence on the syntheses parameters. The higher value of the electrical conductivity was obtained for the oxidant/aniline molar ratio equal to 1 and p-toluenesulfonic acid-TSA/aniline ratio between 3 and 6. UV-Vis-NIR and FTIR spectra of the blend are similar to the doped PANI, indicating that the PANI is responsible for the high electrical conductivity of the blend. The electrical conductivity of blend proved to be stable as a function of temperature decreasing about one order at temperature of 100 °C. The route used to obtain the polymer blend showed to be a suitable alternative in order to obtain PVDF/PANI-TSA blends with high electrical conductivity.     

Synthesis of electrically conductive polypyrrole-polystyrene composites using supercritical carbon dioxide: II. Effects of the doping conditions

A polymer composite of polypyrrole (PPy) and polystyrene (PS) was synthesized in this study. Pyrrole was firstly impregnated within the PS substrate where supercritical carbon dioxide (SCCO₂) at 40 °C and 10.5 MPa was used as the solvent. The resulting polymer composite was then soaked in a solution of metallic salt to form an electrically conductive product. Thermal analyses were carried out in this study. Glass transition temperatures from the DSC curves and thermal decomposition temperatures from the TGA curves were observed. These temperatures rise gradually from pure PS, undoped blend to doped composite that indicates blending took place in SCCO₂, and polymerization was proceeding when the pyrrole/PS blend was soaking in the doping solution. Furthermore, various effects of the doping conditions on the conductivity of the PPy/PS composite were investigated. Water and acetonitrile were used as the solvents where the former yielded a higher conductivity of the product. Various doping temperatures were studied and a maximum conductivity was observed at 25 °C. The conductivity also depends on the nature of the oxidant. A bell-shaped profile of the conductivity with respect to the concentration of each oxidant was obtained. The maximum conductivity of the composites with iron compounds as oxidants decreases in the following order of anions: chloride > sulfate > perchloride > nitrate in aqueous solutions. Comparison of the scanning electron microscope results of the composite was presented where chloride and nitrate anions were used as the oxidant. It was found that the composite with higher conductivity has higher bulk density and less porous morphology.     

Microwave assisted extraction of soy isoflavones

A fast and reliable analytical method using microwave assisted extraction has been developed. Several extraction solvents (methanol (MeOH) and ethanol (EtOH), 30-70% in water and water), temperatures (50-150 °C), extraction solvent volume, as well as the sample size (1.0-0.1 g) and extraction time (5-30 min) were studied for the optimization of the extraction protocol. The optimized extraction conditions for quantitative recoveries were: 0.5 g of sample, 50 °C, 20 min and 50% ethanol as extracting solvent. No degradation of the isoflavones was observed using the developed extraction protocol and a high reproducibility was achieved (>95%).     

Synthesis,characterization, aggregation and thermal properties of a novel polymeric metal-free phthalocyanine and its metal complexes

A novel polymeric metal-free phthalocyanine (M = 2H) and its metal complexes (M = Zn, Cu, Co and Ni) were prepared by the tetramerization reaction of 3,6,9-Tris(p-tolylsulfonyl)-1,11-bis(3,4-dicyanophenoxy)-3,6,9-triazaundecane 5 with the appropriate materials. The electrical conductivities of the metal-free phthalocyanine and the metal complexes, measured in air, were found to be ∼10⁻⁶–10⁻⁵ S m⁻¹. The aggregation property of the zinc complex 7 was investigated with Ni²⁺, Cu²⁺, Co²⁺, Pb²⁺, Cd²⁺ and Ag⁺ cations. Thermal analysis of the polymers were done by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) at a heating rate of 10 °C min⁻¹ under a nitrogen atmosphere. All the novel compounds were characterized by using elemental analysis, UV–Vis, FT–IR, NMR and MS spectral data and DSC, DTA/TG techniques.     

Some solutions to obtain very efficient separations in isocratic and gradient modes using small particles size and ultra-high pressure

The UHPLC strategy which combines sub-2 μm porous particles and ultra-high pressure (>1000 bar) was investigated considering very high resolution criteria in both isocratic and gradient modes, with mobile phase temperatures between 30 and 90 °C. In isocratic mode, experimental conditions to reach the maximal efficiency were determined using the kinetic plot representation for ΔP_max = 1000 bar. It has been first confirmed that the molecular weight of the compounds (MW) was a critical parameter which should be considered in the construction of such curves. With a MW around 1000 g mol⁻¹, efficiencies as high as 300,000 plates could be theoretically attained using UHPLC at 30 °C. By limiting the column length to 450 mm, the maximal plate count was around 100,000. In gradient mode, the longest column does not provide the maximal peak capacity for a given analysis time in UHPLC. This was attributed to the fact that peak capacity is not only related to the plate number but also to column dead time. Therefore, a compromise should be found and a 150 mm column should be preferentially selected for gradient lengths up to 60 min at 30 °C, while the columns coupled in series (3× 150 mm) were attractive only for t_grad > 250 min. Compared to 30 °C, peak capacities were increased by about 20–30% for a constant gradient length at 90 °C and gradient time decreased by 2-fold for an identical peak capacity.     

