Electrochemical cell current requirements for toxic organic waste destruction in Ce(IV)-mediated electrochemical oxidation process

The electrochemical cell for cerium oxidation and reactor for organic destruction are the most important operation units for the successful working mediated electrochemical oxidation (MEO) process. In this study, electrochemical cells with DSA electrodes of two types, single stack and double stack connected in series, were used. The performances towards the electrochemical generation of Ce(IV) in nitric acid media at 80 °C were studied. The current-voltage curves and cerium electrolysis kinetics showed the dependence on number of cell stacks needed to be connected in series for the destruction of a given quantity of organic pollutant. The presence of an optimum region for Ce(III) oxidation with a contribution of oxygen evolution, especially at low Ce(III) concentration (high conversion ratios), was found. The cells were applied for the Ce(IV) regeneration during the organic destruction. The cell and reactor processes were fitted in a simple model proposed and used to calculate the current needed in terms of Ce(III) oxidation rate and the number of cell stacks required for maintaining Ce(IV)/Ce(III) ratio at the same level during the organic destruction. This consideration was based on the kinetic model previously developed by us for the organic destruction in the MEO process.     

Novel method for removal of NO x and SO2 by sustainable electrochemical process using Ag(I)/Ag(II) redox mediator

The objective of this work was to develop a process for removal of industrial waste gases like NO, NO₂ and SO₂ by electrochemically generated Ag(I)/Ag(II) redox mediator system in aqueous nitric acid medium. 100% removal efficiencies were achieved in these studies for removal of NO _x and SO₂ with Ag(II) ions in room temperature and atmospheric pressure. This Ag(I)/Ag(II) redox mediator system can be regenerated continuously during the scrubbing process.     

Cerium(IV)-mediated electrochemical oxidation process for destruction of organic pollutants in a batch and a continuous flow reactor

The mediated electrochemical oxidation (MEO) process with Ce(IV) and nitric acid as the oxidizing medium was employed for the destruction of various model organic pollutants in batch and continuous organic feeding modes. A near complete destruction was observed for all the model organic pollutants studied. The effects of organic concentration, temperature, concentration of Ce(IV), concentration of nitric acid and feeding time on the organic destruction efficiency were investigated. Under the experimental conditions of 80 °C and 0.95 M Ce(IV) in 3 M nitric acid, nearly 90% destruction was achieved based on CO₂ production and 95% based on TOC and COD nearly for all the organic compounds studied in batch organic addition. In the case of continuous organic addition with in situ electroregeneration of Ce(IV) by the electrochemical cell a good destruction efficiency was obtained. For long term organic feeding (120 min) the destruction efficiency was found to be 85% based on CO₂ evolution and 98–99% based on TOC and COD analyses. A model was proposed for calculating the CO₂ formation constant during the continuous process of organic addition. The model predicted a steady state CO₂ evolution pattern for the destruction process during continuous organic feeding. The experimental results obtained confirmed the predicted trends for the destruction process. The changes in enthalpy, entropy, activation energy and free energy for EDTA degradation were found to be 26.7 kJ/mol, −230 J/(mol·K), 29.7 kJ/mol, and 118 kJ/mol respectively.     

A sustainable mediated electrochemical process for the abatement of NOx from simulated flue gas by using Ag(I)/Ag(II) redox mediators

Electrochemical removal of NO and NO₂ by using Ag(I)/Ag(II) redox mediator system in nitric acid medium by two-stage scrubbing process was investigated. Experiments were carried out for the complete removal of NO and NO₂ from the stimulated flue gas at room temperature and atmospheric pressure. The process parameters like current density, Ag(I) concentration, HNO₃ concentration, initial concentration of NO, Ag(I) concentration and temperature were studied and optimized. A removal efficiency of >99% was achieved using this sustainable redox process. Ag(II)/Ag(I) can be regenerated and reused for the scrubbing of waste gases continuously and there is no other gases emission during scrubbing.     

