Sustainable removal of N2O by mediated electrocatalytic reduction at ambient temperature electro-scrubbing using electrogenerated Ni(I) electron mediator.

Direct catalysis is generally proposed for nitrous oxide (N2O) abatement but catalysis is expensive, requires high temperatures, and suffers from media fouling, which limits its lifetime. In the present study, an ambient temperature electroscrubbing method was developed, coupling wet-scrubbing with an electrogenerated Ni(I) ([Ni(I)(CN)4]3-) mediator, to enable N2O reduction in a single process stage. The initial studies of 10 ppm N2O absorption into 9 M KOH and an electrolyzed 9 M KOH solution showed no removal. However, 95% N2O removal was identified through the addition of Ni(I) to an electrolyzed 9 M KOH. A change in the oxidation/reduction potential from -850 mV to -650 mV occurred following a decrease in Ni(I) concentration from 4.6 mM to 4.0 mM, which confirmed that N2O removal was mediated by an electrocatalytic reduction (MER) pathway. Online analysis identified the reaction product to be ammonia (NH3). Increasing the feed N2O concentration increased NH3 formation, which suggests that a decrease in electrolyzed solution reactivity induced by the increased N2O load constrained the side reaction with the carrier gas. Importantly, this study outlines a new regenerable method for N2O removal to commodity product NH3 at ambient temperature that fosters process intensification, overcomes the limitations generally observed with catalysis, and permits product transformation to NH3.

Electrochemically generated bimetallic reductive mediator Cu1+[Ni2+(CN)4]1- for the degradation of CF4 to ethanol by electro-scrubbing.

Remediation of electronic gas CF4 using commercially available technologies results in another kind of greenhouse gas and corrosive side products. This investigation aimed to develop CF4 removal at room temperature with formation of useful product by attempting an electrogenerated Cu1+[Ni2+(CN)4]1- mediator. The initial electrolysis of the bimetallic complex at the anodized Ti cathode demonstrated Cu1+[Ni2+(CN)4]1- formation, which was confirmed by additional electron spin resonance results. The degradation of CF4 followed mediated electrochemical reduction by electrogenerated Cu1+[Ni2+(CN)4]1-. The removal efficiency of CF4 of 95% was achieved by this electroscrubbing process at room temperature. The spectral results of online and offline Fourier transform infrared analyzer, either in gas or in solution phase, demonstrated that the product formed during the removal of CF4 by electrogenerated Cu1+[Ni2+(CN)4]1- by electroscrubbing was ethanol (CH3CH2OH), with a small amount of trifluoroethane (CF3CH3) intermediate.

Surfactant structural effects on mediated electrocatalytic dechlorination: Links between the micellar enhancement of dechlorination reactions and micellar properties.

Electrocatalytic dechlorination mediated by micelle-solubilized electrocatalysts has attracted considerable current interest for pollutant degradation. Aggregation in micellar assemblies and their interactions with the additives in solution are affected by the surfactant structure. By choosing appropriate surfactant molecules, the system properties may be altered to achieve enhanced dechlorination efficiency. Cetyltrimethylammonium bromide-based surfactants with different hydrocarbon lengths and headgroup structures were studied for their structural effects on [Co(I)(bipyridine)3]+-mediated dechlorination reactions. A widely used pollutants allyl chloride derivatives were studied as the substrates. The performance of the surfactants towards various dechlorination reactions was evaluated by cyclic voltammetry (CV) based on the catalytic efficiency. Key micellar parameters were determined by CV and rotating disc electrode using [Co(II)(bipyridine)3]2+ as the micelle-solubilized redox probe. The surfactants affected the dechlorination reaction to different extents, correlating well with their structure. The catalytic efficiency was explained by the interactions of the Co(II)/Co(I) with the surfactant hydrophobic tail and headgroup. This is the first report quantitatively linking the performance of the surfactants in dechlorination reactions with their molecular structure, showing that is possible to use variant surfactant structures to tune the micellar properties for their application towards the enhanced dechlorination of organic pollutants. Substrate structure-susceptibility to reduction relationships were also discussed.

