Sharif Digital Repository

Salicylate selective electrodes based on oxo(phthalocyanato)-vanadium(IV) [VO(Pc), vanadyl phthalocyanine] and oxo(phthalocyanato)molybdenum(IV) [MoO(Pc), molybdenyl phthalocyanine] are described. The electrodes were prepared by incorporating the ionophores into plasticized poly(vinyl chloride) membranes, which were directly coated on the surface of graphite electrodes. The resulting electrodes demonstrate Nernstian responses over a wide linear range (10-7-10-1 M) salicylate. The electrodes have a fast response time, submicromolar detection limit, and could be used over the pH range of 6-9. The proposed sensors revealed selectivity for salicylate over a number of common inorganic and organic... 

A new catalyst based on metallophthalocyanine nanoparticles has been synthesized and characterized by scanning electron microscopy (SEM). The aqueous oxidation of alcohols to the corresponding carbonyl compounds (aldehydes and ketones) has been studied using tetra-n-butyl-ammonium-peroxo-monosulfate (n-Bu4NHSO5) as an oxidant and a catalytic system consisting of copper (II) phthalocyanine nanoparticles in water. The highly selective oxidation gave excellent yields of related aldehydes or ketones without remarkable over-oxidation of the carboxylic acids. Organic co-solvents, surfactants, and co-catalysts were not used in this catalytic strategy. This strategy was green and time effective. The... 

Copper phthalocyanine was used as ion carrier for preparing polymeric membrane selective sensor for detection of iodide. The electrode was prepared by incorporating the ionophore into plasticized poly(vinyl chloride) (PVC) membrane, coated on the surface of graphite electrode. This novel electrode shows high selectivity for iodide with respect to many common inorganic and organic anions. The effects of membrane composition, pH and the influence of lipophilic cationic and anionic additives and also nature of plasticizer on the response characteristics of the electrode were investigated. A calibration plot with near-Nernestian slope for iodide was observed over a wide linear range of five... 

An anion-selective electrode based on rhodium(II) phthalocyanine (RhPc) as a neutral carrier is reported. The prepared electrode displays an anti-Hofmeister behavior with a high selectivity for thiocyanate. The potentiometric response characteristics and selectivities of the membrane electrodes with various ratios of cationic additive to ion-carrier indicate that the observed potentiometric response is based on the formation of a 1:1 complex between RhPc and thiocyanate as an axial ligand. The membrane electrodes containing ∼60 mol percent of cationic additive (relative to ionophore) exhibit a near-Nernstian response in a concentration range of thiocyanate between 1 × 10-6 M to 1 × 10-1 M, a... 

The potentiometric response properties of several PVC-based membrane electrodes using phthalocyanine complexes of aluminum (AlPc), nickel (NiPc) and copper (CuPc) as anion carriers, toward thiosalicylic acid (TSA) were investigated. The influences of lipophilic ionic additives (cationic and anionic) and the pH of the buffered solutions were used for the interpretation of the mechanism of the potentiometric response of sensors. The sensitivity, linear range, detection limit, and potentiometric selectivity of the membrane sensors show a considerable dependence on the nature of central metal of the ionophore. The membrane electrodes based on AlPc demonstrate sub-Nernstian responses toward TSA... 

Voltammetric behavior of two mercaptopyrimidine derivatives (2-thiouracil and 2-thiobarbituric acid) has been studied by cyclic voltammetry at a cobalt phthalocyanine (CoPc)-modified carbon-paste electrode. The results of voltammetric determinations showed that the CoPc in the matrix of modified electrode acts as catalyst for electrooxidation of these thiols (RSH), lowering the overpotential of the reaction and significantly increasing the sensitivity for detection of thiols in neutral conditions. The results of voltammetric and polarization measurements in solutions with various pHs were used for prediction of the mechanism of electrocatalytic oxidation at the surface of modified electrode.... 

A metallophthalocyanine complex with zirconium(IV) ion in the center (as an oxo-zirconium, Zr=O, group) was used in poly vinyl chloride (PVC) membranes for the selective detection of 5-sulfosalicylic acid (SSA). The resulting electrodes demonstrate Nernstian responses over a wide range of sulfosalicylic acid concentration (10-6 to 10-1 mol dm-3) with a slope of about -29 mV per decade. The influence of lipophilic ion-exchanger sites on the response properties of the electrodes was investigated. The optimal potentiometric response was observed for the electrode in the presence of about 150 mol% of cationic additive (relative to ionophore) in the phase membrane. The electrodes have a fast... 

Perovskite solar cells have been constructed under the standard procedure by employing soluble tetratriphenylamine-substituted Zn phthalocyanine as hole transporting material. Solution processed device construction was carried out under ambient conditions of 50–60% ambient humidity. Triphenylamine substitution played the double role of imparting solubility to the core metal phthalocyanine as well as to introduce electron-rich ligands, which could enhance the role of Zn phthalocyanine as hole transporter. Indeed, the obtained material was functional. The present data highlight tetratriphenylamine-substituted Zn phthalocyanine as hole transporting material but also highlight the importance of... 

