Temperature Effect on Hydrogen Evolution Reaction at Au Electrode

The temperature dependence of hydrogen evolution reaction （HER） at a quasi-single crystalline gold electrode in both 0.1 mol/L HCl04 and 0.1 mol/L KOH solutions was investigated by cyclic voltammetry. HER current displays a clear increase with reaction overpotential （η） and temperature from 278-333 K. In 0.1 mol/L HClO4 the Tafel slopes are found to increases slightly with temperature from 118 mV/dec to 146 mV/dec, while in 0.1 mol/L KOH it is ca. 153±15 mV/dec without clear temperature-dependent trend. The apparent activation energy （Ea） for HER at equilibrium potential is ca. 48 and 34 kJ/mol in 0.1 mol/L HC104 and 0.1 mol/L KOH, respectively. In acid solution, Ea decreases with increase in η, from Ea-37 kJ/mol （η=0.2 V） to 30 kJ/mol （η=0.35 V）. In contrast, in 0.1 mol/L KOH, Ea does not show obvious change with U. The pre-exponential factor （A） in 0.1 mol/L HC104 is ca. 1 order higher than that in 0.1 mol/L KOH. Toward more negative potential, in 0.1 mol/L HC104 A changes little with potential, while in 0.1 mol/L KOH it displays a monotonic increase with U. The change trends of the potential-dependent kinetic parameters for HER at Au electrode in 0.1 mol/L HClO4 and that in 0.1 mol/L KOH are discussed.

pH Effect on Oxidation of Hydrogen Peroxide on Au(111) Electrode in Alkaline Solutions

The hydrogen peroxide oxidation reaction (HPOOR) on Au(111) electrode in alkaline solutions with pH values ranging from 10 to 13 was examined systematically. HPOOR activity increased and the slope of the i-E curve decreased with increasing pH. HO2- is suggested to be the main reactive intermediate for HPOOR in alkaline media. The fast kinetics for HPOOR in alkaline solution is facilitated by the electrostatic interaction between the positively charged electrode and the reactive anions (i.e., HO2- and HO-), which increases the concentration of these reactants and the thermodynamic driving force for HO2- oxidation at the reaction plane.

Direct Electrochemistry and Electrocatalysis of Hemoglobin at PAMAM Dendrimer-MWNTs-Au Nanoparticles Composite Film Modified Glassy Carbon Electrode

The direct electron transfer of hemoglobin at the PAMAM-MWNTs-AuNPs composite film modified glassy carbon electrode was studied. In a phosphate buffer solution（PBS, pH=7.0）, the formal potential（E^0） of Hb was -0.105 V versus SCE, the electron transfer rate constant was 4.66 s-1. E^0＇ of Hb at the modified electrode was linearly varied in a pH range of 5.0-8.0 with a slope of-49.2 mV/pH. The Hb/PAMAM-MWNTs-AuNPs/GCE gave an excellent electrocatalytic response to the reduction of hydrogen peroxide. The catalytic current increased linearly with H2O2 concentration in a range of 1.0× 10^-6 to 2.2× 10^-3 mol/L. The detection limit was 2.0× 10^-7 mol/L at a signal to noise ratio of 3. The Michaelis-Menten constant（Km^app） was 2.95 mmol/L.

Preparation and electrocatalytic property of Au-Pt/SnO_2/GC composite electrode

Au-Pt/SnO2/GC composite electrode was prepared by self-assembling Au-Pt nanoparticles on SnO2 film, which was deposited on actived glassy carbon （GC）. Atomic force microscopy （AFM） and scanning electron microscopy （SEM） images revealed that dense and uniform Au-Pt particles with 25-nm diameter were dispersed on SnO2 film. X-ray photoelectron spectroscopy （XPS） results proved that there was an interaction between Au-Pt nanoparticles and SnO2 support. Electrochemical experiments showed that Au-Pt/SnOz/GC composite electrode had a good electrocatalytic activity to the oxidation of methanol

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.

