Role of methoxy and C_(α)-based substituents in electrochemical oxidation mechanisms and bond cleavage selectivity of β-O-4 lignin model compounds

In order to better understand the specific substituent effects on the electrochemical oxidation process of β-O-4 bond, a series of methoxyphenyl type β-O-4 dimer model compounds with different localized methoxyl groups, including 2-(2-methoxyphenoxy)-1-phenylethanone, 2-(2-methoxyphenoxy)-1-phenylethanol, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanol, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanol have been selected and their electrochemical properties have been studied experimentally by cyclic voltammetry, and FT-IR spectroelectrochemistry. Combining with electrolysis products distribution analysis and density functional theory calculations, oxidation mechanisms of all six model dimers have been explored. In particular, a total effect from substituents of both para-methoxy(on the aryl ring closing to Cα) and Cα-OH on the oxidation mechanisms has been clearly observed, showing a significant selectivity on the Cα-Cβbond cleavage induced by electrochemical oxidations.

In-situ oriented oxygen-defect-rich Mn-N-O via nitridation and electrochemical oxidation based on industrial-scale Mn_(2)O_(3) to achieve high-performance aqueous zinc ion battery

As a general problem in the field of batteries,materials produced on a large industrial scale usually possess unsatisfactory electrochemical performances.Among them,manganese-based aqueous rechargeable zinc-ion batteries(ARZBs)have been emerging as promising large-scale energy storage systems owing to their high energy densities,low manufacturing cost and intrinsic high safety.However,the direct application of industrial-scale Mn2O3(MO)cathode exhibits poor electrochemical performance especially at high current rates.Herein,a highly reversible Mn-based cathode is developed from the industrial-scale MO by nitridation and following electrochemical oxidation,which triples the ion diffusion rate and greatly promotes the charge transfer.Notably,the cathode delivers a capacity of 161 m Ah g^(-1) at a high current density of 10 A g^(-1),nearly-three times the capacity of pristine MO(60 m Ah g^(-1)).Impressive specific capacity(243.4 m Ah g^(-1))is obtained without Mn^(2+) additive added in the electrolyte,much superior to the pristine MO(124.5 m Ah g^(-1)),suggesting its enhanced reaction kinetics and structural stability.In addition,it possesses an outstanding energy output of 368.4 Wh kg^(-1) at 387.8 W kg^(-1),which exceeds many of reported cathodes in ARZBs,providing new opportunities for the large-scale application of highperformance and low-cost ARZBs.

Electrochemical oxidation of aniline by a novel Ti/TiO_xH_y/Sb-SnO_2 electrode

Electrochemical oxidation of aniline in aqueous solution was investigated over a novel Ti/TiOxHy/Sb-SnO2 electrode prepared by the electrodeposition method.Scanning electron microscopy,X-ray diffraction,and electrochemical measurements were used to characterize its morphology,crystal structure,and electrochemical properties.Removal of aniline by the Ti/TiOxHy/Sb-SnO2electrode was investigated by ultraviolet-Visible spectroscopy and chemical oxygen demand（COD）analysis under different conditions,including current densities,initial concentrations of aniline,pH values,concentrations of chloride ions,and types of reactor.It was found that a higher current density,a lower initial concentration of aniline,an acidic solution,the presence of chloride ions（0.2wt%NaCl）,and a three-dimensional（3D） reactor promoted the removal efficiency of aniline.Electrochemical degradation of aniline followed pseudo-first-order kinetics.The aniline（200 mL of 100mg·L-（-1）） and COD removal efficiencies reached 100%and 73.5%,respectively,at a current density of 20 mA·cm-（-2）,pH of 7.0,and supporting electrolyte of 0.5 wt%Na2SO4 after 2 h electrolysis in a 3D reactor.These results show that aniline can be significantly removed on the Ti/TiOxHy/Sb-SnO2electrode,which provides an efficient way for elimination of aniline from aqueous solution.

