Electrochemically stable tunnel-type α-MnO2-based cathode materials for rechargeable aqueous zinc-ion batteries.

The purpose of this study is the synthesis of α-MnO2-based cathode materials for rechargeable aqueous zinc ion batteries by hydrothermal method using KMnO4 and MnSO4 as starting materials. The aim is to improve the understanding of Zn2+ insertion/de-insertion mechanisms. The as-prepared solid compounds were characterized by spectroscopy and microscopy techniques. X-ray diffraction showed that the hydrothermal reaction forms α-MnO2 and Ce4+-inserted MnO2 structures. Raman spectroscopy confirmed the formation of α-MnO2 with hexagonal MnO2 and Ce-MnO2 structures. Scanning electron microscopy (SEM) confirmed the formation of nanostructured MnO2 (nanofibers) and Ce-MnO2 (nanorods). The electrochemical performance of MnO2 was evaluated using cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) tests in half-cells. CV results showed the reversible insertion/de-insertion of Zn2+ ions in MnO2 and Ce-MnO2. GCD cycling tests of MnO2 and Ce-MnO2 at 2500 mA/g demonstrated an impressive electrochemical performance, excellent cycling stability throughout 500 cycles, and high rate capability. The excellent electrochemical performance and the good cycling stability of MnO2 and Ce-MnO2 nanostructures by simple method makes them promising cathode materials for aqueous rechargeable zinc-ion batteries.

Electrochemical Analysis of Sulfisoxazole Using Glassy Carbon Electrode (GCE) and MWCNTs/Rare Earth Oxide (CeO2 and Yb2O3) Modified-GCE Sensors.

In this work, new electrochemical sensors based on the modification of glassy carbon electrode (GCE) with multiwalled carbon nanotubes (MWCNTs)-rare metal oxides (REMO) nanocomposites were fabricated by drop-to-drop method of MWCNTs-REMO dispersion in ethanol. REMO nanoparticles were synthesized by precipitation followed by hydrothermal treatment at 180 °C in absence and presence of TritonTM X-100 surfactant. Cyclic voltammetry (CV) analysis using MWCNTs-CeO2@GCE and MWCNTs-Yb2O3@GCE sensors were used for the analysis of sulfisoxazole (SFX) drug in water samples. The results of CV analysis showed that MWCNTs-REMO@GCE sensors have up to 40-fold higher sensitivity with CeO2 compared to the bare GCE sensor. The estimated values of the limit of detection (LoD) of this electrochemical sensing using MWCNTs-CeO2@GCE and MWCNTs-Yb2O3@GCE electrodes reached 0.4 and 0.7 µM SFX in phosphate buffer pH = 7, respectively. These findings indicate that MWCNTs-REMO@GCE electrodes are potential sensors for analysis of sulfonamide drugs in water and biological samples.

Fabrication of Si3N4@Si@Cu Thin Films by RF Sputtering as High Energy Anode Material for Li-Ion Batteries.

Silicon and silicon nitride (Si3N4) are some of the most appealing candidates as anode materials for LIBs (Li-ion battery) due to their favorable characteristics: low cost, abundance of Si, and high theoretical capacity. However, these materials have their own set of challenges that need to be addressed for practical applications. A thin film consisting of silicon nitride-coated silicon on a copper current collector (Si3N4@Si@Cu) has been prepared in this work via RF magnetron sputtering (Radio Frequency magnetron sputtering). The anode material was characterized before and after cycling to assess the difference in appearance and composition using XRD (X-ray Powder Diffraction), XPS (X-ray Photoelectron Spectroscopy), SEM/EDX (Scanning Electron Microscopy/ Energy Dispersive X-Ray Analysis), and TEM (Transmission Electron Microscopy). The effect of the silicon nitride coating on the electrochemical performance of the anode material for LIBs was evaluated against Si@Cu film. It has been found that the Si3N4@Si@Cu anode achieved a higher capacity retention (90%) compared to Si@Cu (20%) after 50 cycles in a half-cell versus Li+/Li, indicating a significant improvement in electrochemical performance. In a full cell, the Si3N4@Si@Cu anode achieved excellent efficiency and acceptable specific capacities, which can be enhanced with further research.

Degradation of hydroxychloroquine by electrochemical advanced oxidation processes.

