Electro-oxidation of chlorophenols at glassy carbon electrodes modified with polyNi(II)complexes

The effect of the ligand macrocycle (phenylporphyrin (PP) or phthalocyanine (Pc)) and of the ligand substituent (NH₂ or SO₃⁻) on the catalytic activity for the electro-oxidation in a pH 11 buffer electrolyte of 2- and 4-chlorophenol (2-CP and 4-CP), 2,4- and 2,6-dichlorophenol (2,4-DCP and 2,6-DCP), 2,4,6-trichlorophenol (2,4,6-TCP), and pentachlorophenol (PCP) at glassy carbon electrodes modified with electropolymerized Ni(II) macrocycles was studied. The polyphenolic residue deposited at the electrode surface was characterized by cyclic voltammetry, impedance measurements, ex situ Fourier transform infrared spectroscopy (FT-IR) and X-ray Photoelectron Spectroscopy (XPS). A band of aliphatic CO stretching in the IR spectrum of the fouling film produced by potential cycling in 2,4,6-TCP indicated that the aromatic ring had been broken, yielding ketones, aldehydes and/or carboxylic acids. The sulphonated Ni(II) polymers, which showed the Ni(III)/Ni(II) process in the CV, had XP spectra typical of paramagnetic Ni(II), indicating that they contained Ni(OH)₂ clusters. On the contrary, the CVs of the amino Ni(II) did not show the Ni(III)/Ni(II) process at all, this process appearing only after previous activation by potential cycling, and only to a small extent. As was to be expected, the XP spectra of activated amino films corresponded to diamagnetic Ni(II), showing that the concentration of Ni(OH)₂ clusters was very small. The amino films were less active than the sulpho films for the oxidation of chlorophenols, in agreement with the lower concentration of Ni(OH)₂ clusters in the former films. For all electrodes the highest activity was observed for 2,4,6-TCP, since its oxidation yields a phenolic residue which is much more porous than those produced by the other CPs.     

Electrocatalytic oxidation of methanol on carbon paste electrode modified by nickel ions dispersed into poly (1,5-diaminonaphthalene) film

Poly (1,5-diaminonaphthalene) film was prepared by using the repeated potential cycling technique in an acidic solution at the surface of carbon paste electrode. Then transition metal ions of Ni(II) were incorporated to the polymer by immersion of the modified electrode in a 1.0 M nickel chloride solution. The electrochemical characterization of this modified electrode exhibits stable redox behavior of the Ni(III)/Ni(II) couple. Also, cyclic voltammetric experiments showed that methanol electrooxidized at the surface of this Ni(II) dispersed polymeric modified carbon paste electrode [Ni/P-1,5-DAN/MCPE]. The mechanism of methanol oxidation changes from diffusion control at low concentration to a catalytic reaction at higher methanol concentration. The effects of both scan rate and methanol concentration on the anodic peak height of the methanol oxidation were discussed.     

The passive behaviour of AISI 316 in alkaline media and the effect of pH: A combined electrochemical and analytical study

In this paper, thin surface films were formed on AISI 316 immersed in alkaline solutions of pH ranging from 13 to 9 under open circuit potential conditions. The electrochemical behaviour of the films formed under these conditions was evaluated by different electrochemical techniques: d.c. potentiodynamic polarisation, capacitance measurements (Mott-Schottky approach) and electrochemical impedance spectroscopy. The chemical composition was studied by X-ray photoelectron spectroscopy (XPS).The results reveal a good agreement between the film composition, the electronic properties and the electrochemical behaviour.The analytical results showed that the composition of the surface film changes with the pH. The films become enriched in Cr(III) and Fe(III) species and depleted in Fe(II) and Ni species, as the pH decreases from 13 to 9. The results are consistent with the formation of a film, presenting a bilayer structure, composed of an outer oxide/hydroxide layer, enriched in iron, and an inner anhydrous layer, rich in chromium and nickel oxides.Impedance measurements reveal that the resistance of the surface film increases during immersion and that the pH influences the evolution of the charge transfer resistance and the evolution of the film capacitance.Capacitance measurements based on the Mott-Schottky approach show that the concentration of electronic defects decreases with pH and that the films formed at pH 13 present the highest density of donors and, therefore, a more conductive behaviour.     

