Transforming Plain LaMnO3 Perovskite into a Powerful Ozonation Catalyst: Elucidating the Mechanisms of Simultaneous A and B Sites Modulation for Enhanced Toluene Degradation.

Herein, we propose preferential dissolution paired with Cu-doping as an effective method for synergistically modulating the A- and B-sites of LaMnO3 perovskite. Through Cu-doping into the B-sites of LaMnO3, specifically modifying the B-sites, the double perovskite La2CuMnO6 was created. Subsequently, partial La from the A-sites of La2CuMnO6 was etched using HNO3, forming novel La2CuMnO6/MnO2 (LCMO/MnO2) catalysts. The optimized catalyst, featuring an ideal Mn:Cu ratio of 4.5:1 (LCMO/MnO2-4.5), exhibited exceptional catalytic ozonation performance. It achieved approximately 90% toluene degradation with 56% selectivity toward CO2, even under ambient temperature (35 °C) and a relatively humid environment (45%). Modulation of A-sites induced the elongation of Mn-O bonds and decrease in the coordination number of Mn-O (from 6 to 4.3) in LCMO/MnO2-4.5, resulting in the creation of abundant multivalent Mn and oxygen vacancies. Doping Cu into B-sites led to the preferential chemisorption of toluene on multivalent Cu (Cu(I)/Cu(II)), consistent with theoretical predictions. Effective electronic supplementary interactions enabled the cycling of multiple oxidation states of Mn for ozone decomposition, facilitating the production of reactive oxygen species and the regeneration of oxygen vacancies. This study establishes high-performance perovskites for the synergistic regulation of O3 and toluene, contributing to cleaner and safer industrial activities.

Effect of size and surface chemistry of gold nanoparticles on their retention in a sediment-water system and Lumbriculus variegatus.

With the increased production, usage, and disposal of engineered nanoparticles (ENPs), there is growing concern over the fate of ENPs in the environment, their potential bioavailability and ecotoxicity. It is assumed that bioavailability and uptake into organisms depend on the environmental conditions as well as the physicochemical properties of ENPs, such as particle size or surface coating. A major sink for nanoparticles is expected to be sediments due to sorption and agglomeration processes. Accordingly, this study, investigated how different sizes (5 and 30 nm) and surface coatings of three different AuENPs based on citrate (AuCIT), mercaptoundecanoic acid (AuMUDA), and bovine serum albumin (AuBSA) affected the retention of ENPs in a sediment-water system and subsequent uptake into sediment-dwelling organism Lumbriculus variegatus (L. variegatus). Surface charge was found to be one of the factors affecting retention of the AuENPs in the sediment-water system. More negatively charged AuENPs had a higher mass fraction in the supernatant after 24 h exposure. Furthermore, the stability of AuENPs in the supernatant depended more on their zeta potential than particle size (5 nm vs. 30 nm). The surface coating was found to play an important role in the uptake (after depuration) of Au in L. variegatus, that is, AuBSA > AuCIT > AuMUDA.

Imaging Features of Sclerosing Angiomatoid Nodular Transformation in Spleen.