Innovative reductive remediation of carbon tetrafluoride at room temperature by using electrogenerated Co1.

Among the non-CO2 greenhouse gases, carbon tetrafluoride (CF4) is the most recalcitrant and should be eliminated from the atmosphere. In the present study, a non-combustion electroscrubbing method was used in an attempt to degrade CF4 with an electrogenerated Co1+ mediator in a highly alkaline medium. The initial absorption experiments revealed 165mgL-1 CF4 gas dissolved in 10M NaOH. Different mediator precursors, [Co(II)(CN)5]3-, [Ni(II)(CN)4]2-, [Cu(II)(OH)4]2-, and [Co(II)(OH)4]2-, were used and the electroscrubbing results showed that the electrogenerated Co1+ or [Co(II)(OH)4]2- precursor effectively degraded up to 99.25% of the CF4 gas. The variations in [Co(II)(OH)4]2- reduction efficiency and cyclic voltammetry revealed CF4 degradation followed by electrogenerated Co1+ mediated reduction. The increased zeta potential (+6mV) of the electrogenerated Co1+ showed that the degradation reaction occurs preferably at the solution interface. Electroscrubbing for CF4 removal and the resulting products were controlled by the carrier gas. Air and H2 carrier gases lead to the formation of CHF3 and COF2. N2 as the carrier gas caused 99.25% degradation with ethanol as a product. An 80% CF4 degradation efficiency with CHF3 as the product was observed when a mixture of N2 and air was used as the carrier gas.

Gaseous trichloroethylene removal using an electrochemically generated homogeneous low-valent ligand-free Co(I) electrocatalyst by electro-scrubbing.

The interest in heterogeneous Co(OH)2 electrocatalysts for energy applications has increased steadily. This study focused on a ligand-free homogeneous electrocatalyst for the degradation of gaseous trichloroethylene (TCE) in NaOH in a divided electrolytic cell. The initial electrolysis results revealed a change in the oxidation reduction potential (ORP) of [Co(II)(OH)4](2-) (Co(II)) from -267 mV to -800 mV on anodized Ti during electrolytic reduction identifies low-valent homogeneous [Co(I)(OH)4](3-)(Co(I)) formation in 10 M NaOH. Cyclic voltammetry analysis of Co(II) at different anodized electrodes, Ag, carbon and Ti, in a 10 M NaOH solution, showed no stripping like peak in the reverse scan only the Ti electrode, supporting the formation of low-valent Co(I). UV-vis spectral analysis of the electrolyzed solution showed an enhanced peak corresponding to metal-to-ligand transition, demonstrates Co(I) formation. Co(II) reduction reached a maximum yield of 18% at 30 mA cm(-2) on an anodized Ti cathode. For gaseous TCE removal, continuous mode electro-scrubbing was adopted and degradation was monitored using an online FTIR gas analyzer that showed 99.75% degradation of TCE in the presence of homogeneous Co(I). Three consecutive regenerations of Co(I) and degradation steps of TCE confirmed the possibility of industrial applications in a sustainable manner.

Nucleation and growth study of nano-PbO2 on Ti in different additives for electrocatalytic oxidation process.

Electrocrystallization of PbO2 on Ti electrode was studied in different bath solutions using cyclic voltammetry (CV), chronoamperometry (CA), and scanning electron microscopy. The cyclic voltammetry studies revealed that the addition of methanol postponed the oxygen evolution region and made over potential nucleation of PbO2 on Ti. Oxidation of PbO2 is preferred in second cycle (a peak) in other studied bath solutions, except the Nafion and aniline containing solution. In the presence of the pyrrole, the PbO2 formed at under deposition potential with less in numbers. Nafion and aniline inclusion turn the process in to progressive nucleation and growth without inhibition. On the other hand, other solutions studied are revealed the instantaneous nucleation and growth or inhibition at high potentials. Surface morphology explained that approximately equal to 300 nm sizes PbO2 particles with vertical nucleation and growth phenomena evidenced the Nafion and aniline are the important dopants. The results indicated that large current density or high potential polarization can be obtained in presence of methanol, Nafion, and aniline, which is one of the most important and necessary factors for forming high surface area PbO2 with strong adherence towards mediated electro-oxidation process.