In this work, the degradation of hydroxychloroquine (HCQ) drug in aqueous solution by electrochemical advanced oxidation processes including electrochemical oxidation (EO) using boron doped diamond (BDD) and its combination with UV irradiation (photo-assisted electrochemical oxidation, PEO) and sonication (sono-assisted electrochemical oxidation, SEO) was investigated. EO using BDD anode achieved the complete depletion of HCQ from aqueous solutions in regardless of HCQ concentration, current density, and initial pH value. The decay of HCQ was more rapid than total organic carbon (TOC) indicating that the degradation of HCQ by EO using BDD anode involves successive steps leading to the formation of organic intermediates that end to mineralize. Furthermore, the results demonstrated the release chloride (Cl-) ions at the first stages of HCQ degradation. In addition, the organic nitrogen was converted mainly into NO3 - and NH4 + and small amounts of volatile nitrogen species (NH3 and NOx). Chromatography analysis confirmed the formation of 7-chloro-4-quinolinamine (CQLA), oxamic and oxalic acids as intermediates of HCQ degradation by EO using BDD anode. The combination of EO with UV irradiation or sonication enhances the kinetics and the efficacy of HCQ oxidation. PEO requires the lowest energy consumption (EC) of 63 kWh/m3 showing its cost-effectiveness. PEO has the potential to be an excellent alternative method for the treatment of wastewaters contaminated with HCQ drug and its derivatives.

Efficient degradation of chloroquine drug by electro-Fenton oxidation: Effects of operating conditions and degradation mechanism.

In this work, the degradation of chloroquine (CLQ), an antiviral and antimalarial drug, using electro-Fenton oxidation was investigated. Due to the importance of hydrogen peroxide (H2O2) generation during electro-Fenton oxidation, effects of pH, current density, molecular oxygen (O2) flow rate, and anode material on H2O2 generation were evaluated. H2O2 generation was enhanced by increasing the current density up to 60 mA/cm2 and the O2 flow rate up to 80 mL/min at pH 3.0 and using carbon felt cathode and boron-doped diamond (BDD) anode. Electro-Fenton-BDD oxidation achieved the total CLQ depletion and 92% total organic carbon (TOC) removal. Electro-Fenton-BDD oxidation was more effective than electro-Fenton-Pt and anodic oxidation using Pt and BDD anodes. The efficiency of CLQ depletion by electro-Fenton-BDD oxidation raises by increasing the current density and Fe2+ dose; however it drops with the increase of pH and CLQ concentration. CLQ depletion follows a pseudo-first order kinetics in all the experiments. The identification of CLQ degradation intermediates by chromatography methods confirms the formation of 7-chloro-4-quinolinamine, oxamic, and oxalic acids. Quantitative amounts of chlorides, nitrates, and ammonium ions are released during electro-Fenton oxidation of CLQ. The high efficiency of electro-Fenton oxidation derives from the generation of hydroxyl radicals from the catalytic decomposition of H2O2 by Fe2+ in solution, and the electrogeneration of hydroxyl and sulfates radicals and other strong oxidants (persulfates) from the oxidation of the electrolyte at the surface BDD anode. Electro-Fenton oxidation has the potential to be an alternative method for treating wastewaters contaminated with CLQ and its derivatives.

Electrochemical Oxidation/Disinfection of Urine Wastewaters with Different Anode Materials.

In the present work, electrochemical technology was used simultaneously for the deactivation of microorganisms and the destruction of micro-pollutants contained in synthetic urine wastewaters. Microorganisms (E. coli) were added to synthetic urine wastewaters to mimic secondary treated sewage wastewaters. Different anode materials were employed including boron-doped diamond (BDD), dimensionally stable anode (DSA: IrO2 and RuO2) and platinum (Pt). The results showed that for the different anode materials, a complete deactivation of E. coli microorganisms at low applied electric charge (1.34 Ah dm-3) was obtained. The complete deactivation of microorganisms in wastewater seems to be directly related to active chlorine and oxygen species electrochemically produced at the surface of the anode material. Complete depletion of COD and TOC can be attained during electrolyses with BDD anode after the consumption of specific electric charges of 4.0 and 8.0 Ah dm-3, respectively. Higher specific electric charges (>25 Ah dm-3) were consumed to removal completely COD and about 75% of TOC during electrolyses with DSA anodes (IrO2 and RuO2). However, the electrolysis using Pt anode can partially remove and even after the consumption of high specific electric charges (>40 Ah dm-3) COD and TOC did not exceed 50 and 25%, respectively. Active chlorine species including hypochlorite ions and chloramines formed during electrolysis contribute not only to deactivate microorganisms but also to degrade organics compounds. High conversion yields of organic nitrogen into nitrates and ammonium were achieved during electrolysis BDD and DSA anodes. The results have confirmed that BDD anode is more efficient than with IrO2, RuO2 and Pt electrodes in terms of COD and TOC removals. However, higher amounts of perchlorates were measured at the end of the electrolysis using BDD anode.