PURPOSE: The purpose of this study was to evaluate the features of sclerosing angiomatoid nodular transformation (SANT) in spleen on the imaging of computed tomography (CT) and magnetic resonance (MR). MATERIALS AND METHODS: From July 2006 to April 2017, 12 patients with SANT confirmed by pathology were evaluated in a retrospective study. Eight patients were with CT imaging only, 2 patients were with MR imaging only, and 2 patients were with both CT and MR. Three professional senior radiologists analyzed the imaging features on CT and MR. The main characteristic analysis included size, margin, density, signal intensity, and enhancement pattern. The significant enhancement was defined as the degree of enhancement of lesion that is higher than the surrounding spleen parenchyma, and the mild enhancement was defined as the degree of enhancement of lesion that is lower than the surrounding spleen parenchyma. RESULTS: All the 12 patients (5 men, 7 women; mean age, 45.8 years; age range, 21-62 years) presented as single lesion without special clinical symptoms. The range of lesions on diameter was from 25 to 80 mm. On CT images, 9 (90%) of 10 presented as hypodense in comparison with the parenchyma of spleen, 1 (10%) of 10 presented as isodense, and calcification was observed in 4 (40%) of 10 cases. On MR images, 4 (100%) of 4 manifested heterogeneous hypointensity on in-phase sequence and 3 (75%) of 4 performed as isointensity on out-of-phase sequence of T1-weighted. On the sequences of T2-weighted and diffusion-weighted image, 4 (100%) of 4 showed hypointensity. On CT and MR enhancement images, the number of significant enhancement and mild enhancement was 2 and 10, respectively. Seven (58%) of 12 showed progressive enhancement with the pattern of "spoke-wheel." CONCLUSIONS: Imaging features on CT and MR have a high diagnostic value for SANT, especially when CT combined with MR examination.

Highly Efficient Interception and Precipitation of Uranium(VI) from Aqueous Solution by Iron-Electrocoagulation Combined with Cooperative Chelation by Organic Ligands.

A new strategy combining iron-electrocoagulation and organic ligands (OGLs) cooperative chelation was proposed to screen and precipitate low concentrations (0-18.52 µmol/L) of uranium contaminant in aqueous solution. We hypothesized that OGLs with amino, hydroxyl, and carboxyl groups hydrophobically/hydrophilically would realize precuring of uranyl ion at pH < 3.0, and the following iron-electrocoagulation would achieve faster and more efficient uranium precipitation. Experimentally, the strategy demonstrated highly efficient uranium(VI) precipitation efficiency, especially with hydrophilic macromolecular OGLs. The uranium removal efficiency at optimized experimental condition reached 99.65%. The decrease of zeta potential and the lattice enwrapping between U-OGLs chelates and flocculation precursor were ascribed to the enhanced uranium precipitation activity. Uranium was precipitated as oxides of U(VI) or higher valences that were easily captured in aggregated micelles under low operation current potential. The actual uranium tailing wastewater was treated, and a satisfied uranium removal efficiency of 99.02% was discovered. After elution of the precipitated flocs, a concentrated uranium solution (up to 106.52 µmol/L) with very few other metallic impurities was obtained. Therefore, the proposed strategy could remove uranium and concentrate it concurrently. This work could provide new insights into the purification and recovery of uranium from aqueous solutions in a cost-effective and environmentally friendly process.

Cu/Mn-mediated electron shuttle and high-valent metals enhance hydroxyl radicals production during the electrochemical oxidation on the CuMn-Sb-SnO2 electrode.

In this work, a novel CuMn-Sb-SnO2 anode is developed by a simple, low-cost preparation process. The doping of Cu and Mn causes surface reconstruction, which optimizes its electronic structure, compared to the Sb-SnO2 anode. Experimental results demonstrate that the levofloxacin degradation kinetics constant in the CuMn-Sb-SnO2 system (0.188 min-1) was 8.5 times higher than that in the Sb-SnO2 system, which is surpassing most reported anodes. Moreover, electrochemical characterization also revealed that the CuMn-Sb-SnO2 anode possessed more active sites, higher OEP potential, and lower charge transfer resistance. Notably, electrochemical characterization and EPR experiments confirmed the formation of Cu (III), highlighting their crucial role in promoting the generation of •OH during the catalytic process. Additionally, theoretical calculations and XPS analysis revealed that Cu and Mn rely on self-mediated redox shuttles to act as "electron porters", significantly accelerating internal electron transfer between Sn and Sb to enhance the production of •OH. Furthermore, the CuMn-Sb-SnO2 anode exhibits great practicability due to its efficient degradation of various antibiotics. This study offers valuable new insights into developing novel electrodes for the efficient degradation of antibiotic wastewater.

Kinetics for ammonium ion removal using a three-dimensional electrode system.