Investigation of ultrasound assisted regeneration of Ni–bentonite with response surface methodology (RSM)

This paper assesses the potential of ultrasonic desorption of toxic heavy metal Ni(II) from bentonite for regeneration purposes. Response surface methodology (RSM) was employed to optimize the desorption of Ni(II) retained on bentonite by varying the amount of adsorbent, contact time, pH and ultrasound time. The results indicated that in the present experimental setup, the pH and the ultrasound time were the most significant variables affecting Ni(II) desorption from bentonite. Based on statistical analysis, the Ni(II) desorption model was highly significant with very low p-values (< 0.0001) and the optimal control parameters were determined as follows: solid/liquid ratio (0.5 g/mL), contact time (6 h), pH (3.37) and ultrasound time (30 min). The experimental value of desorption percentage (59.4%) for regeneration of bentonite under the optimum conditions is in agreement with the predicted value of 64.5%.     

PVA基碱性聚合物电解质Ni(OH)2/AC超级电容器的电化学性能

Polyvinyl alcohol(PVA)-sodium polyacrylate(PAAS)-KOH-H₂O alkaline polymer electrolyte film with high ionic conductivity was prepared by a solution-casting method.Polymer Ni(OH)₂/activated carbon(AC) hybrid supercapacitors with different electrode active material mass ratios(positive to negative) were fabricated using this alkaline polymer electrolyte,nickel hydroxide positive electrodes,and AC negative electrodes.Galvanostatic charge/discharge and electrochemical impedance spectroscopy(EIS) methods were used to study the electrochemical performance of the capacitors,such as charge/discharge specific capacitance,rate charge/discharge ability,and charge/discharge cyclic stability.Experimental results showed that with the decreasing of active material mass ratio m(Ni(OH)₂)/m(AC),the charge/discharge specific capacitance increases,but the rate charge/discharge ability and the charge/discharge cyclic stability decrease.     

Cationic Peptides and Their Cu(II) and Ni(II) Complexes: Coordination and Biological Characteristics

Antimicrobial peptides are a promising group of compounds used for the treatment of infections. In some cases, metal ions are essential to activate these molecules. Examples of metalloantibiotics are, for instance, bleomycin and dermcidin. This study is focused on three new pseudopeptides with potential biological activity. The coordination behavior of all ligands with Cu(II) and Ni(II) ions has been examined. Various analytical methods such as potentiometric titration, UV-Vis and CD spectroscopies, and mass spectrometry were used. All compounds are convenient chelators for metal ion-binding. Two of the ligands tested have histidine residues. Surprisingly, imidazole nitrogen is not involved in the coordination of the metal ion. The N-terminal amino group, Dab side chains, and amide nitrogen atoms of the peptide bonds coordinated Cu(II) and Ni(II) in all the complexes formed. The cytotoxicity of three pseudopeptides and their complexes was evaluated. Moreover, their other model allowed for assessing the attenuation of LPS-induced cytotoxicity and anti-inflammatory activities were also evaluated, the results of which revealed to be very promising.     

Separation and concentration processes of solutions of Co(II), Ni(II), Cr(III), Fe(III) and Mn(II) by extraction with toluene-dissolved rosin

The extraction and stripping of Co(II), Ni(II), Cr(III) and Fe(III) from aqueous solutions by rosin dissolved in toluene has been investigated. Results obtained show that rosin is better extractant than abietic or n-lauric acids under comparable conditions. From these results, and the data of Mn(II) solvent extraction studied previously under the same conditions, a separation and concentration process for these five cations in aqueous solutions has been designed. Saturated solutions of Fe(III), Cr(III), Mn(II) and finally Co(II) and Ni(II) have been obtained successively by extraction and stripping, by addition of ammonium hydroxide to obtain the appropriate pH value, and by modifying adequately the organic phase/aqueous phase volume ratio.     

Fixed-bed column study on removal of Mn(II), Ni(II) and Cu(II) from aqueous solution by surfactant bilayer supported alumina

In the present work, the potential of modified alumina for the removal of heavy metals such as Mn(II), Ni(II) and Cu(II) was evaluated in a fixed-bed column operation. The effects of bed depth, flow rate and initial concentration on the removal of Mn(II), Ni(II) and Cu(II) were investigated at the optimum pH. The modified alumina was found to be very efficient for the removal of such heavy metals from water environment. Bed depth service time (BDST) model was best fitted to adsorption data. The theoretical and experimental breakthrough curves were comparable for all heavy metals.     