Sustainable Furfural Biomass Feedstocks Electrooxidation toward Value-Added Furoic Acid with Energy-Saving H_(2) Fuel Production Using Pt-Decorated Co_(3)O_(4) Nanospheres

Here,furfural oxidation was performed to replace the kinetically sluggish O_(2)evolution reaction(OER).Pt-Co_(3)O_(4)nanospheres were developed via pulsed laser ablation in liquid(PLAL)in a single step for the paired electrocatalysis of an H_(2)evolution reaction(HER)and furfural oxidation reaction(FOR).The FOR afforded a high furfural conversion(44.2%)with a major product of 2-furoic acid after a 2-h electrolysis at 1.55 V versus reversible hydrogen electrode in a 1.0-M KOH/50-mM furfural electrolyte.The Pt-Co_(3)O_(4)electrode exhibited a small overpotential of 290 mV at 10 mA cm^(-2).As an anode and cathode in an electrolyzer system,the Pt-Co_(3)O_(4)electrocatalyst required only a small applied cell voltage of~1.83 V to deliver 10 mA cm^(-2),compared with that of the pure water electrolyzer(OER||HER,~1.99 V).This study simultaneously realized the integrated production of energy-saving H_(2)fuel at the cathode and 2-furoic acid at the anode.

Tuning the reactivity of TiO_(2)layer with uniform distribution of Sub-5 nm Fe_(2)O_(3)particles via in situ voltage-assisted oxidation for robust catalytic reduction

The trade-off between efficiency and stability has limited the application of TiO_(2)as a catalyst due to its poor surface reactivity.Here,we present a modification of a TiO_(2)layer with highly stable Sub-5 nm Fe_(2)O_(3)nanoparticles(NP)by modulating its structure-surface reactivity relationship to attain efficiency-stability balance via a voltage-assisted oxidation approach.In situ simultaneous oxidation of the Ti substrate and Fe precursor using high-energy plasma driven by high voltage resulted in uniform distribution of Fe_(2)O_(3)NP embedded within porous TiO_(2)layer.Comprehensive surface characterizations with density functional theory demonstrated an improved electronic transition in TiO_(2)due to the presence of surface defects from reactive oxygen species and possible charge transfer from Ti to Fe;it also unexpectedly increased the active site in the TiO_(2)layer due to uncoordinated electrons in Sub-5 nm Fe_(2)O_(3)NP/TiO_(2)catalyst,thereby enhancing the adsorption of chemical functional groups on the catalyst.This unique embedded structure exhibited remarkable improvement in reducing 4-nitrophenol to 4-aminophenol,achieving approximately 99%efficiency in 20 min without stability decay after 20 consecutive cycles,outperforming previously reported TiO_(2)-based catalysts.This finding proposes a modified-electrochemical strategy enabling facile construction of TiO_(2)with nanoscale oxides extandable to other metal oxide systems.

Electrochemically reduced graphene oxide with enhanced electrocatalytic activity toward tetracycline detection

An electrochemically reduced graphene oxide sample, ERGO_0.8v, was prepared by electrochemical reduction of graphene oxide （GO） at -0.8 V, which shows unique electrocatalytic activity toward tetracycline （TTC） detection compared to the ERGO-12v （GO applied to a negative potential of-1.2 V）, GO, chemically reduced GO （CRGO）-modified glassy carbon electrode （GC） and bare GC electrodes. The redox peaks of TTC on an ERGO-0.8v-modifled glass carbon electrode （GC/ERGO-0.8v） were within 0-0.5 V in a pH 3.0 buffer solution with the oxidation peak current correlating well with TTC concentration over a wide range from 0.1 to 160 mg/L Physical characterizations with Fourier transform infrared （FT-IR）, Raman, and X-ray photoelectron spectroscopies （XPS） demonstrated that the oxygen-containing functional groups on GO diminished after the electrochemical reduction at -0.8 V, yet still existed in large amounts, and the defect density changed as new sp2 domains were formed. These changes demonstrated that this adjustment in the number of oxygen-containing groups might be the main factor affecting the electrocatalytic behavior of ERGO. Additionally, the defect density and sp2 domains also exert a profound influence on this behavior. A possible mechanism for the TTC redox reaction at the GC/ERGO-0.8v electrode is also presented. This work suggests that the electrochemical reduction is an effective method to establish new catalytic activities of GO by setting appropriate parameters.

Electrochemical oxidation of rhodamine B by PbO_2/Sb-SnO_2/TiO_2 nanotube arrays electrode

A PbO2/Sb-SnO2/TiO2 nanotube array composite electrode was successfully synthesized and its electrochemical oxidation properties were investigated.Field-emission scanning electron microscopy(FE-SEM)and X-ray diffraction(XRD)results showed that the PbO2 coating was composed of anα-PbO2 inner layer and aβ-PbO2 outer layer.Accelerated life measurement indicated that the composite electrode had a lifetime of 815 h.Rhodamine B(RhB)was employed as a model pollutant to analyze the electrocatalytic activity of the electrode.The effects of initial RhB concentration,current density,initial pH,temperature,and chloride ion concentration on the electrochemical oxidation were investigated in detail.Inductively coupled plasma atomic emission spectroscopy(ICP-AES)results suggested that the concentration of leached Pb^2+in the electrolyte during the electrocatalytic oxidation process can be neglected.Finally,the degradation mechanism during the electrocatalytic oxidation process was proposed based on the results of solid-phase micro-extraction-gas chromatography-mass spectrometry(SPME-GC-MS).The high electrocatalytic performance of the composite electrode makes it a promising anode for the treatment of organic pollutants in aqueous solution.