Copper phthalocyanine can effectively act as alternative small molecule hole transporting material in perovskite solar cells. In order to produce solution processed devices, a soluble copper phtalocyanine has been synthesized by n-butyl substitution and it was compared to commercially available tert-butyl substituted copper phthalocyanine. It was found that the configuration of the butyl chain plays a very important role in film conductivity and in the subsequent efficiency of solar cells, n-bytyl derivative being the most effective hole transporter. Such a result is due to the fact that n-butyl derivative allows better packing of the molecules in the film and stronger π-π interaction  

Perovskite solar cells have been constructed under ambient conditions by using 2,2',7,7'-Tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene (spiro-OMeTAD) mixed with a small quantity of soluble tetra-n-butyl substituted copper phthalocyanine as hole transporting material. The introduction of the phthalocyanine derivative resulted in an impressive increase of cell efficiency, which changed from 10.4% in the absence to 15.4% in the presence of phthalocyanine. This effect is related to the creation of deep traps in the hole transporting phase which block back-travelling electrons as well as to the improvement of the structural quality of the spiro-OMeTAD film in the presence of... 

Perovskite solar cells have been constructed under ambient conditions by using 2,2',7,7'-Tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene (spiro-OMeTAD) mixed with a small quantity of soluble tetra-n-butyl substituted copper phthalocyanine as hole transporting material. The introduction of the phthalocyanine derivative resulted in an impressive increase of cell efficiency, which changed from 10.4% in the absence to 15.4% in the presence of phthalocyanine. This effect is related to the creation of deep traps in the hole transporting phase which block back-travelling electrons as well as to the improvement of the structural quality of the spiro-OMeTAD film in the presence of... 

Two new macrocyclic ligands containing 17- and 19-membered O2N3-donor aza-crowns anchored to [60]Fullerene were synthesized and characterized by employing HPLC, electrospray ionization mass (ESI-MS), 1H and 13C NMR, UV–vis, IR spectroscopies, as well as powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA) in solid state. TGA measurements revealed that upon linking each of these macrocycle rings to [60]Fullerene, the decomposition point measured for [60]Fullerene moiety was increased, indicating on the promoted stability of [60]Fullerene backbone during binding to these macrocyclic ligands. Moreover, the ground state non-covalent interactions of [60]Fullerene derivatives of... 

The fabrication of efficient perovskite solar cells (PSCs) using all-vacuum processing is still challenging due to the limitations in the vacuum deposition of the hole transporting layer (HTL). Herein, inverted PSCs using copper (II) phthalocyanine (CuPC) as an ideal alternative HTL for vacuum processing are fabricated. After proper optimization, a PSC with a power conversion efficiency (PCE) of 20.3% is achieved, which is much better than the PCEs (16.8%) of devices with solution-based CuPC. As it takes a long time to dissolve CuPC in the solution-based device, the evaporation approach has better advantage in terms of fast processing. In addition, the device with the evaporated CuPC HTL... 

A film composed of carbon nanoparticles and poly(diallyldimethylammonium chloride) or CNP-PDDAC is formed in a layer-by-layer deposition process at tin-doped indium oxide (ITO) substrates. Excess positive binding sites within this film in aqueous phosphate buffer at pH 9.5 are quantified by adsorption of iron(III)phthalocyanine tetrasulfonate and indigo carmine. Both anionic redox systems bind with Langmuirian characteristics (K ≈ 105 mol-1 dm3) and show electrochemical reactivity throughout the film at different thicknesses. Therefore, the electrical conductivity in CNP-PDDAC films is good and the positive binding sites are approximately 140 pmol cm-2 per layer. Structural instability of... 

An efficient electrocatalyst for Pt-free I−/I3 − reduction has been synthesized by high temperature treatment of graphene oxide-cobalt phthalocyanine mixtures. The graphitic material was characterized by various techniques and was found to consist of reduced graphene oxide carrying CoN3 entities, obtained by thermal decomposition of cobalt phthalocyanine. This material had an ionization potential equal to 4.9±0.1 eV and thus it was judged appropriate to act as reduction electrocatalyst for the I−/I3 − redox electrolyte. It was subsequently deposited as thin film on FTO electrodes, which were employed as counter electrodes for dye-sensitized solar cells. Its capacity to reduce I−/I3 − redox... 

H2S and CO2 are the main impurities in raw natural gas, which needs to be purified before use. However, the comprehensive utilization of H2S and CO2 has been ignored. Herein, we proposed a fully resource-based method to convert toxic gas H2S and greenhouse gas CO2 synchronously into CO and elemental S by using a novel electrochemical reactor. The special designs include that, in the anodic chamber, H2S was oxidized rapidly to S based on the I−/I3− cyclic redox system to avoid anode passivation. On the other hand, in the cathodic chamber, CO2 was rapidly and selectively reduced to CO based on a porous carbon gas diffusion electrode (GDE) modified with polytetrafluoroethylene and cobalt... 

Organometal halide perovskite solar cells have been constructed using soluble tetra-n-butyl-copper phthalocyanine as hole transporting material. Devices were constructed and characterized under ambient conditions of 50–60% ambient humidity. Soluble copper phthalocyanine gave a modest PCE of 7.3% but when a buffer layer of either Al2O3 or graphene oxide was introduced between the perovskite and the hole transporting layer the cell efficiency extensively increased and reached 14.4% in the presence of graphene oxide. Corresponding data obtained by employing the standard spiro-OMeTAD as hole transporter gave equivalent performance. Combination then of tetra-n-butyl-copper phthalocyanine with...