Investigation on the electrode process of the Mn(II)/Mn(III) couple in redox flow battery

The Mn(II)/Mn(III) couple has been recognized as a potential anode for redox flow batteries to take the place of the V(IV)/V(V) in all-vanadium redox battery (VRB) and the Br₂/Br⁻ in sodium polysulfide/bromine (PSB) because it has higher standard electrode potential. In this study, the electrochemical behavior of the Mn(II)/Mn(III) couple on carbon felt and spectral pure graphite were investigated by cyclic voltammetry, steady polarization curve, electrochemical impedance spectroscopy, transient potential-step experiment, X-ray diffraction and charge-discharge experiments. Results show that the Mn(III) disproportionation reaction phenomena is obvious on the carbon felt electrode while it is weak on the graphite electrode owing to its fewer active sites. The reaction mechanism on carbon felt was discussed in detail. The reversibility of Mn(II)/Mn(III) is best when the sulfuric acid concentration is 5 M on the graphite electrode. Performance of a RFB employing Mn(II)/Mn(III) couple as anolyte active species and V(III)/V(II) as catholyte ones was evaluated with constant-current charge-discharge tests. The average columbic efficiency is 69.4% and the voltage efficiency is 90.4% at a current density of 20 mA cm⁻². The whole energy efficiency is 62.7% close to that of the all-vanadium battery and the average discharge voltage is about 14% higher than that of an all-vanadium battery. The preliminary exploration shows that the Mn(II)/Mn(III) couple is electrochemically promising for redox flow battery.     

High surface area-activated carbon from Glycyrrhiza glabra residue by ZnCl2 activation for removal of Pb(II) and Ni(II) from water samples

A high-surface-area activated carbon was prepared by chemical activation of Glycyrrhiza glabra residue with ZnCl₂ as active agent. Then, the adsorption behavior of Pb(II) and Ni(II) ion onto produced activated carbon has been studied. The experimental data were fitted to various isotherm models. According to Langmuir model, the maximum adsorption capacity of Pb(II) and Ni(II) ions were found to be 200 and 166.7 mg g⁻¹, respectively, at room temperature. Kinetic studies showed the adsorption process followed pseudo second-order rate model. High values of intra-particle rate constants calculated shows the high tendency of activated carbon for removal of Pb(II) and Ni(II) ions.     

Electrochemical impedance spectroscopy of lead(II) ion-selective solid-state membranes

Silver sulphide/lead sulphide membranes were studied using electrochemical impedance spectroscopy. The influence of the electrolyte concentration and the membrane thickness were evaluated. The complex impedance plots have shown two capacitive loops: one at high frequency range, related with the charge transfer resistance at the interface membrane-Ag and a second one at low frequency range, associated with the diffusion process through the membrane. A simple model was used to take into account the experimental results: the changes of the potential with the time and the electrolyte concentration; the changes of the charge transfer resistance and the diffusion resistance with the electrolyte concentration. An empirical equation was used to calculate the diffusion coefficient of Ag⁺ inside the membrane.     

Adsorption of Ni(II) and Co(II) Using Microballoons Containing Mg-Silicate and CYANEX923 Prepared by the Emulsion Liquid Membrane System

Abstract

The Mg-silicate microballoons containing CYANEX923 were prepared by W/O/W emulsion. The diameter of obtained micro-sphere particles was ～10 µm and shell thickness was 2 µm. The adsorption of Co(II) and Ni(II) from aqueous solutions using prepared micro-sphere particles was investigated. Experiments were carried out as a function of solute concentration and temperature (25–60°C). Several kinetic models were used to test the experimental rate data and to examine the controlling mechanism of the adsorption process. Equilibrium adsorption data were analyzed using Langmuir isotherm model. The results indicated that prepared micro-sphere particles can be used as an efficient adsorbent for the removal of Ni(II) and Co(II) from aqueous solution.     

Oxidation of 4‐nitrophenol in water over Fe(III), Co(II), and Ni(II) impregnated MCM41 catalysts