Electrochemical oxidation of ammonium ions (NH(4)(+)) by using a three-dimensional electrode (TDE) composed of IrO(2)-Ta(2)O(5)/Ti anode and bamboo carbon was carried out in this paper. Experimental results reveal that the NH(4)(+) oxidation follows first-order kinetics at lower NH(4)(+) concentration and the rate constant is highly dependent on the applied current density, dosage of chlorine ions and initial NH(4)(+) concentration. In addition, increasing current density, more Cl(-) dosage and higher initial NH(4)(+) concentration are beneficial for NH(4)(+) removal. By inspecting the relation between rate constant and those operating factors, an overall empirical equation for estimation of the rate constant of NH(4)(+) oxidation is presented. The estimated model is in good agreement with the experimental results and it could also be used for accurate design of the TDE system.

Preparation of SnO2-Sb/attapulgite (AP) clay particulate electrode for efficient phenol electrochemical oxidation.

A novel SnO2-Sb/AP (attapulgite) particle electrode was prepared for three-dimensional electrocatalytic oxidation (3D/EO) of organic pollutants using a co-sintering method. The electrochemical properties and micromorphology were determined using polarization, cyclic voltammetry (CV), and field emission scanning electron microscope (FE-SEM), and compared with activated carbon (AC), AP, and TiO2/AP particle electrodes. Besides, their potential application in the electrochemical degradation of phenol was investigated. The SnO2-Sb/AP particle electrode exhibited higher electrochemical activity than other particle electrodes due to its large number of active sites, low transfer coefficient (α, 0.12), and high-volt ampere charge (q*, 1.18 C·cm-2). The electrochemical CODCr degradation efficiency (100%) of phenol on SnO2-Sb/AP particle electrodes is much higher than for other particle electrodes. Moreover, an excellent stability of the SnO2-Sb/AP particle electrode is also verified by repeated experiments. These results indicate that the SnO2-Sb/AP particle electrodes broaden the application area of clays and are expected to be a promising method for 3D/EO.

Boosting photocatalytic H2 evolution on UIO-66-NH2/covalent triazine-based frameworks composites by constructing a covalent heterojunction.

Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have been proved as efficient catalysts for photocatalytic hydrogen (H2) evolution, thanks to their tunable functionalities, permanent porosity, excellent visible light response, and physicochemical stability. Herein, a series of photocatalysts (termed NUBC) was fabricated by loading different amounts of Zr-UiO-66-NH2 (NU) onto a benzoic acid-modified covalent triazine-based framework (BC) based on post-synthetic covalent modification. The resulting NUBC catalysts exhibited a type-II Z-scheme heterojunction structure formed via the amide covalent bonds between the amine groups on NU and carboxyl groups on BC. The optimal loading of NU on BC is 30 wt.% (30NUBC) and the corresponding photocatalytic H2 evolution rate was 378 µmol h-1 g-1, almost 445 and 2 times than that of NU and BC, respectively. The synergistic effect between the type-II Z-scheme heterojunctions and amide bonds was conducive to boosting visible light harvesting and facilitating charge transportation and separation. Furthermore, the prepared NUBC catalysts show great reusability and stability. Overall, this work sheds light on the design of novel MOF/COF hybrid materials and provides a systematic exploration of their photocatalytic H2 evolution properties.

Electron transfer enhancing the Mn(II)/Mn(III) cycle in MnO/CN towards catalytic ozonation of atrazine via a synergistic effect between MnO and CN.

