Search results for: metal(II) phthalocyanines

Authors: Ipek Gunay, Efe B. Orman, Metin Ozer, Bekir Salih, Ali R. Ozkaya

Abstract:

Phthalocyanines with macrocyclic ring containing at least three heteroatoms have nine or more membered structures. Metal-free phthalocyanines react with metal salts to obtain chelate complexes. This is one of the most important features of metal-free phthalocyanine as ligand structure. Although phthalocyanines have very similar properties with porphyrins, they have some advantages such as lower cost, easy to prepare, and chemical and thermal stability. It’s known that Pc compounds have shown one-electron metal-and/or ligand-based reversible or quasi-reversible reduction and oxidation processes. The redox properties of phthalocyanines are critically related to the desirable properties of these compounds in their technological applications. Thus, Pc complexes have also been receiving increasing interest in the area of fuel cells due to their high electrocatalytic activity in dioxygen reduction and fuel cell applications. In this study, novel phthalocyanine complexes coordinated with Fe(II) and Co (II) to be used as catalyst were synthesized. Aiming this goal, a new nitrile ligand was synthesized starting from 4-hydroxy-3,5-dimethoxy benzyl alcohol and 4-nitrophthalonitrile in the presence of K2CO3 as catalyst. After the isolation of the new type of nitrile and metal complexes, the characterization of mentioned compounds was achieved by IR, H-NMR and UV-vis methods. In addition, the electrochemical behaviour of Pc complexes was identified by cyclic voltammetry, square wave voltammetry and in situ spectroelectrochemical measurements. Furthermore, the catalytic performances of Pc complexes for oxygen reduction were tested by dynamic voltammetry measurements, carried out by the combined system of rotating ring-disk electrode and potentiostat, in a medium similar to fuel-cell working conditions.

Keywords: phthalocyanine, electrocatalysis, electrochemistry, in-situ spectroelectrochemistry

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Authors: G. Fomo, O. J. Achadu, T. Nyokong

Abstract:

Nanoconjugates of graphene quantum dots (GQDs) and 4-(tetrakis-5-(trifluoromethyl)-2-mercaptopyridinephthalocyanine (H₂Pc(OPyF₃)₄) or 4-(tetrakis-5-(trifluoromethyl)-2-mercaptopyridinephthalocyaninato) zinc (II) (ZnPc(OPyF₃)₄) were synthesized via a novel in situ one-step route. The bottom-up approach for the prepared conjugates could ensure the intercalation of the phthalocyanines (Pcs) directly onto the edges or surface of the GQDs and or non-covalent coordination using the π-electron systems of both materials. The as-synthesized GQDs and their Pcs conjugates were characterized using different spectroscopic techniques and their photophysicochemical properties evaluated. The singlet oxygen quantum yields of the Pcs in the presence of GQDs were enhanced due to Förster resonance energy transfer (FRET) occurrence within the conjugated hybrids. Hence, these nanoconjugates are potential materials for photodynamic therapy (PDT) and photocatalysis applications.

Keywords: graphene quantum dots, metal free fluorinated phthalocyanine, zinc fluorinated phthalocyanine, photophysicochemical properties

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Authors: Maryam Mirabediny, Tsz Tin Yu, Jun Sun, Matthew Lee, Denis M. O’Carroll, Michael J. Manefield, Björn Akermark, Biswanath Das, Naresh Kumar

Abstract:

Branched perfluorooctane sulfonic acid (PFOS) is recognized as a threatening environmental pollutant due to its high persistence and bioaccumulation in various environmental matrices as well as for its toxic effects on humans and wildlife, even at very low concentrations. This study reports the first investigation of branched PFOS defluorination catalyzed by metal phthalocyanines. The reaction conditions were optimized using the different reductants and temperatures. Cobalt phthalocyanine, when combined with Ti citrate as a reducing agent, was able to defluorinate 10.9% of technical PFOS within 8 hours. In contrast, vitamin B12 only showed 2.4% defluorination during the same period under similar conditions. The defluorination mediated by cobalt phthalocyanine and Ti citrate system corresponds to 54.5% of all branched PFOS isomers (br-PFOS isomers). Isomer-specific degradation was also investigated via high-resolution LC-orbitrap, followed by their relative rates. The difference in catalytic efficacy of various phthalocyanine complexes is rationalized by their structures and electrochemical response. Lastly, a new defluorination mechanism is proposed based on the newly detected degradation products after the phthalocyanines treatment and the previous studies.