Enhancing the performance of electro-peroxone by incorporation of UV irradiation and BDD anodes.

In this work, the treatment of 4-nitrophenol (NP) in water by ozonation, electrolysis, electro-peroxone (EP), and photo-electro-peroxone (PEP) processes was investigated. PEP process is based on the combination of ozonation, UV irradiation, and electrolysis using a carbon felt cathode and a boron-doped diamond (BDD) anode. In this process, H2O2 is electrochemically generated from reduction of O2 in the ozone generator effluent at a carbon felt cathode. The in situ generated H2O2 is simultaneously decomposed by UV-photolysis and by reaction with O3 to form HO• radicals that can rapidly and non-selectively oxidize organic pollutants. The results showed that PEP is the most efficient process for a rapid NP degradation in water than the other individual and combined methods. In addition, PEP process was able to completely remove total organic carbon (TOC) from NP solution after consumption of 4.1 kWh/kg TOC removed. Hydroquinone, 1,2,4-trihydroxybenzene, oxalic and maleic acids were identified as the main intermediates of NP degradation. The addition of iron to NP solution did not significantly affect the efficiency of PEP process. The results demonstrated that the incorporation of BDD anodes and UV light in PEP process can significantly enhance the kinetics and minimize energy requirements.

The contribution of mediated oxidation mechanisms in the electrolytic degradation of cyanuric acid using diamond anodes.

In this work, the contribution of mediated oxidation mechanisms in the electrolytic degradation of cyanuric acid using boron-doped diamond (BDD) anodes was investigated in different electrolytes. A complete mineralization of cyanuric acid was obtained in NaCl; however lower degrees of mineralization of 70% and 40% were obtained in Na2SO4 and NaClO4, respectively. This can be explained by the nature of the oxidants electrogenerated in each electrolyte. It is clear that the contribution of active chlorine (Cl2, HClO, ClO(-)) electrogenerated from oxidation of chlorides on BDD is much more important in the electrolytic degradation of cyanuric acid than the persulfate and hydroxyl radicals produced by electro-oxidation of sulfate and water on BDD anodes. This could be explained by the high affinity of active chlorine towards nitrogen compounds. No organic intermediates were detected during the electrolytic degradation of cyanuric acid in any the electrolytes, which can be explained by their immediate depletion by hydroxyl radicals produced on the BDD surface. Nitrates and ammonium were the final products of electrolytic degradation of cyanuric acid on BDD anodes in all electrolytes. In addition, small amounts of chloramines were formed in the chloride medium. Low current density (≤10mA/cm(2)) and neutral medium (pH in the range 6-9) should be used for high efficiency electrolytic degradation and negligible formation of hazardous chlorate and perchlorate.

Mechanism and kinetics of electrochemical degradation of uric acid using conductive-diamond anodes.

Uric acid (UA) is one of the principal effluents of urine wastewaters, widely used in agriculture as fertilizer, which is potentially dangerous and biorefractory. Hence, the degradation of UA (2,6,8-trihydroxy purine) in aqueous solution of pH 3.0 has been studied by conductive-diamond electrochemical oxidation. Hydroxyl radicals formed from water oxidation at the surface of boron-doped diamond anodes were the main oxidizing agents. Effects of current density and supporting electrolyte on the degradation rate and process efficiency are assessed. Results show that the increase of current density from 20 to 60 mA cm(-2) leads to a decrease in the efficiency of the electrochemical process. In addition, the best degradation occurred in the presence of NaCl as conductive electrolyte. Interestingly, an almost total mineralization of 50 ppm UA was obtained when anodic oxidation was performed at low current densities (20 mA cm(-2)) and in the presence of NaCl. This result confirmed that the electrolysis using diamond anodes is a very interesting technology for the treatment of UA. The identification of UA transformation products was performed by high-performance liquid chromatography (HPLC). HPLC analysis of treated solutions revealed that oxalic acid and urea were the two intermediates found. Oxalic acid was the most persistent product. Based on detected intermediates and bibliographic research, a mechanism of UA mineralization by anodic oxidation has been proposed. Ionic chromatography analysis confirmed the release of [Formula: see text] and [Formula: see text] ions during UA mineralization.