酞菁铅在石墨烯表面吸附行为的拉曼光谱研究

利用石墨烯增强拉曼散射效应可以获得与石墨烯接触的某些分子的拉曼增强信号, 并且对于不同的分子或振动模, 其拉曼增强因子不同. 根据这一特征, 本工作利用拉曼光谱技术对石墨烯表面上酞菁铅(PbPc)分子Langmuir-Blodgett (LB)膜在退火过程中吸附构型的变化进行了跟踪研究. 发现随着退火温度的升高, 石墨烯表面上PbPc分子的拉曼信号经历了一个先增强后减弱的过程, 在升华温度点附近强度达到最大, 表明PbPc发生了由直立向平躺取向的转变; 同时, 在PbPc分子升华温度点附近, 由于对称性破坏导致散射截面低的振动模出现, 并且该振动模强度随着退火温度的进一步升高而增强, 表明非平面的PbPc分子受石墨烯π-π相互作用的影响而形变加剧, 向平面结构转变; 在更高的退火温度下, 则出现一些不属于PbPc分子的拉曼振动峰, 表明PbPc分子在石墨烯表面由Pb(II)被还原成Pb(0).     

A study of the removal of heavy metals from aqueous solutions by Moringa oleifera seeds and amine-based ligand 1,4-bis[N,N-bis(2-picoyl)amino]butane

Uptake for lead, copper, cadmium, nickel and manganese from aqueous solution using the Moringa oleifera seeds biomass (MOSB) and amine-based ligand (ABL) was investigated. Experiments on two synthetic multi-solute systems revealed that MOSB performed well in the biosorption and followed the decreasing orders Pb(II) > Cu(II) > Cd(II) > Ni(II) > Mn(II) and Zn(II) > Cu(II) > Ni(II). The general trend of the heavy metal ions uptake by the amine-based ligand followed decreased in the order Mn > Cd > Cu > Ni > Pb, which is the reverse trend for what was observed for MOSB. Comparing the single- and multi-metal solutions, there was no clear effect in the biosorption capacity of MOSB suggesting the presence of sufficient active binding sites for all metal ions studied. The MOSB performance is also not affected by pH in the range 3.5–8.     

Self-standing single lithium ion conductor polymer network with pendant trifluoromethanesulfonylimide groups: Li diffusion coefficients from PFGSTE NMR

Solid electrolyte materials have the potential to improve performance and safety characteristics of batteries by replacing conventional solvent-based electrolytes. For this purpose, new candidate single ion conductor self-standing networks were synthesized with trifluoromethane-sulfonylimide (TFSI) lithium salt based monomer using poly(ethyleneglycol) dimethacrylate (PEGDM 750) as crosslinker. The highest ionic conductivity was 3.4 × 10⁻⁷ S cm⁻¹ at 30 °C in the dry state. Thermal and mechanical analyses showed good thermal stability up to 190 °C and rubbery-like properties at ambient temperature. A direct relationship between ionic conductivity and glassy or rubbery state of the membranes was found. Vogel–Tammann–Fulcher behavior was observed in the dry state which is consistent with a lithium conductivity correlated with polymer chain mobility. By swelling the network in propylene carbonate, a self-standing electrolyte gel could be obtained with an ionic conductivity as high as 1 × 10⁻⁴ S cm⁻¹ at 30 °C. The individual diffusion coefficients of mobile species in the material (¹⁹F and ⁷Li) were measured and quantified using pulsed-field gradient nuclear magnetic resonance (PFG-NMR). Diffusion coefficients for the most mobile components of the lithium cations and fluorinated anions at 100 °C in dry membranes have been found to be 3.4 × 10⁻⁸ cm² s⁻¹ and 2.1 × 10⁻⁸ cm² s⁻¹ respectively.     

