Sharif Digital Repository

Nowadays cobalt is mostly produced through the electrowinning process of sulfate solutions. Regarding to the competition between the precipitation of cobalt ions and evolution of hydrogen gas on the cathode surface during the reduction process in a sulfate bath, investigation on the mechanism of metal precipitation is of great importance. In the present work, study on the kinetics of cobalt electrowinning and the mechanism of the involved reactions have been carried out. The obtained results, confirm the mechanism of cobalt precipitation by depletion of hydroxides. The effects of temperature and scan rate parameters were studied on electrowinning of cobalt by cyclic voltammetry technique.... 

Electrochemical oxidation of acetaminophen (N–acetyl–p–aminophenol) (1) has been studied in the presence of dimethylamine (2) as a nucleophile in aqueous solution, by means of cyclic voltammetry and controlled-potential coulometry. The results indicate the participation of electrochemically generated N-acetyl-p-quinoneimine (1a) in Michael reaction with dimethylamine (2). Based on ECE mechanism, the observed homogeneous rate constant (kobs) of the above mentioned reaction is estimated by comparing the experimental cyclic voltammograms with the digital simulated results. Further more; kinetics and mechanism of the reaction were studied with ab initio calculation, Monte Carlo and QM/MM... 

The electrochemical response of sodium levo-thyroxin (T4) at the surface of an edge plane pyrolytic graphite (EPPG) electrode is investigated using cyclic voltammetric technique in the presence of 0.1M HCl as supporting electrolyte. T4 underwent totally irreversible oxidation at this system and a well-defined peak at 821mV was obtained. Compared to the signals obtained in the optimized conditions at bare glassy carbon and carbon paste electrodes, the oxidation current of T4 at an EPPG electrode was greatly enhanced. The electrochemical process of T4 was explored and the experimental conditions were optimized. The oxidation peak current represented a linear dependence on T4 concentration from... 

The electrochemical behavior of the anti-inflammatory drug piroxicam is studied at the surface of a plain pyrolytic graphite electrode modified with chitosan-doped carbon nanoparticles. An electroactive surface was produced by drop-casting a suspension of the modifier and characterized by atomic force microscopy. A remarkable enhancement is found in studies on the cyclic voltammetric response towards piroxicam. This is described on the basis of the thin-layer mass transport regimes within the porous films, which leads to a considerable increase in the active surface area of the electrode. The electrode shows a linear response to piroxicam in the range of 0.05-50 μM, with a detection limit of... 

The complexes of zinc tetraphenylporphyrin (ZnTPP) with the azacrown macrocycles bearing pyridine moiety (bp, 1p) as the axial ligand were synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR, 1H and 13C NMR, fluorescence, UV–Vis, together with TD DFT calculations. Solution study by employing 1H NMR spectroscopy for ZnTPPbenz and ZnTPPH complexes elucidated that the pyridine moiety was bonded through the fifth-coordination site on the zinc metal atom. The observation of hypsochromic shifts of ca. 15 nm for Q(0,1) (the strongest emission) as well as ca. 15 nm for Q(0,0) (the second) bands testified to significant difference in the fluorescence of ZnTPPbenz... 

This paper reports on a novel low-temperature method for preparing curcumin-reduced graphene oxide (Cur-rGO) from graphene oxide (GO) and investigates their cyclic voltammetry (CV) and photoluminescence (PL) properties. GO sheets were synthesized using modified Hummers’ method and then were chemically reduced using polyphenol curcumin into graphene sheets. Atomic force microscopy, transmission electron microscopy and x-ray photoelectron spectroscopy were used to confirm the formation of Cur-rGO and revealed their functionalization with polyphenol curcumin. The electrochemical and optical properties of the Cur-rGO sheets were investigated using CV and PL spectroscopy. According to the PL and... 