BACKGROUND: Nitrophenols are toxic constituents of the effluents of petroleum, textile, dye, iron and steel, foundries, pharmaceutical and electrical manufacturing industries. Aromatic nitro compounds are particularly resistant to normal chemical or biological oxidation making them environmentally persistent. Advanced oxidation using appropriate catalysts mineralize these organics to harmless final products. In this work, MCM41‐based catalysts incorporating Fe(III)‐, Co(II)‐ and Ni(II)‐ cations were used for oxidizing 4‐nitrophenol in water under variable conditions of reaction time, pH, mole ratio of the reactant and the oxidant, catalyst load, feed concentration, and temperature. RESULTS: The catalysts prepared were characterized with X‐ray diffraction (XRD) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), cation exchange capacity (CEC) and atomic absorption spectrometry (AAS) measurements. In typical reaction conditions of temperature 353 K, time 300 min, catalyst load 2 g L^?1 and 10^?3 mol L^?1 4‐nitrophenol, the oxidation was 48.7, 52.2 and 55.2% with H₂O₂ and 42.5, 56.6 and 60.2% without H₂O₂ for Fe(III)‐, Co(II)‐ and Ni(II)‐MCM41, respectively. Pseudo‐first‐order kinetics with kinetic constant of 2.0 × 10^?3 to 5.5 × 10^?3 Lg^?1 min^?1 was proposed along with a possible mechanism. 4‐nitrocatechol, 4‐nitropyrogallol, 1,2,4‐trihydroxybenzene, hydroquinone, acrylic acid, malonic acid, and oxalic acid were identified in the oxidation products. CONCLUSION: Introduction of Fe(III)‐, Co(II)‐ and Ni(II)‐ into MCM‐41 by impregnation produced effective catalysts for wet oxidation of 4‐nitrophenol. The catalysts were able to oxidize 4‐NP even without the presence of an oxidizing agent. The results suggest that the transition metal loaded MCM41 brings about a more effective interaction between 4‐NP molecules and OH radicals. Copyright © 2008 Society of Chemical Industry     

Removal of Ni(II) ions from wastewater by micellar enhanced ultrafiltration using mixed surfactants

Ni(II) ions were removed from aqueous waste using micellar enhanced ultrafiltration (MEUF) with a mixture of surfactants. The surfactant mixture was the nonionic surfactant Tween 80 (TW80) mixed with the anionic surfactant sodium dodecyl sulfate (SDS) in different molar ratios ranging from 0.1–1.5. The operational variables of the MEUF process such as pH, applied pressure, surfactant to metal ion ratio and nonionic to ionic surfactant molar ratio (α) were evaluated. Rejection of Ni and TW80 was 99% and 98% respectively whereas that for SDS was 65%. The flux and all resistances (fouling resistance, resistance due to concentration polarization) were measured and calculated for entire range of α respectively. A calculated flux was found to be declined with time, which was mainly attributed to concentration polarization rather than resistance from membrane fouling.     

Calcined tetrabutylammonium kaolinite and montmorillonite and adsorption of Fe(II), Co(II) and Ni(II) from solution

Kaolinite and montmorillonite were modified with tetrabutylammonium (TBA) bromide, followed by calcination. The structural changes were monitored with XRD, FTIR, surface area and cation exchange capacity measurements. The modified clay minerals were used for adsorption of Fe(III), Co(II) and Ni(II) ions from aqueous solution under different conditions of pH, time and temperature. The uptake of the metal ions took place by a second order kinetics. The modified montmorillonite had a higher adsorption capacity than the corresponding kaolinite. The Langmuir monolayer capacities for the modified kaolinite and montmorillonite were Fe(III): 9.3 mg g^− 1 and 22.6 mg g^− 1; Co(II): 9.0 mg g^− 1 and 22.3 mg g^− 1; and Ni(II): 8.4 mg g^− 1 and 19.7 mg g^− 1. The modified kaolinite interacted with Co(II) in an endothermic manner, but all the other interactions were exothermic. The decrease of the Gibbs energy in all the cases indicated spontaneous adsorption.     

Preconcentration of Heavy Metals and Matrix Elimination using Silica Gel Chemically Modified with 2,3‐Dihydroxybenzaldehyde

Abstract

Many direct methods cannot easily be used to measure analytes such as Cd(II), Cu(II), Ni(II), Pb(II), and Zn(II) ions in sea and river water since these elements are present at very low concentration and the sample has a very complex matrix. In this study a method was developed to preconcentrate these ions by solid phase extraction within a column system using a newly synthesised 2,3‐dihydroxy benzaldehyde modified silica gel (SGDHB). Different parameters, such as pH, resin amount, eluent type, eluent volume, sample flow rate, preconcentration factors, and resin capacity were determined for the preconcentration of metal ions with the resin. Samples (125–500 ml) containing metal ions were passed through the column filled with SGDHB resin so that metal ions were retained on the column. The preconcentrated analytes were then eluted with 15 mL of 0.1 M HCl. The metal concentrations in the eluate were measured by FAAS. A sample and eluent flow rate of 1.12 and 0.56 ml/min respectively was used. Estimates of accuracy, precision, and detection limits were determined. In addition, analysis of the CRM LGC 6156 harbor sediment was undertaken, using the resin to isolate the analytes from potential interferences. Good agreement with certified values was obtained, indicating that the method is equally applicable to the analysis of water samples and to digests of solid materials.     