Mediated electrochemical oxidation of phenol in continuous feeding mode using Ag (II) and Ce (IV) mediator ions in nitric acid: A comparative study

Mediated electrochemical oxidation (MEO) process is one among the latest treatment technologies for the destruction of toxic organic pollutants under ambient temperatures and at atmospheric pressure. The process is a further extension of the conventional electrochemical treatment for the removal of toxic organics with powerful mediator oxidants in acidic medium. In this report the experimental results of using silver and cerium as mediator ions were compared with respect to their electro-oxidation behavior within the limitations of each mediator metal ion and their destruction efficiencies were compared for destructing phenol in continuous feeding mode. The following conclusions were drawn: (i) the optimum nitric acid concentration was found to be 8 and 3 M and the optimum temperature was found to be 60 and 80 °C for silver and cerium electro-oxidations, respectively; (ii) in the case of Ag (II)-MEO of phenol the maximum destruction efficiency achieved was 98% at 70 °C based on CO₂ evolved; (iii) for Ce (IV)-MEO of phenol the maximum destruction efficiency achieved was 93% at 90 °C based on CO₂. The results may provide baseline information on the use of suitable mediator metal ion in treating the target organic wastes by MEO process.     

Characterization of Ag(I), Co(II) and Cu(II) removal process from aqueous solutions using dolomite powder

Dolomite, a natural adsorbent, was used for removal of Ag(I), Cu(II) and Co(II) from aqueous solutions. Adsorption parameters including pH, temperature and contact time have been investigated to obtain adsorption mechanism. The results of experiments showed that adsorption of the metal ions increased by increasing pH values up to 5.5. The adsorption process was initially fast. Equilibrium isotherm data were analyzed using Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. Maximum adsorption capacity of Ag(I), Cu(II) and Co(II) was 1.34, 1.63 and 2.84 mg/g at 20 oC, respectively. Kinetic models including Lagergren first-order and pseudo-second-order were used to test kinetic data. The results showed that pseudo-second-order has good agreement with experimental data. Thermodynamic parameters of the process were also investigated at different temperatures. The negative values of Gibbs free energy and enthalpy changes for Ag(I), Cu(II) and Co(II) indicated the spontaneous and exothermic nature of the adsorption process.     

Removal of H2S using a new Ce(IV) redox mediator by a mediated electrochemical oxidation process

BACKGROUND: Hydrogen sulfide (H₂S) from industrial activities and anaerobic manure decomposition in commercial livestock animal operations is an offensive malodorous and toxic gas even in small concentrations, causing serious discomfort and health and social problems. The objective of this study was to employ for the first time a novel, attractive, low cost, environmentally benign mediated electrochemical oxidation (MEO) process with Ce(IV) as the redox catalyst for H₂S gas removal from an H₂S–air feed mixture. RESULTS: The influence of liquid flow rate (Q_L) from 2–4 L min^?1, gas flow rate (Q_G) from 30–70 L min^?1, H₂S concentration in the H₂S–air feed mixture from 5–15 ppm, and Ce(III) pre‐mediator concentration in the electrochemical cell from 0.1–1 mol L^?1 on H₂S removal efficiency were investigated. Both liquid and gas flow rates influenced the removal efficiencies, but in opposite directions. Nearly 98% H₂S removal was achieved when the concentration of Ce(IV) mediator ion in the flowing scrubbing liquid reached 0.08 mol L^?1. CONCLUSIONS: The new MEO method proved promising for H₂S removal, achieving high removal efficiency. Integration of the electrochemical cell with the scrubber set‐up ensured continuous regeneration of the mediator and its repeated reuse for H₂S removal, avoiding use of additional chemicals. Since the process works at room temperature and atmospheric pressure utilizing conventional transition metal oxide electrodes more commonly used in industrial applications, it is also safe and economical. Copyright © 2008 Society of Chemical Industry     

Adsorption of cadmium(II) from aqueous solution by surface oxidized carbon nanotubes