Keywords: branched isomers, catalyst, reductive defluorination, water remediation

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Authors: Vladimir A. Basiuk, Laura J. Flores-Sanchez, Victor Meza-Laguna, Jose O. Flores-Flores, Lauro Bucio-Galindo, Elena V. Basiuk

Abstract:

Noncovalent nanohybrid materials combining carbon nanotubes (CNTs) with phthalocyanines (Pcs) is a subject of increasing research effort, with a particular emphasis on the design of new heterogeneous catalysts, efficient organic photovoltaic cells, lithium batteries, gas sensors, field effect transistors, among other possible applications. The possibility of using unsubstituted Pcs for CNT functionalization is very attractive due to their very moderate cost and easy commercial availability. However, unfortunately, the deposition of unsubstituted Pcs onto nanotube sidewalls through the traditional liquid-phase protocols turns to be very problematic due to extremely poor solubility of Pcs. On the other hand, unsubstituted free-base H₂Pc phthalocyanine ligand, as well as many of its transition metal complexes, exhibit very high thermal stability and considerable volatility under reduced pressure, which opens the possibility for their physical vapor deposition onto solid surfaces, including nanotube sidewalls. In the present work, we show the possibility of simple, fast and efficient noncovalent functionalization of single-walled carbon nanotubes (SWNTs) with a series of 3d metal(II) phthalocyanines Me(II)Pc, where Me= Co, Ni, Cu, and Zn. The functionalization can be performed in a temperature range of 400-500 °C under moderate vacuum and requires about 2-3 h only. The functionalized materials obtained were characterized by means of Fourier-transform infrared (FTIR), Raman, UV-visible and energy-dispersive X-ray spectroscopy (EDS), scanning and transmission electron microscopy (SEM and TEM, respectively) and thermogravimetric analysis (TGA). TGA suggested that Me(II)Pc weight content is 30%, 17% and 35% for NiPc, CuPc, and ZnPc, respectively (CoPc exhibited anomalous thermal decomposition behavior). The above values are consistent with those estimated from EDS spectra, namely, of 24-39%, 27-36% and 27-44% for CoPc, CuPc, and ZnPc, respectively. A strong increase in intensity of D band in the Raman spectra of SWNT‒Me(II)Pc hybrids, as compared to that of pristine nanotubes, implies very strong interactions between Pc molecules and SWNT sidewalls. Very high absolute values of binding energies of 32.46-37.12 kcal/mol and the highest occupied and lowest unoccupied molecular orbital (HOMO and LUMO, respectively) distribution patterns, calculated with density functional theory by using Perdew-Burke-Ernzerhof general gradient approximation correlation functional in combination with the Grimme’s empirical dispersion correction (PBE-D) and the double numerical basis set (DNP), also suggested that the interactions between Me(II) phthalocyanines and nanotube sidewalls are very strong. The authors thank the National Autonomous University of Mexico (grant DGAPA-IN200516) and the National Council of Science and Technology of Mexico (CONACYT, grant 250655) for financial support. The authors are also grateful to Dr. Natalia Alzate-Carvajal (CCADET of UNAM), Eréndira Martínez (IF of UNAM) and Iván Puente-Lee (Faculty of Chemistry of UNAM) for technical assistance with FTIR, TGA measurements, and TEM imaging, respectively.

Keywords: carbon nanotubes, functionalization, gas-phase, metal(II) phthalocyanines

Procedia PDF Downloads 102

Authors: Milos Beran, Josef Drahorad, Ondrej Vltavsky, Martin Fronek, Jiri Sova

Abstract:

While most nanofibers are produced using electrospinning, this technique suffers from several drawbacks, such as the requirement for specialized equipment, high electrical potential, and electrically conductive targets. Consequently, recent years have seen the increasing emergence of novel strategies in generating nanofibers in a larger scale and higher throughput manner. The centrifugal spinning is simple, cheap and highly productive technology for nanofiber production. In principle, the drawing of solution filament into nanofibers using centrifugal spinning is achieved through the controlled manipulation of centrifugal force, viscoelasticity, and mass transfer characteristics of the spinning solutions. Engineering efforts of researches of the Food research institute Prague and the Czech Technical University in the field the centrifugal nozzleless spinning led to introduction of a pilot plant demonstrator NANOCENT. The main advantages of the demonstrator are lower investment cost - thanks to simpler construction compared to widely used electrospinning equipments, higher production speed, new application possibilities and easy maintenance. The centrifugal nozzleless spinning is especially suitable to produce submicron fibers from polymeric solutions in highly volatile solvents, such as chloroform, DCM, THF, or acetone. To date, submicron fibers have been prepared from PS, PUR and biodegradable polyesters, such as PHB, PLA, PCL, or PBS. The products are in form of 3D structures or nanofiber membranes. Unique self-supporting nanofiber membranes were prepared from the biodegradable polyesters in different mixtures. The nanofiber membranes have been tested for different applications. Filtration efficiencies for water solutions and aerosols in air were evaluated. Different active inserts were added to the solutions before the spinning process, such as inorganic nanoparticles, organic precursors of metal oxides, antimicrobial and wound healing compounds or photocatalytic phthalocyanines. Sintering can be subsequently carried out to remove the polymeric material and transfer the organic precursors to metal oxides, such as Si02, or photocatalytic Zn02 and Ti02, to obtain inorganic nanofibers. Electrospinning is more suitable technology to produce membranes for the filtration applications than the centrifugal nozzleless spinning, because of the formation of more homogenous nanofiber layers and fibers with smaller diameters. The self-supporting nanofiber membranes prepared from the biodegradable polyesters are especially suitable for medical applications, such as wound or burn healing dressings or tissue engineering scaffolds. This work was supported by the research grants TH03020466 of the Technology Agency of the Czech Republic.

Keywords: polymeric nanofibers, self-supporting nanofiber membranes, biodegradable polyesters, active inserts

Procedia PDF Downloads 150