Treatment of synthetic urine by electrochemical oxidation using conductive-diamond anodes.

In this work, the electrochemical oxidation of synthetic urine by anodic oxidation using boron-doped diamond as anode and stainless steel as cathode was investigated. Results show that complete depletion of chemical oxygen demand (COD) and total organic carbon (TOC) can be attained regardless of the current density applied in the range 20-100 mA cm(-2). Oxalic and oxamic acids, and, in lower concentrations, creatol and guanidine were identified as the main intermediates. Chloride ions play a very important role as mediators and contribute not only to obtain a high efficiency in the removal of the organics but also to obtain an efficient removal of nitrogen by the transformation of the various raw nitrogen species into gaseous nitrogen through chloramine formation. The main drawback of the technology is the formation of chlorates and perchlorates as final chlorine products. The increase of current density from 20 to 60 mA cm(-2) led to an increase in the rate of COD and TOC removals although the process becomes less efficient in terms of energy consumption (removals of COD and TOC after applying 18 Ah dm(-3) were 93.94 and 94.94 %, respectively, at 20 mA cm(-2) and 89.17 and 86.72 %, respectively, at 60 mA cm(-2)). The most efficient conditions are low current densities and high temperature reaching total mineralization at an applied charge as low as 20 kAh m(-3). This result confirmed that the electrolysis using diamond anodes is a very interesting technology for the treatment of urine.

Kinetic and mechanistic investigations of mesotrione degradation in aqueous medium by Fenton process.

In this work, chemical oxidation of mesotrione herbicide by Fenton process in acidic medium (pH 3.5) was investigated. Total disappearance of mesotrione and up to 95% removal of total organic carbon (TOC) were achieved by Fenton's reagent under optimized initial concentrations of hydrogen peroxide (H(2)O(2)) and ferrous iron (Fe(2+)) at pH 3.5. The time-dependent degradation profiles of mesotrione were satisfactorily fitted by first-order kinetics. Competition kinetic model was used to evaluate a rate constant of 8.8(± 0.2) × 10(9)M(-1) s(-1) for the reaction of mesotrione with hydroxyl radicals. Aromatic and aliphatic intermediates of mesotrione oxidation were identified and quantified by high performance liquid chromatography (HPLC). It seems that the degradation of mesotrione by Fenton process begins with the rupture of mesotrione molecule into two moieties: cyclohexane-1,3-dione derivative and 2-nitro-4-methylsulfonylbenzoic acid. Hydroxylation and release of sulfonyl and/or nitro groups from 2-nitro-4-methylsulfonylbenzoic acid lead to the formation of polyhydroxylated benzoic acid derivatives which undergo an oxidative opening of benzene ring into carboxylic acids that end to be transformed into carbon dioxide.

Treatment of aqueous wastes contaminated with Congo Red dye by electrochemical oxidation and ozonation processes.

Synthetic aqueous wastes polluted with Congo Red (CR) have been treated by two advanced oxidation processes: electrochemical oxidation on boron doped diamond anodes (BDD-EO) and ozonation under alkaline conditions. For same concentrations, galvanostatic electrolyses have led to total COD and TOC removals but ozonation process can reach only 85% and 81% of COD and TOC removals, respectively. UV-vis qualitative analyses have shown different behaviors of CR molecules towards ozonation and electrochemical oxidation. Rapid discoloration has been observed during ozonation, whereas color persistence till the end of galvanostatic electrolyses has been seen during BDD-EO process. It seems that the oxidation mechanisms involved in the two processes are different: simultaneous destruction of azoic groups is suggested during ozonation process but consecutive destruction of these groups is proposed during BDD-EO. However, energetic study has evidenced that BDD-EO appears more efficient and more economic than ozonation in terms of TOC removals. These results have been explained by the fact that during BDD-EO, other strong oxidants electrogenerated from the electrolyte oxidation such as persulfates and direct-oxidation of CR and its byproducts on BDD anodes complement the hydroxyl radicals mediated oxidation to accomplish the total mineralization of organics.