Examination of in situ Generation of Hydroxyl Radicals and Ozone in a Flow-through Electrochemical Reactor

Generation of hydroxyl radicals and ozone in a low ionic strength influent (0.001 M Na₂SO₄) treated in a continuous flow electrochemical (EC) reactor equipped with a cobalt-promoted lead dioxide anode was examined using p-chlorobenzoic acid (pCBA) and indigotrisulfonate (ITS) probes. EC generation of hydroxyl radicals via the oxidation of water was determined to precede that of ozone. OH· current yields were affected virtually solely by the current density, with almost negligible effects of variations of pH and carbonate concentrations. Absolute values of the current yields of EC generated OH· radicals were close to 1.0% for current densities > 30 mA/cm². The EC generation of ozone was suppressed in the presence of organic species, primarily due to the interception of OH· radicals that react with oxygen to form ozone. Apparent kinetic constants of major reactions associated with the EC generation of ozone were determined based on a steady-state model of an EC-controlled continuous flow reactor.     

Applicability of coumarin for detecting and measuring hydroxyl radicals generated by photoexcitation of TiO2 nanoparticles

Applicability of coumarin (COU) as fluorescent probe to detect and measure hydroxyl radicals generated by UV irradiation of aqueous suspension of TiO₂ was investigated under aerobic and anaerobic conditions. The fluorescent 7-hydroxycoumarin (7HC) was formed in argon-saturated suspension when silver ion was used as electron acceptor. The luminescence intensity increased with irradiation time until the deposition of silver on the surface of TiO₂ was completed and then the luminescence intensity was constant and proportional to the initial concentration of the silver ion. The low yield of 7HC related to the deposited silver (0.32%) indicates the appearance of efficient side reactions of hydroxyl radicals and holes. It has also been demonstrated that efficient electron donors reacting directly with photogenerated holes such as oxalic acid significantly reduce the yield of 7HC. Using oxalic acid of relatively high concentration in aerated suspension leads to the production of hydroxyl radical in thermal reactions followed by primary electron transfer steps.     

Enhancement of Wastewater Disinfection Efficiency in Full-Scale Ozone Bubble-Diffuser Contactors

Tracer and disinfection tests were performed with the ozone bubble-diffuser contactors at the Belmont and Southport Advanced Wastewater Treatment Plants operated by the City of Indianapolis, Department of Public Works. The objective of the study was to develop a better understanding for the role of hydrodynamics and contactor design on the disinfection efficiency achieved in these contactors. Tracer tests were performed at varying gas and wastewater flow rates. The results indicated that high backmixing occurred within each chamber of the over-under ozone bubble-diffuser contactor trains. The addition of three baffles to one of the contactor trains resulted in a decrease in overall contactor backmixing. Low contactor backmixing was observed at high wastewater flow rates combined with high or medium gas flow rates for both the modified and original trains. Monitoring of effluent fecal coliform concentrations for both the original and modified contactor trains revealed lower average concentrations in the modified train effluent as compared to the original train.     

Photocatalytic inactivation of Escherischia coli: Effect of concentration of TiO2 and microorganism, nature, and intensity of UV irradiation

The efficiency of photocatalytic disinfection, used to inactivate Escherischia coli K12 under different physico-chemical parameters, was examined. The photocatalyst chosen was the semiconductor TiO₂ degussa P25 and the irradiation was produced by an HPK 125 lamp. The effect of titania concentration was investigated using two E. coli concentrations. The photocatalyst concentration ranged from 0.1 to 2.5 g/L. The evolution of E. coli inactivation as function of time was discussed depending on the E. coli and TiO₂ concentrations. The optimal concentration of the photocatalyst, 0.25 g/L, is lower than that necessary to absorb all photons and to degrade the organic compounds. Some hypotheses are presented to explain this behaviour. The effect of the different domains of UV light (UVA, UVB, and UVC) was also studied and modification of the light irradiation intensity is discussed. No bacteria photolysis was obtained with UVA but the use UVC had, on the contrary, a detrimental effect on bacteria survival. The addition of titania at a low concentration, 0.25 g/L, improved the inactivation of E. coli in the presence of UVA and UVB, but a detrimental effect was observed under UVC. The disinfection efficiency increases as a function of light intensity, whatever the photocatalytic conditions (different TiO₂ concentrations and different UV domains). No bacterial growth was observed after disinfection, whether the system contained titania or not.     