In this study, manganese oxide (MnO) dispersed on CN (Mn-nCN) was fabricated as a catalyst in heterogeneous catalytic ozonation (HCO), achieving excellent catalytic performance on refractory organic pollutant degradation via the synergistic effects between MnO and CN. The study demonstrated that the C-N-Mn and C-O-Mn bonds constructed in the catalyst linking MnO and CN created the synergistic effects which could overcome typical problems, such as metal leaching etc. The C-N-Mn and C-O-Mn bonds could promote electron transfer from cation-π reactions to form electron-rich Mn(II) sites and electron-poor CN sites. The electron-rich Mn(II) sites as active sites supplied electrons to ozone which then further evolved into reactive oxygen species (ROS). The electron-poor CN sites captured electrons from the pollutant intermediate radicals to electron-rich Mn(II) sites via cation-π reactions with the help of C-N-Mn and C-O-Mn bonds, which promote the redox reactions of Mn. The surface hydroxyl groups also participated in ozone decomposition and ROS production. Additionally, •OH was the dominant ROS of the Mn-nCN HCO processes. This study presents the excellent HCO performance of Mn-nCN, as well as provides views on the electron transfer route between the catalyst, pollutant and ozone, which is crucial for the design of the catalyst.

Catalytic ozonation for imazapic degradation over kelp-derived biochar: Promotional role of N- and S-based active sites.

It is a feasible strategy to prepare reliable biochar catalysts for heterogeneous catalytic ozonation (HCO) processes by using inexpensive, high quality, and easily available raw materials. Here, an environmentally friendly, simple, and green biochar catalyst rich in nitrogen (N) and sulfur (S) has been prepared by the pyrolysis of kelp. Compared with directly carbonized kelp biomass (KB), acid-activated KB (KBA) and base-activated KB (KBB) have higher specific surface areas and more extensive porous structures, although only KBB displays effective ozone activation. Imazapic (IMZC), a refractory organic herbicide, was chosen as the target pollutant, which has apparently not hitherto been investigated in the HCO process. Second-order rate constants (k) for the reactions of IMZC with three different reactive oxygen species (ROS), specifically kO3, IMZC, kOH, IMZC, and k1O2, IMZC, have been determined as 0.974, 2.48 × 109, and 6.23 × 105 M-1 s-1, respectively. The amounts of graphitic N and thiophene S derived from the intrinsic N and S showed good correlations with the IMZC degradation rate, implicating them as the main active sites. OH and O2- and 1O2 were identified as main ROS in heterogeneous catalytic ozonation system for IMZC degradation. This study exemplified the utilization of endogenous N and S in biological carbon, and provided more options for the application of advanced oxidation processes and the development of marine resources.

Constructed electron-dense Mn sites in nitrogen-doped Mn3O4 for efficient catalytic ozonation of pyrazines: Degradation and odor elimination.

In this study, N-doped Mn3O4 catalysts (Mn-nN) with electron-dense Mn sites were synthesized and employed in heterogeneous catalytic ozonation (HCO). These catalysts demonstrated excellent performance in pyrazines degradation and odor elimination. The synthesis of Mn-nN was achieved through a facile urea-assisted heat treatment method. Experimental characterization and theoretical analyses revealed that the MnN structures in Mn-nN, played a crucial role in facilitating the formation of electron-dense Mn sites that served as the primary active sites for ozone activation. In particular, Mn-1N exhibited excellent performance in the HCO system, demonstrating the highest 2,5-dimethylpyrazine (2,5-DMP) degradation efficiency. •OH was confirmed as the primary reactive oxygen species involved in the HCO process. The second-order rate constants for 2,5-DMP degradation with O3 and •OH, were determined to be (3.75 ± 0.018) × 10-1 and (6.29 ± 0.844) × 109 M-1 s-1, respectively. Seventeen intermediates were identified through GC-MS analysis during the degradation of 2,5-DMP via HCO process with Mn-1N. The degradation pathways were subsequently proposed by considering these identified intermediates. This study introduces a novel approach to synthesize N-doped Mn3O4 catalysts and demonstrates their efficacy in HCO for the degradation of pyrazines and the elimination of associated odors. The results show that the catalysts are promising for addressing odor-related environmental issues and provide valuable insights about the broader significance of catalytic ozonation processes.

Contribution of electrolyte in parametric optimization of perfluorooctanoic acid during electro-oxidation: Active chlorinated and sulfonated by-products formation and distribution.