Effect of Sb dopant amount on the structure and electrocatalytic capability of Ti/Sb-SnO_2 electrodes in the oxidation of 4-chlorophenol

Ti/Sb-SnO2 anodes were prepared by thermal decomposition to examine the influence of the amount of Sb dopant on the structure and electrocatalytic capability of the electrodes in the oxidation of 4-chlorophenol. The physicochemical properties of the Sb-SnO2 coating were markedly influenced by different amounts of Sb dopant. The electrodes, which contained 5% Sb dopant in the coating, presented a much more homogenous surface and much smaller mud-cracks, compared with Ti/Sb-SnO2 electrodes containing 10% or 15% Sb dopant, which exibited larger mud cracks and pores on the surface. However, the main microstructure remained unchanged with the addition of the Sb dopant. No new crystal phase was observed by X-ray diffraction （XRD）. The electrochemical oxidation of 4-chlorophenol on the Ti/SnO2 electrode with 5% Sb dopant was inclined to electrochemical combustion; while for those containing more Sb dopant, intermediate species were accumulated. The electrodes with 5% Sb dopant showed the highest efficiency in the bulk electrolysis of 4-chlorophenol at a current density of 20 mA/cm^2 for 180 min; and the removal rates of 4-chlorophenol and COD were 51.0% and 48.9%, respectively.

Preparation and application of pharmaceutical wastewater treatment by praseodymium doped SnO_2/Ti electrocatalytic electrode

Praseodymium was selected as a promoter for SnO2/Ti electrode to improve the electrocatalytic performance by electrodeposition in pharmaceutical wastewater treatment; the micrograph and the structure were characterized by SEM and XRD. Mixture uniform design was used in the optimization of the electrolytic conditions; mathematical model was established according to the rate of wiping COD off, which revealed the relationship between the current intensity, time of electrolysis, the amount of doped Pr, and the ratio of area （SnOJTi：Al）. On the basis of the analysis of the empirical model, the optimized parameters had been obtained; the rate of wiping COD off was up to 94.9%, it decreased from 392 to 20 mg/L. Experimental results showed that the electrocatalytic performance of the electrode doped with Pr was superior for the treatment of pharmaceutical wastewater.

Enhancing Capacitance Performance of Ti3C2Tx MXene as Electrode Materials of Supercapacitor: From Controlled Preparation to Composite Structure Construction

Ti3C2Tx,a novel two-dimensional layer material,is widely used as electrode materials of supercapacitor due to its good metal conductivity,redox reaction active surface,and so on.However,there are many challenges to be addressed which impede Ti3C2Tx obtaining the ideal specific capacitance,such as restacking,re-crushing,and oxidation of titanium.Recently,many advances have been proposed to enhance capacitance performance of Ti3C2Tx.In this review,recent strategies for improving specific capacitance are summarized and compared,for example,film formation,surface modification,and composite method.Furthermore,in order to comprehend the mechanism of those efforts,this review analyzes the energy storage performance in different electrolytes and influencing factors.This review is expected to predict redouble research direction of Ti3C2Tx materials in supercapacitors.

Surface Modification Process by Electrical Discharge Machining with Ti Powder Green Compact Electrode

This paper describes a new method of surface modification by Electrical Discharge Machining (EDM). By using ordinary EDM machine tool and kerosene fluid, a hard ceramic layer can be created on the workpiece surface with Ti or other compressed powder electrode in a certain condition. This new revolutionary method is called Electrical Discharge Coating (EDC). The process of EDC begins with electrode wear during EDM,then a kind of hard carbide is created through the thermal and chemical reaction between the worn electrode material and the carbon particle decomposed from kerosene fluid under high temperature. The carbide is piled up on a workpiece quickly and becomes a hard layer of ceramic about 20 μm in several minutes. This paper studies the principle and process of EDC systemically by using Ti powder green compact electrode. In order to obtain a layer of compact ceramic film, it is very important to select proper electric pulse parameters, such as pulse width, pulse interval, peak current. Meantime, the electrode materials and its forming mode will effect the machining surface quality greatly. This paper presents a series of experiment results to study the EDC process by adopt different technology parameters. Experiments and analyses show that a compact TiC ceramic layer can be created on the surface of metal workpiece. The hardness of ceramic layer is more 3 times higher than the base body, and the hardness changes gradiently from surface to base body. The method will have a great future because many materials can be easily added to the electrode and then be coated on the workpiece surface. Gearing the parameters ceramic can be created with different thickness. The switch between deposition and removal process is carried out easily by changing the polarity, thus the gear to the thickness and shape of the composite ceramic layer is carried out easily. This kind of composite ceramic layer will be used to deal with the surface of the cutting tools or molds possibly, in order to lengthen their life. It also can be found wide application in the fields of surface repairing and strengthening of the ship or aircraft.