Influence of Hydrodynamics on Giardia Cyst Inactivation by Ozone. Study by Kinetics and by “CT” Approach

This Research Note deals with the problem of providing appropriate disinfection from one of the most resistant microorganisms (the Giardia cysts) while trying to provide a more strict and logical approach to the “CT” concept. A further discussion of the U.S. Environmental Protection Agency (EPA) disinfection requirements in accordance with the kinetics and hydraulics of the ozonation process will be made in order to reconsider the definition of detention time. The main objective is the comparison of two possible approaches for determination of the disinfection conditions. The first implies consideration of the kinetics and hydraulics of the ozonation process. The second is based only on the hydrodynamics data and the use of an additional hypothesis known as the concept of the “CT” value.     

Study of the coupling reactions between electrochemically generated aromatic radical anions and methyl, alkyl and benzyl radicals

Alkyl radicals produced in the indirect reduction of alkyl halides or alkyldimethylsulfonium salts by electrochemically generated aromatic radical anions couple fast with the latter and alkylated or dialkylated dihydro compounds are formed. Rate constants measured for the coupling reaction between on one hand methyl, primary, secondary and tertiary alkyl radicals as well as benzyl and cumyl radicals and on the other hand a wide spectrum of electrochemically generated aromatic radical anions are found to be about 1×10⁹ M⁻¹ s⁻¹. Previous measurements of coupling rate constants for primary alkyl radicals have been re-evaluated since they were affected by the presence of an S_N2 reaction occurring between the alkyl halides used as radical precursors and the aromatic radical anions. New experiments are also included using alkyldimethylsulfonium salts as precursors in order to prevent such S_N2 artefacts. It is concluded that sterical hindrance does not play a significant role for the radical-radical anion coupling reactions. In general the rate constants for the coupling reactions are all close to 10⁹ M⁻¹ s⁻¹.     

Electrochemical and spectral properties of meta-linked 1,3,5-tris(aryl)benzenes and 2,4,6-tris(aryl)-1-phenoles, and their polymers

We present electrochemical and spectral properties of symmetric monomers 1,3,5-tris(aryl)benzenes and 2,4,6-tris(aryl)-1-phenols and their polymers. These compounds contain thienyl, furyl or EDOT moieties attached to central benzene or phenol ring at the meta-position, synthesized by a Stille cross-coupling procedure. All monomers are electroactive and undergo electropolymerization creating thin films on an electrode surface. Polymers with meta-linkages were obtained by electrochemical oxidation. Detailed cyclic voltammetry and in situ UV-vis spectroelectrochemistry show that polymers with hydroxy groups exhibit higher conductivity and better stability than with benzene core. Interesting and different behavior occurs for 2,4,6-tris(2-thienyl)-1-phenol, for which the characteristic, sharp, redox peak is observed.     

Control of hydroxyl group content in silica particle synthesized by the sol-precipitation process

This study investigated the control of hydroxyl groups, one of key factors determining the surface properties of silica particles synthesized by the sol-precipitation of tetraethyl orthosilicate (TEOS). Thus, a thermal gravity analysis (TGA) was used to facilitate quantitative measurements of the hydroxyl groups on the silica particles, while BET and FT-IR were used to analyze the specific surface area and functional silane groups on the silica particles, respectively. In the sol-precipitation process, silanes that include various hydroxyl groups are formed as intermediates based on the hydrolysis and condensation of TEOS. Thus, NH₃, as a basic catalyst initiating the nucleophilic substitution of TEOS, was found to accelerate the hydrolysis and increase the hydroxyl group content on the silica particles. Plus, the hydroxyl group content was also increased when increasing the concentrations of TEOS and water as the hydrolysis reactants. However, the hydroxyl group content was reduced when increasing the temperature, due to the promotion of condensation. Based on the weight loss of the particles according to the thermal analysis, the hydroxyl group content on the silica particles varied from 5.6–42.7 OH/nm² under the above reaction conditions.     

不饱和羟基脂肪酸原位改性炭黑补强EPDM的结构和形态

测试了三元乙丙橡胶(EPDM)混炼胶的结合橡胶含量，硫化胶的表现交联密度，采用FT-IR表征了不饱和羟基脂肪酸在EPDM硫化胶中的反应，DMTA研究了硫化胶的动态力学性能，SEM观察了EPDM硫化胶中炭黑的表面形貌。结果表明：EPDM混炼胶的结合橡胶含量随着不饱和羟基脂肪酸的加入出现一个峰值，表观交联密度略有下降；不饱和羟基脂肪酸参与了EPDM硫化胶的反应，提高了常温范围内EPDM硫化胶的损耗因子；适量的不饱和羟基脂肪酸可以改善炭黑在EPDM橡胶中的分散。最后提出了一个不饱和羟基脂肪酸补强橡胶的模型，认为不饱和羟基脂肪酸在EPDM硫化胶中起到柔性桥键的作用．阻碍了炭黑聚集体的形成．是硫化胶屈挠疲劳性能显著改善的主要原因。     