The present study investigated the roles of peroxydisulfate (PDS) radicals and sulfate radicals (SO4•-) that formed from sulfate (SO42-) during electrochemical oxidation of perfluorooctanoic acid (PFOA). The effect of operating parameters such as different types of electrolytes (NaCl, NaClO4, and Na2SO4), initial pH, current density, dose of electrolyte, and initial concentration of PFOA using electrochemical oxidation for perfluorooctanoic acid (PFOA) decomposition study was investigated. A difference in the removal efficiency with different electrolytes (i.e., Cl-, ClO4-, and SO42-) illustrated an increasing effect of electrooxidation of PFOA in the order of ClO4- < Cl- < SO42-, which suggested that •OH induced oxidation and direct e- transfer reaction continued to play a crucial role in oxidation of PFOA. At the optimum treatment condition of j = 225.2 Am-2, Na2SO4 concentration = 1.5 gL-1, [PFOA]o = 50 mgL-1 and initial pH = 3.8 maximum PFOA removal of 92% and TOC removal of 80% was investigated at 240 min. The formation of three shorter-chain perfluorocarboxylates (i.e., perfluoroheptanoic acid (PFHpA), perfluorohexanoic acid (PFHxA), and perfluoropentanoic acid (PFPeA) and formate (HCOO-) ions were detected as by-products of PFOA electro-oxidation, showing that the C-C bond first broken in C7F15 and then mineralized into CO2, and fluoride ion (F-). The fluorine recovery as F- ions and the organic fluorine as the shorter-chain by-products were also obtained. The degradation kinetic has also been studied using the nth-order kinetic model.

Modeling approach to phenol oxidation by a sand-based packed-bed electrode system (SPBEs).

A comparative study of phenol oxidation using pure electrolysis (PEs) and sand-based packed-bed electrode systems (SPBEs) was performed under conditions of phenol concentration 800 mg L(-1), initial pH 6.5, current density 100 A m(-2) and sodium sulfate (Na(2)SO(4)) 3.0% (w/w) on IrO(2)-Ta(2)O(5)/Ti anode. The results show quartz sand, a non-conducting material is incapable of expanding the electrode area and the phenol oxidation in SPBEs commences only at the electrode surface. From the theoretical description of the mass transport coefficient and chemical oxygen demand (COD), we confirm that the enhancement of the COD removal efficiency, current and space-time yields in SPBEs is due to the improvement of mass transport properties. The proposed SPBEs shows superiority to the PEs on saving energy at the same applied voltage, however, when operated under the same applied current density the energy consumption of the former would be much higher than that of the latter because of the rise of the applied cell voltage.

Highly active Fenton-like catalyst derived from solid waste-iron ore tailings using wheat straw pyrolysis.

The pollutants degradation rate of iron ore tailings-based heterogeneous catalysts is the main factor limiting its application. Herein, an iron ore tailings-based Fenton-like catalyst (I/W(3:1)-900-60) with a relatively fast catalysis rate was constructed by co-pyrolysis (900°C, 60 min holding time) of iron ore tailings and wheat straw with a mass ratio of 3:1. With wheat straw blending, the generated I/W(3:1)-900-60 presented a larger surface area (24.53 m2/g), smaller pore size (3.76 nm), reduced iron species (Fe2+ from magnetic), and a higher catalytic activity (0.0229 min-1) than I-900-60 (1.32 m2/g, 12.87 nm, 0.012 min-1) pyrolyzed using single iron ore tailing under the same pyrolysis conditions. In addition, biochar and iron ore tailings in I/W(3:1)-900-60 were tightly combined through chemical bonding. The optimal catalyst remains active after three cycles, indicating its catalytic stability and recyclability. The good Fenton-like methylene blue degradation efficiency of I/W(3:1)-900-60 was ascribed to the sacrificial role of biochar, as well as the electron transfer between biochar and iron active sites or the redox cycles of ≡Fe3+/Fe2+. This finding provides a facile construction strategy for highly active iron ore tailings-based Fenton-like catalyst and thereby had a great potential application in wastewater treatment.