Carbon nanotubes (CNTs) were oxidized with H₂O₂, KMnO₄ and HNO₃. Their physicochemical properties were investigated by BET N₂ adsorption, laser particle examination, Boehm’s titration, zeta potential measurement and cadmium(II) adsorption. The experimental results suggest that cadmium(II) adsorption capacities for three kinds of oxidized CNTs increase due to the functional groups introduced by oxidation compared with the as-grown CNTs. The cadmium(II) adsorption capacity of the as-grown CNTs is only 1.1 mg g⁻¹, while it reaches 2.6, 5.1 and 11.0 mg g⁻¹ for the H₂O₂, HNO₃ and KMnO₄ oxidized CNTs, respectively, at the cadmium(II) equilibrium concentration of 4 mg l⁻¹. Adsorption of cadmium(II) by CNTs was strongly pH-dependent and the increase of adsorption capacities for HNO₃ and KMnO₄ oxidized CNTs is more obvious than that of the as-grown and H₂O₂ oxidized CNTs at lower pH regions. The experiments of CNT dosage effect on the cadmium(II) adsorption show that the adsorption capacity for KMnO₄ oxidized CNTs has a sharper increase at the CNT dosage from 0.03 to 0.08 g per 100 ml than the as-grown, H₂O₂ and HNO₃ oxidized CNTs and its removal efficiency almost reaches 100% at CNT dosage of 0.08 g per 100 ml. Analysis revealed that the KMnO₄ oxidized CNTs hosted manganese residuals, and these surely contributed to cadmium sorption to a yet-undefined extent.     

Adsorption of Cd(II), Pb(II), and Ag(I) in aqueous solution on hollow chitosan microspheres

Cross‐linked chitosans synthesized by the inverse emulsion cross‐link method were used to investigate adsorption of three metal ions [Cd(II), Pb(II), and Ag(I)] in an aqueous solution. The chitosan microsphere, was characterized by FTIR and SEM, and adsorption of Cd(II), Pb(II), and Ag(I) ions onto a cross‐linked chitosan was examined through analysis of pH, agitation time, temperature, and initial concentration of the metal. The order of adsorption capacity for the three metal ions was Cd²⁺ > Pb²⁺ > Ag⁺. This method showed that adsorption of the three metal ions in an aqueous solution followed the monolayer coverage of the adsorbents through physical adsorption phenomena and coordination because the amino (? NH₂) and/or hydroxy (? OH) groups on chitosan chains serve as coordination sites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Growth mechanisms of CuSCN films electrodeposited on ITO in EDTA-chelated copper(II) and KSCN aqueous solution

Electrodeposition of β-CuSCN films was investigated on transparent conducting ITO substrates in an aqueous electrolyte containing EDTA-chelated Cu(II) and KSCN. It has been observed that the instability of CuSO₄ and KSCN aqueous solution without EDTA is due to the formation of Cu(SCN)₂ precipitation, which can transform into CuSCN and (SCN)_x at room temperature. Research results illuminate that the deposited film at −0.5 V versus Ag/AgCl_sat at 298 K is uniform and dense and composed of nanocrystals. The film is p-type with stoichiometric excess of SCN and a direct transition gap of 3.7 eV. Deposition mechanisms of CuSCN films at varied temperatures are studied based on the proposed energetic model. At or below room temperature, the electron quantum tunnel through deposition layer is predominant at the very beginning. However, the growth is limited when the thickness of CuSCN film reaches the size comparable to the diffusion length of electrons. Above room temperature, the thermal activation of surface states plays an important role in the continuous growth of large crystals through holes transport in the valence band. The calculated activation energy for crystal growth is 0.5 eV.     