Synthesis and properties of cationic photopolymerizable hyperbranched polyesters with terminal oxetane groups by the couple-monomer polymerization of carboxylic anhydride with hydroxyl oxetane

The hyperbranched polyesters with terminal oxetane groups were synthesized via couple-monomer methodology based on carboxylic anhydride and hydroxyl oxetane. Two competitive reactions, ring-opening reaction of carboxylic group with oxetane group and esterification of carboxylic group with hydroxyl group, occurred synchronously during the polymerization. The results showed that the hyperbranched polyesters, poly(SA-EHO) and poly(SA-EHPO), were synthesized successfully when succinic anhydride (SA) was selected to react with 3-Ethyl-3-(hydroxymethyl)oxetane (EHO) and 3-ethyl-3-((4-hydroxymethyl)phenoxymethyl)oxetane (EHPO), respectively. The degree of branching was determined to be about 0.7 for poly(SA-EHO) from the ¹H NMR result, which was higher than those reported in literature, indicating that the esterification was dominant. The glass transition temperatures (T_g)s were measured as −11.5 °C for poly(SA-EHO) and 14.3 °C for poly(SA-EHPO) by DSC. The number average molecular weights were 1914 g/mol and 2108 g/mol with the polydispersity indices of 2.39 and 2.28 for poly(SA-EHO) and poly(SA-EHPO), respectively. Both poly(SA-EHO) and poly(SA-EHPO) were added to bisphenol A epoxy resin, EP828, with different contents and cured under UV exposure. From the DMTA and tensile results, the UV cured poly(SA-EHPO) showed higher T_g and tensile strength compared with poly(SA-EHO) because of the existence of phenyl group in poly(SA-EHPO) chain. Moreover, both the T_gs and mechanical strength decreased, whereas the elongation percents at break increased with poly(SA-EHO) and poly(SA-EHPO) increased. This indicates that the flexibility of cured films was improved by the addition of poly(SA-EHO) and poly(SA-EHPO) in the formulations.     

Mineralization of Para-Chlorobenzoic Acid in Water by Cobalt-Incorporated MCM-41 Catalyzed Ozonation

Cobalt-incorporated MCM-41(Co-MCM-41) was used as a heterogeneous catalyst for the ozonation of para-chlorobenzoic acid (p-CBA) in aqueous solution. Cobalt oxide supported on MCM-41(Co/MCM-41) was synthesized for comparison. Their textural properties were elucidated by various characterization techniques to understand the relationship between surface texture and catalytic activity. TOC removal at 60 min reached 91% with Co-MCM-41, 83% with Co/MCM-41 and only 52% with ozone alone, respectively. Observations from diffuse reflection spectroscopy demonstrated that different metal phases were formed in these cobalt-modified molecular sieves samples. Radical scavenger experiments indicated the formation of hydroxyl radicals that were responsible for the effective degradation of p-CBA. An integrated approach to the catalytic mechanism was proposed by considering the variation of pH in the course of ozonation as well as its subsequent influence on the dissociation of targeted compounds and surface charge of the catalyst. In the reusability experiments, the reused Co-MCM-41 was able to regain the same catalytic capability as the fresh one within 5 cycles. X-ray photoelectron spectroscopy results indicated that a part of Co²⁺ was oxidized to Co³⁺ after oxidation reaction.     

Spontaneous and Electrochemical Reduction of Silver by Polypyrrole Deposits

Abstract

Polypyrrole (ppy) coatings doped with p-toluene sulfonate sodium on stainless steel mesh (SSM) have been electrosynthesized in aqueous solution. The removal of Ag⁺ ions from acidic solutions was investigated through spontaneous reduction (SR) and electrochemical reduction (ER) procedures using reduced composite ppy-SSM. Higher removal efficiencies and current efficiencies were obtained by ER process for ppy-SSM rather than SR process for ppy-SSM and ER process for SSM under comparable conditions. Due to its high efficiency and simplicity, ER was supposed to be an alternative advantageous method for the recovery of low-level silver concentration in industrial wastewater. Cyclic voltammetry was carried out to characterize the electrochemical behavior of ppy-SSM in acid solutions containing Ag⁺. Metallic silver deposited on ppy-SSM has been evidenced by scanning electron microscopy (SEM) analysis.     