Gas- and solid/liquid-phase reactions during pyrolysis of softwood and hardwood lignins

Pyrolytic reactions of Japanese cedar (Cryptomeria japonica, a softwood) and Japanese beech (Fagus crenata, a hardwood) milled wood lignins (MWLs) were studied with thermogravimetry (TG) and by pyrolysis in a closed ampoule reactor (N₂/600 °C). The data were compared with those of guaiacol/syringol as simple lignin model aromatic nuclei. Several DTG peaks were observed around 300-350, 450, 590 and 650 °C. The first DTG peak temperature (326 °C) of beech was lower than that (353 °C) of cedar. This indicates that the volatile formation from cedar MWL is slightly delayed in heating at 600 °C. The gas-phase reactions via GC/MS-detectable low MW products were explainable with the temperature-dependent reactions observed for guaiacol/syringol in our previous paper. The methoxyl groups became reactive at ∼450 °C, giving O-CH₃ homolysis products (catechols/pyrogallols) and OCH₃ rearrangement products (cresols/xylenols). The former homolysis products were effectively converted into gaseous products (mainly CO) at >550-600 °C. However, the GC/MS-detectable tar yields, especially syringyl unit-characteristic products, were much lower than those from guaiacol/syringol. Thus, contributions of higher MW intermediates and solid/liquid-phase reactions are more important in lignin pyrolysis. From the results of stepwise pyrolysis of char + coke fractions at 450 and 600 °C, the methoxyl group-related reactions (450 °C) and intermediates gasification (600 °C) were suggested to occur also in the solid/liquid phase. This was consistent with the DTG peaks observed around these temperatures. These solid/liquid-phase reactions reduced the tar formation, especially catechols/pyrogallols and PAHs. Different features observed between these two MWLs are also focused.     

Synthesis,thermal stability and structural characterisation of iron(II) phthalocyanine complex with 4-cyanopyridine

A new complex of bis-axially coordinated iron(II) phthalocyanine by 4-cyanopyridine (4-CNpy) has been obtained in crystalline form as an adduct with two 4-CNpy molecules. The [FePc(4-CNpy)₂] · 2(4-CNpy) crystallises in the monoclinic system, space group P2₁/c with two molecules in the unit cell. The iron(II) coordinates four isoindole nitrogen atoms of the almost planar phthalocyaninato(2−) macroring and axially two nitrogen atoms of 4-CNpy molecules. The coordination polyhedron around the Fe(II) atom approximates to a tetragonal by-pyramid. Four equatorial Fe–N bonds are shorter (1.936(2) Å) than two axial Fe–N bonds (2.027(2) Å). The centrosymmetric FePc(4-CNpy)₂ molecules form alternating sheets parallel to the bc crystallographic plane and solvated 4-CNpy molecules that are anti-parallel oriented by their polar cyano groups are located between the sheets of FePc(4-CNpy)₂ molecules. Ligation of the intermediate-spin iron(II) phthalocyanine by 4-CNpy molecules leads to the low spin Fe(II) complex. The importance of the d(π) → π^∗(Pc) back donation is manifested in the difference between the values of C–N isoindole and C–N azamethine bond lengths of the Pc macrocycle. The thermal analysis of the crystals of [FePc(4-CN)₂] · 2(4-CNpy) shows two steps responsible for a loss of solvated (∼170 °C) and coordinated (∼235 °C) 4-CNpy molecules.     

Novel α-fluorinated cyclic phosphite and phosphinite ligands and their Rh-complexes as suitable catalysts in hydroformylation

Asymmetrical cyclic phosphite and phosphinite ligands of a novel type bearing either trifluoromethyl or pentafluorophenyl group were synthesized using >PCl or >PN< species and racemic fluorinated alcohols. The P-ligands were converted to complexes of Rh^III(L)(Cp^∗)Cl₂ type (where L = phosphite or phosphinite) and, in two instances, their stereostructures were evaluated by X-ray analysis. These complexes along with in situ systems, formed from Rh(CO)₂(acac) precursor and the corresponding ligand, were tested in the hydroformylation of styrene. Both systems provided excellent hydroformylation activities at 100 °C. Using the Rh^I in situ systems, moderate and high regioselectivities towards the branched aldehyde (2-phenyl-propanal) were obtained at 100 and 40 °C, respectively.     

Extrinsic and intrinsic structural change during heat treatment of polyaniline

HCl doped polyaniline (PAni) was synthesized electrochemically and heat treated at 150 °C, 200 °C and 250 °C for 30 min in vacuum. Different intrinsic and extrinsic structural changes due to heat treatment were determined from XRD, TGA, FT-IR, conductivity and solubility measurement. When HCl doped PAni is subjected to heat treatment, different changes are taking place in the system like doping, dedoping (extrinsic), oxidation, chain scission, cross-linking and changes in crystal structure (intrinsic). Mechanism for doping, dedoping, oxidation, chain scission and cross-linking is proposed.