Electrochemical Oxidation of Methyl Orange in an Active Carbon Packed Electrode Reactor (ACPER): Degradation Performance and Kinetic Simulation.

The efficient removal and kinetic modelling of methyl orange (MO) degradation using an electrocatalytic oxidation method in an activated carbon (AC) packed electrode reactor (ACPER) were conducted. A significantly high (81.2%) chemical oxygen demand (COD) and 100.0% MO decolorization efficiency were observed under the experimental conditions of current density of 3.0 mA·cm-2, flow velocity of 0.3 L·h-1, and treatment duration of 1.68 h using a ß-PbO2/Ti anode. The high removal efficiency is ascribed to the anode expansion effect after AC packing. The anode expansion coefficient (λ) of the ACPER was calculated to be 0.63 from the cyclic voltammetry (CV) measurement, which means the further current utilization for MO oxidation. Based on the current utilization efficiency on anodic and particle electrode surfaces, a phase-reaction kinetics model was proposed for the simulation of MO COD removal efficiency. Our simulation results showed that the newly established average current efficiency (ACE) and energy consumption (Esp) model well matched the MO experimental degradation data. Our work broadens the scope of the application of ACPER in the treatment industry wastewater containing organics and provides a new strategy for the energy utilization evaluation during the removal of organic matter by electrocatalytic oxidation.

The Aggregation and Dissolution of Citrate-Coated AgNPs in High Ammonia Nitrogen Wastewater and Sludge from UASB-Anammox Reactor.

Silver nanoparticles (AgNPs) are released into the sewage pipes and ultimately wastewater treatment plants during manufacturing, use, and end-life disposal. AgNPs in wastewater treatment plants aggregate or dissolve, and may affect the microbial community and subsequent pollutant removal efficiency. This study aims to quantitatively investigate the fate of AgNPs in synthetic high ammonia nitrogen wastewater (SW) and sludge from an up-flow anaerobic sludge blanket (UASB) anammox reactor using a nanoparticle tracking analysis (NTA), dynamic light scattering (DLS), transmission electron microscope (TEM), and atomic absorption spectroscopy (AAS). Results showed that 18.1 mM NH4+, 2.11 mM Mg2+ in SW caused less negative zeta potential (ζ-potential, -18.4 vs. -37.4 mV), aggregation (388.8 vs. 21.5 nm), and settlement (80%) of citrate-coated AgNPs (cit-AgNPs) in 220 min. The presence of 18.5 mM Cl- in SW formed AgCl2-, AgCl(aq) and eventually promoted the dissolution (9.3%) of cit-AgNPs. Further exposure of SW-diluted AgNPs to sludge (42 mg L-1 humic acid) and induced a more negative ζ-potential (-22.2 vs. -18.4 mV) and smaller aggregates (313.4 vs. 388.8 nm) due to the steric and hindrance effect. The promoted Ag dissolution (34.4% vs. 9.3%) was also observed after the addition of sludge and the possible reason may be the production of Ag(NH3)2+ by the coexistence of HA from sludge and NH4+ from SW. These findings on the fate of AgNPs can be used to explain why AgNPs had limited effects on the sludge-retained bacteria which are responsible for the anammox process.

Highly selective electrocatalytic reduction of CO2 to HCOOH over an in situ derived hydrocerussite thin film on a Pb substrate.

A metal oxide electrode has been developed for the electrochemical CO2 reduction reaction (eCO2RR). It exhibits superior activity and product selectivity towards eCO2RR by circumventing the previously encountered problem of self-reduction with high-valence metals. Specifically, a hydrocerussite [Pb3(CO3)2(OH)2] thin film has been synthesized in situ on a Pb substrate (denoted as ER-HC) by an electroreduction method using a lead-based metal-organic framework (Pb-MOF) as a precursor. The ER-HC electrode exhibits a high selectivity of 96.8% towards HCOOH production with a partial current density of 1.9 mA cm-2 at -0.88 V vs. the reversible hydrogen electrode (RHE). A higher HCOOH partial current density of 7.3 mA cm-2 has been achieved at -0.98 V vs. RHE. Physicochemical and electrochemical characterization results demonstrate that the defective hydrocerussite surface exhibits appropriate adsorption free energy of formate (HCOO-) and a lower reaction free energy for HCOOH production from CO2, which greatly boosts the eCO2RR activity and HCOOH production selectivity. The structure and eCO2RR performance of the hydrocerussite thin film remain stable in 0.1 M KHCO3 as electrolyte, ensuring its durability. Overall, this work not only provides a metal oxide electrode (metal hydroxide, to be more precise) with excellent eCO2RR performance, but also expands the in situ electrochemical derivatization strategy for the fabrication of metal oxide electrodes.