The electrochemical behavior of a tin electrode in citric acid solutions of different concentrations was studied by electrochemical techniques. The E/I curves showed that the anodic behavior of tin exhibits active/passive transition. Passivation is due to the formation of Sn(OH)4 and/or SnO2 film on the electrode surface. Addition of NaCl to citric acid solution, enhances the active dissolution of tin and tends to breakdown the passivity at a certain breakdown potential. Cyclic voltammetry and galvanostatic measurements allow the pitting potential (Epit) and the repassivation potential (Erp) to be determined. Potentiostatic measurements showed that the overall anodic processes can be... 

The electrochemical behavior of catechol in the presence of propylthiouracil (PTU) and methylthiouracil (MTU) at a glassy carbon electrode is thoroughly investigated. The cyclic voltammetric studies of the systems are performed in different pHs and sweep rates. The results of the voltammetric foundations show an electrocatalytic oxidation of catechol in the presence of PTU and MTU, leading to a remarkable increase in the anodic peak current of catechol together with the contemporaneous disappearance of the corresponding cathodic wave. The presented mechanism shows the nucleophilic addition/reduction of the electro-generated o-quinone by the PTU or MTU, which produced chemically reduced... 

The voltammetric behavior of thioglycolic acid (TGA) was studied at a carbon paste electrode modified with cobalt phthalocyanine (CoPc). The CoPc-modified electrode shows high electrocatalytic activity toward oxidation of TGA, lowering substantially the overpotential of anodic reaction. Results of the cyclic voltammetry show that TGA undergoes a two-step oxidation (each step with one electron) resulting the dimer of thiol. Enhancement of the rate of electron transfer results in a near-Nernstian behavior of modified electrode to the concentration of TGA and makes it as a suitable potentiometric sensor for the detection of this compound. This electrode shows a near-Nernstian response in a wide... 

The new dinuclear copper(II) complexes, Cu(II)M(II) (M = Mn, Co, Ni, Cu), of a phenol-based compartmental ligand, having dissimilar N(amine)2O2 and N(imine)2O2 coordination sites have been synthesized. In this system there are two different compartments, one has piperazinyl nitrogens and phenolic oxygens and the other compartment has meso-stilbenediamine nitrogens and phenolic oxygens as coordinating sites. The complexes were characterized by elemental analysis, IR and electronic spectra as well as conductivity measurements. Dinuclear complexes were prepared through the CuIIPbII precursor complex by transmetalation of the Pb(II) for the M(II) ion. The electrochemistry and catecholase-like... 

A multi-walled carbon nanotube paste electrode (MWCPE) is prepared as an electrochemical sensor with high sensitivity and selectivity in responding to isoniazid. The electrochemical oxidation of isoniazid is investigated in buffered solution by cyclic and differential pulse voltammetry. The electrode is shown to be very effective for the detection of isoniazid in the presence of other biological reductant compounds. The electrochemical oxidation of cysteine, due to the high overvoltage, is completely stopped at the surface of MWCPE. The electrode exhibits a very good resolution between the voltammetric peak of isoniazid and the peaks of ascorbic acid (AA) and dopamine (DA). A resolution of... 

The mechanism of electrochemical behavior of catechol in the presence of thiaproline is investigated by cyclic voltammetry, controlled-potential coulometry and spectrophotometric tracing of the reaction coordinate. The results indicate that thiaproline participate in with an ECEC mechanism in a nucleophilic (Michael) addition to o-quinone. Effect of pH of buffer solution on reaction pathway is studied and showed that addition of thiaproline to the o-quinone is performed only in solutions with pHs higher than 5. These results indicate that the addition of thiaproline is occurred first from amine functional group. In the second step, the addition of carboxylate group of thiaproline to C-5 of... 

A carbon-paste electrode chemically modified with a Schiff-base complex of cobalt (cobalt(II)-4-chlorosalophen, CoClSal) is utilized to investigate the voltammetric response of propylthiouracil (PTU). The mechanism of electrocatalytic oxidation of the compound is investigated by means of cyclic voltammetric studies applying various pHs to the buffered solutions. The modified electrode exhibits effective catalytic properties that lower the anodic overpotential and enhance the rate of electron transfer for the electrochemical oxidation of PTU. The results of the cyclic voltammetric (CV) and differential pulse voltammetric (DPV) techniques showed that the modified electrode exhibits good... 