Electrochemical analysis and convection-enhanced mass transfer synergistic effect of MnO_x/Ti membrane electrode for alcohol oxidation

The different electrocatalytic reactors could be constructed for the electrocatalytic oxidation of 2,2,3,3-tetrafluoro-1-propanol(TFP) with two typical MnO_x/Ti electrodes, i.e.the electrocatalytic membrane reactor(ECMR) with the Ti membrane electrode and the electrocatalytic reactor(ECR) with the traditional Ti plate electrode.For the electro-oxidation of TFP, the conversion with membrane electrode(70.1%) in the ECMR was 3.3 and 1.7 times higher than that of the membrane electrode without permeate flow(40.8%) in the ECMR and the plate electrode(21.5%) in the ECR, respectively.Obviously, the pore structure of membrane and convection-enhanced mass transfer in the ECMR dramatically improved the catalytic activity towards the electro-oxidation of TFP.The specific surface area of porous electrode was 2.22 m^2·g^(-1).The surface area of plate electrode was 2.26 cm^2(1.13 cm^2× 2).In addition, the electrochemical results showed that the mass diffusion coefficient of the MnO_x/Ti membrane electrode(1.80 × 10^(-6) cm^2·s^(-1)) could be increased to 6.87 × 10^(-6) cm^2·s^(-1) at the certain flow rate with pump, confirming the lower resistance of mass transfer due to the convection-enhanced mass transfer during the operation of the ECMR.Hence, the porous structure and convection-enhanced mass transfer would improve the electrochemical property of the membrane electrode and the catalytic performance of the ECMR,which could give guideline for the design and application of the porous electrode and electrochemical reactor.

Electrochemical oxidation of Rhodamine B with cerium and sodium dodecyl benzene sulfonate co-modified Ti/Pb0_(2)electrodes:Preparation,characterization,optimization,application

Regulation of the electronic structure and interface property becomes a major strategy in the preparation of electrocatalyst.This paper reports the synthesis of cerium(Ce)and sodium dodecyl benzene sulfonate(SDBS)comodified Ti/PbO_(2)electrodes(Ti/PbO2CeSDBS).Ce and SDBS could greatly change the electronic structure and interface property of PbO2.Ti/PbO_(2)CeSDBS exhibited excellent electrocatalytic activity and stability in Rhodamine B(RhB)electrocatalytic oxidation reaction.The improved electrocatalytic activity associates with the synergistic effect of electronic and interface factors.In the electrochemical degradation of RhB,the removal efficiencies of RhB and COD are about 0.880 and 0.694 respectively after the electrolysis of 220 min with Ti/PbO_(2)Ce4SDBS40,which are higher than the contrast Ti/PbO_(2)electrodes.In the meantime,the accelerated lifetime of Ti/PbO_(2)Ce4SDBS40 is more than 6.2 times than that of Ti/PbO_(2).

Electrochemical treatment of COD in biologically pretreated coking wastewater using Ti/RuO2-IrO2 electrodes combined with modified coke

The electrochemical treatment of COD contained in biologically pretreated coking wastewater treated by a three-dimensional electrode system with modified coke as the particle electrode was investigated. And the electrochemical perromance of the coke modified with various active components was studied. The results show that the coke modified with Fe（NO3）2 has the lowest energy consumption and higher COD removal rate under the same condition, and the modified coke has better surface characteristics for the purpose of this study. In addition, the kinetic constant was also calculated. The study shows that the three-dimensional electrode system with Fe （NO3）z-modified coke can give a satisfactory solution in biologically pretreated coking wastewater.

Electro-catalytic oxidation of phenol with Ti-base lead dioxide electrode

The Ti base PbO 2 electrode prepared by electrodeposition of PbO 2 on the surface of titanium was used for electro catalytic oxidation of phenol in waste water. The experimental results show that the electrodeposition of PbO 2 at a higher current density for a short time, then followed by a lower current density can get a compact and combinative PbO 2 layer. The properties of a Ti/PbO 2 electrode with an interlayer of oxide are the best. When this kind of electrode is used to treat phenol containing waste water, the phenol removal rate is higher and the slot voltage is lower. In addition, by using the phenol removal rate as an index, the influences of electrolysis current density, mass transfer condition and pH were studied and the optimal condition was confirmed.