Nano-Ag-Nafion modified Pt electrode for oxidation of volatile organic compounds: an electrochemical study.

In this work, we describe Nano-Ag-Nafion coated pt electrode for oxidation of volatile organic compound (VOC), here acetaldehyde. Electrochemically synthesized Nano-Ag-Nafion film on Pt was analyzed by electrochemically in various electrolyte solutions like nitric acid, sulfuric acid, potassium nitrate, and potassium hydroxide for its stability. High stability of Nano-Ag-Nafion film appeared in potassium hydroxide medium among electrolyte solutions studied. Electrocatalysis of acetaldehyde was occurred only in acid and neutral medium. A catalytic oxidative peak during cathodic voltammetric reduction scan was observed at 1.75 V, which, unusual redox behavior, follows EC' reaction path way between electrogenerated Ag(II) and acetaldehyde. For Nano-Ag potential applicability, a calibration plot was drawn from various concentration range of acetaldehyde to check the maximum concentration level of acetaldehyde degradation in air.

Extraction and recovery of methylene blue from industrial wastewater using benzoic acid as an extractant.

Liquid-liquid extraction (LLE) of methylene blue (MB) from industrial wastewater using benzoic acid (extractant) in xylene has been studied at 27 degrees C. The extraction of the dye increased with increasing extractant concentration. The extraction abilities have been studied on benzoic acid concentration in the range of 0.36-5.8x10(-2) M. The distribution ratio of the dye is reasonably high (D=49.5) even in the presence of inorganic salts. Irrespective of the concentration of dye, extraction under optimal conditions was 90-99% after 15 min of phase separation. The extracted dye in the organic phase can be back extracted into sulphuric acid solution. The resultant recovered organic phase can be reused in succeeding extraction of dye with the yield ranging from 99 to 87% after 15 times reused, depending on the concentration of the initial feed solution. Experimental parameters examined were benzoic acid concentration, effect of diluent, effect of pH, effect of initial dye concentration, effect of equilibration time, various stripping agents, aqueous to organic phase ratio in extraction, organic to aqueous phase ratio in stripping and reusability of solvent.

Dechlorination of beta-methylallyl chloride by electrogenerated [Co(I)(bipyridine)3]+: an electrochemical study in the presence of cationic surfactants.

We have investigated the electrocatalytic dehalogenation of beta-methylallyl chloride (beta-mAC), widely used in the polymer industry, using [Co(I)(bpy)3]+ (where bpy=2,2'-bipyridine) electrochemically generated in situ from [Co(II)(bpy)3]2+ at a glassy carbon electrode in the presence of three different cationic surfactants in aqueous solution. Cetyltrimethylammonium bromide (CTAB), tetradecyltrimethylammonium bromide (TDTAB), and cetylbenzyldimethylammonium chloride (CBDAC) were employed in the present investigation. The [Co(II)(bpy)3]2+-cationic surfactant systems show excellent electrocatalytic activity toward dehalogenation of beta-mAC. The dependence of the catalytic current, the corresponding potential, and the current function on the potential scan rate has been analyzed to assess the nature of the catalytic reaction. The second-order rate constant, kchem, for the reaction between the beta-mAC substrate and the electrogenerated-micelle stabilized-Co(I) complex has been calculated by a cyclic voltammetry technique. The reduction products after 3 h of bulk electrolysis have been identified by GC/MS to be one nonchloro compound (2-methyl-1,5-hexadiene (IV)) and two chloro compounds (1-chloro-2,5-dimethyl-2,5-hexadiene (V) and spiro[1.2]cylopropyl-6-chloro-5-methyl-hex-4-ene (VI)). Based on the electrochemical results and the mass spectral data, a reaction scheme involving all the reduction products has been proposed. Finally, a good correlation between the catalytic efficiency and the structural features of the surfactant molecules is demonstrated. The present study emphasizes the need for further optimization work to achieve maximum yield of nonchloro compound (IV) to employ the present [Co(II)(bpy)3]2+-cationic surfactant systems with a high catalytic efficiency as promising for possible applications.