Kinetic and equilibrium studies of Pb(II) and Cd(II) removal from aqueous solution onto colemanite ore waste

The adsorption characteristics of Pb(II) and Cd(II) onto colemanite ore waste (CW) from aqueous solution were investigated as a function of pH, adsorbent dosage, contact time, and temperature. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models were applied to describe the adsorption isotherms. Langmuir model fitted the equilibrium data better than the Freundlich isotherm. The adsorption capacity of CW was found to be 33.6 mg/g and 29.7 mg/g for Pb(II) and Cd(II) ions, respectively. Analyte ions were desorbed from CW using both 1 M HCl and 1 M HNO₃. The recovery for both metal ions was found to be higher than 95%. The mean adsorption energies evaluated using the D-R model indicated that the adsorption of Pb(II) and Cd(II) onto CW were taken place by chemisorption. The thermodynamic parameters (ΔG^o, ΔH^o and ΔS^o) showed that the adsorption of both metal ions was feasible, spontaneous and exothermic at 20-50 °C. Adsorption mechanisms were also investigated using the pseudo-first-order and pseudo-second-order kinetic models. The kinetic results showed that the adsorption of Pb(II) and Cd(II) onto CW followed well pseudo-second order kinetics.     

Studies on promising cell performance with H2SO4 as the catholyte for electrogeneration of Ag2+ from Ag+ in HNO3 anolyte in mediated electrochemical oxidation process

Electrochemical performance of a divided cell with electrogeneration of Ag²⁺ from Ag⁺ in 6 M HNO₃ anolyte has been studied with 6 M HNO₃ or 3 M H₂SO₄ as the catholyte. This work arose because in mediated electrochemical oxidation (MEO) processes with Ag(II)/Ag(I) redox mediator, HNO₃ is generally used as catholyte, which, however, produces NO _x gases in the cathode compartment. The performance of the cell with 6 M HNO₃ or 3 M H₂SO₄ as the catholyte has been compared in terms of (i) the acid concentration in the cathode compartment, (ii) the Ag⁺ to Ag²⁺ conversion efficiency in the anolyte, (iii) the migration of Ag⁺ from anolyte to catholyte across the membrane separator, and (iv) the cell voltage. Studies with various concentrations of H₂SO₄ catholyte have been carried-out, and the cathode surfaces have been analyzed by SEM and EDXA; similarly, the precipitated material collected in the cathode compartment at higher H₂SO₄ concentrations has been analyzed by XRD to understand the underlying processes. The various beneficial effects in using H₂SO₄ as catholyte have been presented. A simple cathode surface renewal method relatively free from Ag deposit has been suggested.     

Host (nanocavity of zeolite-Y)/guest (Mn(II), Co(II), Ni(II) and Cu(II) complexes of pentadendate Schiff-base ligand) nanocomposite materials (HGNM): application in the heterogeneous oxidation of cyclohexene

Transition metal (M = Mn(II), Co(II), Ni(II) and Cu(II)) complexes with pentadendate Schiff-base ligand; N,N′-bis(salicylidene)-2,6-pyridinediaminato, H₂ [sal-2,6-py]; was entrapped in the nanocavity of zeolite-Y by a two-step process in the liquid phase: (i) adsorption of bis(salicylaldiminato)metal(II); [M(sal)₂]-NaY; in the supercages of the zeolite, and (ii) in situ Schiff condensation of the metal(II) precursor complex with the corresponding 2,6-pyridinediamine; [M(sal-2,6-py)]-NaY. The new materials were characterised by several techniques: chemical analysis, spectroscopic methods (DRS, BET, FTIR and UV/Vis), conductometric and magnetic measurements. Analysis of the data indicates that the M(II) complexes are encapsulated in the nanodimensional pores of zeolite-Y and exhibit different from those of the free complexes, which can arise from distortions caused by steric effects due to the presence of sodium cations, or from interactions with the zeolite matrix. The Host–Guest Nanocomposite Materials (HGNM); [M(sal-2,6-py)]-NaY; catalyzes the oxidation of cyclohexene with tert-butylhydroperoxide (TBHP). Oxidation of cyclohexene with HGNM gave 2-cyclohexene-1-one, 2-cyclohexene-1-ol and 1-(tert-butylperoxy)-2-cyclohexene. [Mn(sal-2,6-py)]-NaY shows significantly higher catalytic activity than other catalysts.     