Colour and organic removal of biologically treated coffee curing wastewater by electrochemical oxidation method

The treatment of biologically treated wastewater of coffee-curing industry by the electrochemical oxidation using steel anode was investigated. Bench-scale experiments were conducted for activated sludge process on raw wastewater and the treated effluents were further treated by electrochemical oxidation method for its colour and organic content removal. The efficiency of the process was determined in terms of removal percentage of COD, BOD and colour during the course of reaction. Several operating parameters like time, pH and current density were examined to ascertain their effects on the treatment efficiency. Steel anode was found to be effective for the COD and colour removal with anode efficiency of 0.118 kgCOD\5h -1\5A -1\5m -2 and energy consumption 20.61 kWh\5kg -1 of COD at pH 9. The decrease in pH from 9 to 3 found to increase the anode efficiency from 0.118 kgCOD\5h -1\5A -1\5m -2 to 0.144 kWh\5kg -1 of COD while decrease the energy consumption from 20.61 kWh\5kg -1 of COD to 12.86 kWh\5kg -1 of COD. The pH of 5 was considered an ideal from the present treatment process as it avoids the addition of chemicals for neutralization of treated effluents and also economical with respect to energy consumption. An empirical relation developed for relationship between applied current density and COD removal efficiency showed strong predictive capability with coefficient of determination of 96.5%.

Electrochemical oxidation of reactive brilliant orange X-GN dye on boron-doped diamond anode

In this study,the electrochemical oxidation of reactive brilliant orange X-GN dye with a boron-doped diamond(BDD)anode was investigated.The BDD electrodes were deposited on the niobium(Nb)substrates by the hot filament chemical vapor deposition method.The effects of processing parameters,such as film thickness,current density,supporting electrolyte concentration,initial solution pH,solution temperature,and initial dye concentration,were evaluated following the variation in the degradation efficiency.The microstructure and the electrochemical property of BDD were characterized by scanning electron microscopy,Raman spectroscopy,and electrochemical workstation;and the degradation of X-GN was estimated using UV-Vis spectrophotometry.Further,the results indicated that the film thickness of BDD had a significant impact on the electrolysis of X-GN.After 3 h of treatment,100%color and 63.2%total organic carbon removal was achieved under optimized experimental conditions:current density of 100 mA/cm2,supporting electrolyte concentration of 0.05 mol/L,initial solution pH 3.08,and solution temperature of 60°C.

Comparison Between Performances of PbO_2 and F^--doped PbO_2 Anodes for Electrochemical Degradation of Aniline

The paper deals with the influence of anode material on the efficiency of degradation for organic pollutants in water system.The electrochemical performance of fluorine ion doped lead dioxide（F--PbO2） electrode for the degradation of aniline was compared with that of undoped lead dioxide（PbO2） electrode by ultraviolet-visible（UV-Vis） spectroscopy,linear voltammetry and other analytical methods,such as the measurement by chemical oxygen demand analyzer,high performance liquid chromatography and scanning electron micrography.It was shown that both PbO2 electrode and F--PbO2 electrode could make aniline be mineralized completely and have the same degradation course,but F--PbO2 electrode has much higher electrocatalytic activity than undoped PbO2 electrode for the electrochemical degradation of aniline.The experimental results confirm that F--PbO2 electrode has much higher potential for oxygen evolution than undoped PbO2 electrode.

Indirect Electrochemical Oxidation of 4-Amino-dimethyl-aniline Hydrochloride

The indirect dectrechemical oxidation of 4-amino-dimethyl-aniline hydrochloride containing wastewater generated from vanillin production is presented. Experiments were conducted at a constant current density of 30 rnA/cm^2 via a Ti/Bu-Ti-Sn ternary oxide coated anode and an undivided reactor. During the various stages of the electrolysis, parameters such as the values of chemical oxygen demand（COD） and total organic carbon（TOC） were determined in order to evaluate the feasibility of the electrochemical treatment. The energy consumption and the current efficiency during the electrolysis were calculated. The present study proves the effectiveness of the electrochemical treatment for wastewater resulted from vanillin production.