Impedance study of the passive film on stainless steel 304 in pH 8 carbonate solution

The effects of applied d.c. potential and polarization time on the passivation of stainless steel 304 (SS304) were investigated in deaerated 1 M NaHCo₃ aqueous solutions at pH 8. Electrochemical impedance spectroscopy was used in conjunction with a rotating disc electrode. The data were analysed by considering an equivalent circuit. The changes in impedance parameters at applied d.c. potential signal changes in the properties of passive films on SS304 and allow to distinguish the parameters at low potential (–0.6 to 0.3 V vs SCE) from a different one at high potential (0.5 to 0.8 V vs SCE). The oxidation reactions were controlled by both charge transfer and mass transfer processes. Diffusional resistance was high for both passive films and was considered to represent the resistance to movement of ions or vacancies through the surface layer of oxide films. It is deduced that the passive film present in the low potential region is partially dissolved at 0.4 V vs SCE and that a new passive film is formed in the higher potential region. The equivalent circuit used to obtain the best fit and the fitting parameters was dependent on the electrode potential and the polarization time. The reproducibility of the impedance spectra at constant potentials demonstrate that the passive film formation is highly irreversible process. No traces of localized corrosion were detected but, for a high potential and long polarization time, the electrode surface coloration to a uniform gold colour confirms the film thickening.     

A new kinetic model for Ni(II) ion flotation based on gene expression programming

ABSTRACT

The Ni(II) ion flotation kinetics with sodium dodecylsulfate as collector was studied with the aim of developing new models to predict the flotation rate constant (k) of Ni(II) ions and water removal during the process of Ni(II) ion flotation. In this regard, the most influential parameters on Ni(II) ion flotation efficiency including the ratio of collector concentration on the Ni(II) ion concentration, impeller speed, activity coefficient, and pH were used to develop predictive models. The results show that the proposed gene expression programming models can be used to predict the flotation rate constant of Ni(II) ions and water removal.     

Preparation of Poly(acrylamide-maleic Acid) Resin by Template Polymerization and Its Use for Adsorption of Co(II) and Ni(II)

Poly(acrylamide-maleic acid) resin P(AAm-MA) was prepared by template polymerization. Polyacrylamide PAAm was used as a template for the polymerization of MA in an aqueous solution using gamma rays as the initiator. The effects on the capacity of P(AAm-MA), such as concentration of maleic acid and amount of template polymer, were investigated. P(AAm-MA) has been utilized as an adsorbent for the removal of Co(II) and Ni(II) ions from an aqueous solution. The effects of time of equilibrium, pH, temperatures, and dosage of the adsorbent on the removal of Co(II) and Ni(II) ions have been studied. The equilibrium data were analyzed using the Langmuir and Freundlich isotherm models. The equilibrium process was described well by the Langmuir isotherm model.     

Electrochemical synthesis of Cr(II) at carbon electrodes in acidic aqueous solutions

The electrochemical synthesis of Cr(II) has been investigated on a vitreous carbon rotating disc electrode and a graphite felt electrode using cyclic voltammetry, impedance spectroscopy and chronoamperometry. The results show that in 0.1 M Cr(III) + 0.5 M sulphuric acid and in 0.1 M Cr(III) + 1 M hydrochloric acid over an electrode potential range of –0.8 to 0.8 V vs SCE, the electrochemical reaction at carbon electrodes is essentially a surface process of proton adsorption and desorption, without significant hydrogen evolution and chromium(II) formation. At electrode potentials more negative than –0.8 V vs SCE, both hydrogen evolution and chromium(II) formation occurred simultaneously. At electrode potentials –0.8 to –1.2 V vs SCE, the electrochemical reduction of Cr(III) on carbon electrodes is controlled mainly by charge transfer rather than mass transport. Measurements on vitreous carbon and graphite felt electrodes in 1 M HCl, with and without 0.1 M CrCl₃, allowed the exchange current density and Tafel slope for hydrogen evolution, and for the reduction of Cr(III) to Cr(II), to be determined. The chromium(III) reduction on vitreous carbon and graphite electrodes can be predicted by the extended high field approximation of the Butler–Volmer equation, with a term reflecting the conversion rate of Cr(III) to Cr(II).