Electrodeposition of the Co-Ni/Cu multilayer films was carried out in sulfate solution. Cyclic voltammetry and current transient techniques were utilized to characterize the multilayer system and to obtain the nucleation and growth mechanism. The cyclic voltammograms clearly showed that electrodeposition of cobalt-nickel alloy layer was controlled by a kinetic process, where copper ions were reduced under diffusion-controlled mechanism. In addition, the current transients revealed that nucleation mechanism was instantaneous with a typical three-dimensional growth process. The microstructure of the Co-Ni/Cu films was also changed with overpotential. In this system, the growth of multilayer... 

A modified carbon-paste electrode (CPE) is prepared by incorporating thionine-nafion supported on multi-walled carbon nanotube (MWCNT). The electrochemical behavior of dopamine (DA) and ascorbic acid (AA) on the surface of the modified electrode is investigated by cyclic voltammetry (CV). The results show that thionine effectively immobilized in the matrix of the paste by using an appropriate mixture of nafion/MWCNT under the ultrasonic condition. On the other hand, presence of nafion enhances the stability of the thionine supported by MWCNT in the composite electrode and improves the reproducibility of the surface of the modified electrode under renewing process by polishing. The results of... 

Hydrogen evolution and electrosorption on/in TiHg alloy have been investigated in acidic solution using cyclic voltammetry, open circuit potential transient, steady-state polarization, chronopotentiometry and electrochemical impedance measurements. Comparison has been made with pure Ti. Cyclic voltammetry and open circuit potential measurements show that hydrogen absorption into the electrode material occurs during proton discharge. The steady-state polarization curves in the course of positive and negative potential scans illustrate that the formation of absorbed hydrogen slightly improves the electrocatalytic properties of the electrode. The hydrogen diffusion coefficient into the bulk of... 

The electrocatalytic oxidation of cephalexin and cefazolin has been studied at a carbon paste electrode modified with cobalt salophen (CoSal) by cyclic voltammetry. The selectivity of the carbon paste modified with CoSal in detecting cephalexin and cefazolin was examined. To suggest the electrocatalytic mechanism for electro-oxidation of cefazolin, the electrochemical behavior of ceftriaxone was investigated which has a thiol group out of the beta lactam ring. The electrocatalytic oxidation of these antibiotics is shown to be irreversible at the CoSal modified electrode. Scan rate dependence of cefazolin, which is a sulfur-containing compound, has been examined. The results indicated that... 

Nickel-dimethylglyoxime complex (NiDMG) modified nickel electrode (Ni/NiDMG) showed a catalytic activity towards methanol oxidation in NaOH solution. The modified electrode prepared by the dimethylglyoxime anodic deposition on Ni electrode in the solution containing 0.20 mol L-1 NH4Cl + NH4OH (pH 9.50) and 1.0 × 10-4 mol L-1 dimethylglyoxime. The modified electrode conditioned by potential recycling in a potential range of 100-700 mV (vs. SCE) by cyclic voltammetry in alkaline medium (0.10 M NaOH). The results show that the NiODMG film on the electrode behaves as an efficient catalyst for the electrooxidation of methanol in alkaline medium via Ni(III) species formed on the electrode with the... 

The electro-catalytic oxidation of methanol on a Ni-Cu alloy (NCA) with atomic ratio of 60/40 having previously undergone 50 potential sweep cycles in the range 0-600 mV vs. (Ag/AgCl) in 1 m NaOH was studied by cyclic voltammetry (CV), chronoamperometry (CA) and impedance spectroscopy (EIS). The electro-oxidation was observed as large anodic peaks both in the anodic and early stages of the cathodic direction of potential sweep around 420 mV vs. (Ag/AgCl). The electro-catalytic surface was at least an order of magnitude superior to a pure nickel electrode for methanol oxidation. The diffusion coefficient and apparent rate constant of methanol oxidation were found to be 2.16 × 10-4 cm2 s-1 and...