Study on superoxide and hydroxyl radicals generated in indirect electrochemical oxidation by chemiluminescence and UV-Visible spectra

The generation and transformation of radicals on the cathode of indirect electrochemical oxidation were studied by chemilumines- cence(CL)and UV-Visible spectra in the reactor with a salt bridge that connected the separated chambers.The CL intensity of 4×10^(-9)mol/L luminol on the cathode with bubbling oxygen was about seven times that of the intensity without it,which was because of the generation of reactive oxygen species(ROS).The existence of ROS,especially the generation of the superoxide radical,coul...

Electrochemical Oxidation of L-Cystenine in SDS/BA/H_2O Microemulsion

The electrochemical oxidation of L-cysteine in an SDS/BA/H_2O microemulsion system was studied with the methods of ultramicroelectrode cyclic voltammetry and AC impedance. The catalytic efficiency of the microemulsion on the electrochemical oxidation increases with the increase of BA or SDS content, but decreases with the increase of the water content because of the effects of BA, SDS and water on the solubilization of L-cysteine in the microemulsion. Furthermore, the catalytic efficiency of the bicontinuous structure is greater than that of an O/W microemulsion system. The results derived from both the rate constant k0 and Gibbs free energy ΔG≠ accord with those from the catalytic efficiency.

Mechanism study of electrochemical oxidation in the terylene diaphragm cell

By using a self-made carbon/polytetrafluoroethylene （C/PTFE） O2-fed as cathode and Ti/IrO2/RuO2 as anode, the effects of electrochemical oxidation of phenol and the coal-gas wastewater containing phenol were studied. The terylene diaphragm which kept pH〉12 in cathodic compartment and pH〈1 in the anodic compartment was selected in the experiment in comparison with the other types of diaphragm. Furthermore, hydroxyl radical （HO·） was determined in the cathodic compartment of the diaphragm cell by electron spin resonance spectrum（ESR） and the fluorescence spectra. Compared with pH, the accumulated HzO2 and the COD removal of the no-diaphragm cell, the mechanism of electrochemical oxidation in the terylene diaphragm cell was supposed. The degradation of phenol was supposed to be cooperative oxidation by direct or indirect electrochemical oxidation at the anode and H2O2, HO· produced by oxygen reduction at the cathode. The mineralization of phenol in the diaphragm cell was better than that in the no-diaphragm cell. When the coal-gas wastewater was treated by the electrolysis system with terylene diaphragm, the average removal efficiency of the volatile phenol and COD were 100% and 79.6%, respectively.

Electrochemical oxidation of ammonia-containing wastewater using Ti/RuO_2-Pt electrode

The electrochemical oxidation degradation processes for artificial and actual wastewater containing ammonia were carried out with a Ti/RuO2-Pt anode and a Ti plate cathode. We studied the effects of different current densities, space sizes between the two electrodes, and amounts of added NaCl on ammonia-containing wastewater treatm.ent. It was shown that, after a 30-min treatment under the optimal conditions, which were a current density of 20 mA/cm2, a space size between the two electrodes of I cm, and an added amount of 0.5 g/L of NaC1, the COD concentration in municipal wastewater was 40 mg/L, a removal rate of 90%; and the NH3-N concentration was 7 mg/L, a removal rate of 88.3%. The effluent of municipal wastewater qualified for Class A of the Discharge Standard of Pollutants for Municipal Wastewater Treatment Plant （GB 18918-2002）.

Surface State of Carbon Fibers Modified by Electrochemical Oxidation

Surface of polyacrylonitrile (PAN)-based carbon fibers was modified by electrochemical oxidation. The modification effect on carbon fibers surface was explored using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). Results showed that on the modified surface of carbon fibers, the carbon contents decreased by 9.7% and the oxygen and nitrogen contents increased by 53.8% and 7.5 times, respectively. The surface roughness and the hydroxyl and carbonyl contents also increased. The surface orientation index was reduced by 1.5% which decreased tensile strength of carbon fibers by 8.1%, and the microcrystalline dimension also decreased which increased the active sites of carbon fiber surface by 78%. The physical and chemical properties of carbon fibers surface were modified through the electrochemical oxidative method, which improved the cohesiveness between the fibers and resin matrix and increased the interlaminar shear strength (ILSS) of carbon fibers reinforced epoxy composite (CFRP) over 20%.