Electrochemical behavior of poly(3-hexylthiophene). Controlling factors of electric current in electrochemical oxidation of poly(3-hexylthiophene)s in a solution

Electrochemical response of regio-random and regio-controlled poly(3-hexylthiophene), P3HexTh, was investigated by cyclic voltammetry. P3HexTh underwent electrochemical oxidation at about 0.4 V vs. Ag⁺/Ag in a THF solution, and the peak anode electric current, i_pa, was proportional to the sweeping rate v; i_pa=const×v^1/2. These data indicated that diffusion of the P3HexTh molecule in the solution was important to determine i_pa. Application of a Matsuda's equation with assumptions gave a diffusion coefficient, D, of about 1×10⁻⁷ cm² s⁻¹ at molecular weight of about 5000, and the D value steeply decreased with increase in the molecular weight.     

Sorptive removal of Pb(II) ions from aqueous solution using sweetmeat waste: Batch and column study

This article deals with removal of Pb(II) ions from aqueous media using sweet industry byproduct, that is, sweetmeat waste (SMW). The SEM images revealed highly heterogeneous sorbent surface. XRD and FTIR studies were done. The sorption equilibrium time was found 45 min only, and the sorption followed pseudo-second-order reaction model, indicating chemisorption as the rate-limiting step. Pb(II) removal followed Langmuir isotherm model best, and the maximum sorption capacity was 11.38 mg/g. The fixed bed column study was performed and analyzed using Logit, Bohart-Adams and Wolborska models. The sorption rate and capacity constants were 0.143(±0.017) L/mg.h and 39(±7) mg/L, respectively.     

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.     

Extracting Cu(II) from aqueous solutions with hydrophobic room-temperature ionic liquid in the presence of a pyridine-based ionophore to attempt Cu recovery: A laboratory study

Extraction of Cu(II) from neutral aqueous solutions with the hydrophobic room-temperature ionic liquid (IL) N-butyl-N-methylpyrrolidinium bis((trifluoromethyl)sulfonyl)imide (BMP-TFSI) in the presence of the pyridine-based ionophore N¹,N¹,N⁴,N⁴-tetrakis(2-(pyridin-2-yl)ethyl)butane-1,4-diamine (C₄N₂Py₄) is demonstrated in this study. Although the distribution coefficients, D_M, of Cu(II) extraction depend on the concentration of Cu(II) in aqueous solutions, all values were higher than 200, indicating extremely high extraction efficiency. Based on spectrophotometric, electrochemical, and X-ray crystallography studies, the coordination number of the C₄N₂Py₄-coordinated Cu(II) ions was determined as 2. The voltammetric behavior of Cu(I), Cu(II), and their C₄N₂Py₄ complex ions were also studied. The recovery of Cu from the IL was conducted by washing the IL phase containing the extracted Cu(II) complex with an acidic aqueous phase or by controlled-potential electrolysis. The IL containing C₄N₂Py₄ was employed for two complete rounds and a decrease in extraction efficiency was only observed when higher concentration of Cu(II) was used.     

Enhanced adsorption and recovery of Pb(II) from aqueous solution by alkali‐treated persimmon fallen leaves

Persimmon fallen leaves were employed to prepare a renewable and low‐cost biosorbent named as NPFL. Effects of initial pH, contact time, initial Pb(II) concentration, coexisting metal ions, and ionic strength on adsorption of Pb(II) from aqueous solution by NPFL were studied in detail. Enhanced removal capacity of NPFL toward Pb(II) was observed, and the maximum adsorption capacity was evaluated as 256 mg g^?1 by Langmuir modeling calculation. The fast adsorption process and the well‐fitted kinetics data with pseudo‐second‐order model indicated that chemisorption is the main rate‐limiting step for the adsorption process. NPFL had superior adsorption selectivity for Pb(II) from aqueous solution with coexisting metal ions. Characterization of NPFL and adsorption mechanism (electrostatic attraction, ion exchange, and chelation) were performed using XRD, SEM‐EDS, FT‐IR, XPS, and TGA. The results suggested that NPFL could be utilized as a potential candidate for the preconcentration of Pb(II) recovery and its removal in practice. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43656.