Determination of reaction rate constants for phenol oxidation using SnO2/Ti anodes coupled with activated carbon adsorption in the presence of TiO2 as catalyst.

Series of experiments for phenol degradation with assistance of TiO2 catalyst at pH of 6.5 and temperature of 25 degrees C were conducted using a lab-scale electrochemical reactor constructed in our laboratory. According to the results, at the presence of the TiO2 catalyst the removal of phenol was increased and first-order kinetics could describe the evolution of phenol concentration. For inspecting the relationship between rate constants and dosage of TiO2, two possible kinetics were proposed in this study. Contrasted to the abundant experimental data, a reasonable kinetics was obtained for the estimation of phenol concentration effluent during continuous flow of raw wastewater, especially when the TiO2 dosage was less than 0.5g L(-1). The model obtained from these experiments could employed for the calculation of rate constants at different TiO2 dosage and the necessary dosage of catalyst when a discharge standard was designed.

A new strategy for determination of current efficiency during electro-oxidation of aromatic compounds in a packed-bed system.

The electro-oxidation of aromatic compounds in 4,4'-diaminostilbene-2,2'-disulfonic (DSD) acid wastewater on IrO2-Ta2O5/Ti anodes was studied. The current efficiency was evaluated in terms of chemical oxygen demand (COD) by introducing a new factor, the fraction of the Faradaic current to the total cell current (beta) through the network analysis of packed bed electrode system (PBEs). Experimental results using an up-flow PBEs at current intensities ranging from 5 to 16 A m(-2), flow rates ranging from 20 to 80 L h(-1) and inter-electrode distance of 5 to 50 cm are in good agreement with the proposed equation. In addition, lower current density, increasing flow rate and larger inter-electrode distance are beneficial to enhance the current efficiency.

Effect of current density and pH on the electrochemically generated active chloro species for the rapid mineralization of p-substituted phenol.

The aim of present study is increasing the degradation and mineralization of 4-chlorophenol (4-CP) during electrochemical oxidation with Ti/RuO2 anodes. Innovatively, the evolution of chlorine-related species and the formations of various inorganic ions were investigated by electrolytic analysis in order to set up whether the formation and consumption of these byproducts associated with either chemical or electrochemical reactions. The effect of operating parameters such as current density, solution pH, treatment time, and electrolyte concentration has been studied. The formation of Cl2, chlorite (ClO2-), and chlorate (ClO3-) were detected by adding the known concentration of Cl- ions at different pH and current densities. Concentration trends of active chloro-species indicate that the degradation of 4-CP and chemical oxygen demand (COD) removal was formed maximum at pH 6 and j of 225.2 Am-2 in presence of 0.0085 M NaCl. Thus, the 4-CP degradation mainly depends on the radicals and active chlorine formation and a mineralization mechanism was proposed based on intermediates byproducts formation such as catechol, hydroquinone, 1, 4-benzoquinone, and organic acids identify by using the GC-MS and HPLC analysis at the optimum treatment condition. Total organic carbon (TOC) at different pH and current density, mass balance analysis of carbon and inorganic species formation were determined at the optimum treatment conditions of 4-CP. The degradation kinetic of 4-CP was followed the pseudo-first order kinetic model during the each parameters optimization. Specific energy consumption and current efficiency were also used to identify the technical feasibility of the process.