Degradation of chlorophenol by in－situ electrochemically generated oxidant

A novel in-situ electrochemical oxidation method was applied to the degradation of wastewater containing chlorophenol. Under oxygen sparging, the strong oxidant, hydrogen dioxide, could be in-situ generated through the reduction of oxygen on the surface of the cathode. The removal rate ofchlorophenol could be increased 149% when oxygen was induced in the electrochemical cell. The promotion factor was estimated to be about 82.63% according to the pseudo-first-order reaction rate constant (min^-1). Important operating parameters such as current density, sparged oxygen rate were investigated. Higher sparged oxygen rate could improve the degradation of chlorophenol. To make full use of oxygen, however, sparged oxygen rate of 0.05 m3/h was adopted in this work. Oxidation-reduction potential could remarkably affect the generation of hydrogen peroxide. It was found that the removal rate of chlorophenol was not in direct proportion to the applied current density. The optimum current density was 3.5 mA/cm^2 when initial chlorophenol concentration was 100 mg/L and sparged oxygen rate was 0.05 m^3/h.

The effects of electrochemical oxidation on in-vivo fluorescence and toxin content in Microcystis aeruginosa culture

The increasing occurrence of cyanobacterial blooms in water bodies is a serious threat to the environment. Efficient in-lake treatment methods for the control of cyanobacteria proliferation are needed, their in-vivo detection to obtain a real-time response to their presence, as well as the information about their physiological state after the applied treatment. In-vivo fluorescence measurements of photosynthetic pigments have proved to be effective for quantitative and qualitative detection of phytoplankton in a water environment. In the experiment, chlorophyll and phycocyanin fluorescence sensors were used concurrently to detect stress caused by electrochemical oxidation applying an electrolytic cell equipped with borondoped diamond electrodes on a laboratory culture of cyanobacteria Microcystis aeruginosa PCC 7806. The inflicted injuries were reflected in a clear transient increase in the phycocyanin fluorescence signal(for 104 %? 43%) 24 h after the treatment, which was not the case for the chlorophyll fluorescence signal. In the next 72 h of observation, the fluorescence signals decreased(on 40% of the starting signal) indicating a reduction of cell number, which was confirmed by cell count(24% reduction of the starting concentration) and analysis of extracted chlorophyll and phycocyanin pigment. These results demonstrate the viability of the combined application of two sensors as a useful tool for in-vivo detection of induced stress, providing real-time information needed for the evaluation of the efficiency of the in-lake treatment and decision upon the necessity of its repetition. The electrochemical treatment also resulted in a lower free microcystins concentration compared to control.

Enhanced electrochemical oxidation of phenol by introducing ferric ions and UV radiation

The mineralization of phenol in aerated electrochemical oxidation has been investigated.The results show that a cathodic Fenton process can occur when the Ti-0.3Mo-0.8Ni alloy material is used as cathode in solution containing ferric or ferrous ions; moreover,the reinforcement of cathodic Fenton process on the total organic carbon (TOC) removal rate of phenol is quite distinct.Among the metallic ions investigated,the ferric ion is the best catalyst for the electrochemical mineralization of phenol at initial...

The pharmacokinetic study of rutin in rat plasma based on an electrochemically reduced graphene oxide modified sensor

An electrochemical method based on a directly electrochemically reduced graphene oxide （ERGO） film coated on a glassy carbon electrode （GCE） was developed for the rapid and convenient determination of rutin in plasma. ERGO was modified on the surface of GCE by one-step electro-deposition method. Electrochemical behavior of rutin on ERGO/GCE indicated that rutin underwent a surface-controlled quasi-reversible process and the electrochemical parameters such as charge transfer coefficient （α）, electron transfer number （n） and electrode reaction standard rate constant （ks） were 0.53, 2 and 3.4 s -1, respectively. The electrochemical sensor for rutin in plasma provided a wide linear response range of 4.70 × 10 ^-7 1.25 × 10^-5 M with the detection limit （s/n=3） of 1.84 × 10^-8 M. The assay was success- fully used to the pharmacokinetic study of rutin. The pharmacokinetic parameters such as elimination rate half-life （t1/2）, area under curve （AUC）, and plasma clearance （CL） were calculated to be 3.345 ± 0.647 rain, 5750 ±656.0 μg min/mL, and 5.891± 0.458 mL/min/kg, respectively. The proposed method utilized a small sample volume of 10 μL and had no complicated sample pretreatment （without deproteinization）, which was simple, eco-friendly, and time- and cost-efficient for rutin pharmacokinetic studies.