Electrochemical synthesis of selenium nanotubes by using CTAB soft-template

The single-crystalline Se nanotubes were synthesized on the surface of Au sheet electrode by cyclic voltammetry. In synthesis process, cetyltrimethyl ammonium bromide (CTAB) was used as soft-template. The formation mechanism of Se nanotubes was discussed. Furthermore, the deposits with other morphologies were also obtained by modulating parameters in the synthesis process. The products as-prepared were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and laser Raman spectrograph (LRS). The electrochemical behavior of the Se nanotubes was studied by the linear scan voltammetry.     

Electrochemical properties of boron-carbon-nitride films formed by magnetron sputtering

The electrochemical behavior of B_1.0C_2.4N_1.0 thin film was investigated in acidic, neutral and alkaline solutions. The anodic polarization curve of the film in 1 M NaOH showed the anodic dissolution of the film. The curve of the film in 1 M HCl showed no anodic dissolution. The cathodic polarization curve in 1 M NaCl showed shift to a negative potential side, but the anodic polarization curve was the same as that of Pt. The anodic dissolution in 1 M NaOH depended on potentials, that is, no anodic dissolution was recognized in a potential range of −0.2 to 0.1 V but the dissolution rate increased with increasing potential in a range of 0.1-0.6 V. The anodic current density of the film is directly proportional to the dissolution rate at potentials higher than 0.1 V. The dissolution rate of the film was increased with increasing solution pH.     

Investigation of structure and ORR reactivity of fuel cell catalysts by in-situ STM

In order to provide insight into the interfacial relationships at fuel cell electrodes, a measuring technique based on a scanning tunneling microscope working in an electrochemical cell has been developed. The structure of model electrodes consisting of carbon supported Pt and ionomer mixtures as well as MEA electrode surfaces is imaged by the electrochemical scanning tunneling microscope (EC-STM) from microscale to nanoscale. Images with subnanometer resolution are obtained indicating that some ordering of the particles on the carbon support is present in the model system and in the MEA. It is demonstrated that in both cases nanometer structures can be imaged reliably and that the interface is rather clean and active under reaction conditions. In addition, a technique has been developed to measure the local reactivity by using the STM tip as a sensor electrode for the ORR.     

Rearrangements of electrochemically generated cation radicals: The quest for regiochemical control and an application to total synthesis

Herein we provide an overview of our efforts to achieve regiochemical control in the rearrangement of the cation radicals derived from housanes, and to apply the chemistry to the total synthesis of a natural product.     

Wastewater Disinfection by Ozone: Influence of Water Quality and Kinetics Modeling

Wastewater disinfection by ozone was investigated at pilot scale on different effluents. The organic matter (COD and TOC) was shown to have the biggest influence on the ozone demand of the effluents. Disinfection of fecal indicators could be modeled as the reaction on a double population. The presence of more resistant microorganisms results in the need for higher treatment doses and a tertiary filtration when the effluent has to meet the stringent Title 22 standard. Eventually, the high virucidal power of ozone makes it very attractive when viruses are targeted.     

Electrochemical properties of Cu2O/Cu composite particles prepared by a novel and facile method

Cu₂O/Cu composite particles were synthesized by a novel and facile chemical reduction method without any template or surfactant. X-ray diffraction (XRD) results showed that the product mainly consisted of the Cu₂O phase coexisting with a few Cu phases. Typical FE-SEM images indicated that the particles with an octahedral shape were Cu₂O. In addition, the electrochemical performance of the Cu₂O/Cu particles as the working electrode material in alkaline solution was systematically investigated. The particles showed a maximum discharge capacity of 222.9 mAh g⁻¹ at a discharge current density of 60 mA g⁻¹ and a high value of 109.1 mAh g⁻¹ after 50 charge–discharge cycles. The results of cyclic voltammetry demonstrated that the reaction between Cu₂O and Cu is the major electrochemical reaction during the charging and discharging process. The results of electrochemical impedance spectroscopy indicated that the formation of Cu₂O on the surface of Cu particles significantly increased the contact resistance and the charge transfer resistance of the electrode during the discharging process.     

电化学处理选磷尾矿水的回水选矿试验

磷矿浮选的尾矿水在无隔膜电化学处理槽中经电化学方法处理后作循环用回水,与清水进行开路与闭路浮选对比试验的结果表明：经电化学处理后的磷矿浮选尾矿水用于浮选,其操作条件稳定,能改善浮选环境,在相当的磷精矿品位和回收率的情况下,使用电化处理的回水可降低Ｎａ２ＣＯ３的耗量２５％。