The Electrode Process of Titanium Subchlorides and Electrodeposition of Titanium in LiCl-KCl Fused Salts

The electrochemical behaviour of Ti(Ⅲ) and Ti(Ⅱ) in LiCl-KCl eutectic system has been studied by cyclic voltammetry and chronoamperometry.The cathodic reduction of Ti(Ⅲ) and Ti(Ⅱ) has been found to be stepwise:Ti(Ⅲ)+e=Ti(Ⅱ),Ti(Ⅱ)+2e =Ti.The reductions are diffusion controlled.When an equilibrium between Ti subchlorides and excess metallic Ti was estab- lished by reaction 2TiCl_3+Ti=3TiCl_2 in LiCl-KCl melt at 475℃,then the average valence of Ti is less than 2.1.In this system the diffusion coefficient for Ti(Ⅱ) ion was calculated as D=2.5×10^(-5)cm^2·s^(-1).The chronoamperometric studies showed that the initial nucleation stage and growth of nuclei were observed when Ti ions were electrodeposited on low carbon steel substrate. The investigation of nucleation of metal may provide the method for obtaining smooth,coherent and adherent deposits of titanium.

Environment-Friendly Determination of Low Concentration Azobenzene β-Cyclodextrin-Modified Electrode

Objective To study environment-friendly determination of azobenzene in trace amounts using β-cyclodextrin （β-CD）-modified Au electrode. Methods β-CD-modified Au electrode was fabricated with a two-step approach, and then a gold electrode modified with β-CD was used to detect azobenzene by employing Osteryoung square wave voltammetry. Results The modified electrode could detect azobenzene, showing a good linearity between the electrochemical current and concentration. Conclusion Although the electrochemical current is related with concentration, the detection limit is around 1 .0 ×10^-10 mol/L. This study may provide a new environment-friendly approach for monitoring water quality.

An EQCM Study of the Electrochemical Behaviors of Polycrystalline Gold Electrode in Sulfuric Acid Solution

The electrochemical quartz crystal microbalance (EQCM) was applied to study the electrochemical behaviors of polycrystalline Au in sulfuric acid solution. The large mass change observed in the doublelayer region was attributed to the partly discharged adsorption of sulfate anions with the co-adsorption of H2O. According to the observed EQCM frequency response, the formation mechanism of surface oxide was reasonably postulated, in which the roles of the adsorbed anions and the co-adsorbed H2O were particularly emphasized.

A Study on a Partially Immersed Gold Electrode Using an Electrochemical Quartz Crystal Impedance System

The electrochemical quartz crystal impedance system (EQCIS) has been used for the study of a partially immersed Au electrode in 0.2 mol/L NaClO4 aqueous solution. The influences of the immersed area and height of the electrode on the EQCIS responses were evaluated, showing the highest response sensitivity to liquid loading at the center of the piezoelectric quartz crystal electrode. The increase in the immersed height of the Au electrode at oxygen reduction potentials during potential cycling was measured by this technique.

Synthesis and Temperature-dependent Electrochemical Properties of Boron-doped Diamond Electrodes on Titanium

On the sand-blasting-treated titanium（Ti） substrate, the boron-doped diamond（BDD） electrodes with a wide potential window were prepared by microwave plasma chemical vapor deposition（MPCVD）. The electrochemi- cal oxidation ratios of phenol at BDD/Ti electrodes at elevated temperatures（from 20 ℃ to 80 ℃） were examined by the chemical oxygen demand（COD） of phenol electrolyte during electrolysis. The results show that the COD removal was increased at high temperatures and the optimized temperature for enhancing the electrochemical oxidation ratio of phenol is 60 ℃. The mechanism for the temperature-dependent electrochemical oxidation ratios of phenol at the electrodes was investigated. The study would be favorable for further improving the performance of BDD/Ti elec- trodes, especially working at high temperatures.

Photoelectrocatalytic Oxidation of Ethinylestradiol on a Ti/TiO₂Electrode: Degradation Efficiency and Search for By-Products

The degradation of ethinylestradiol (EE, an orally bio-active estrogen) in an aqueous-methanolic solution using a Ti/TiO2 thin-film electrode and UV radiation (a photoelectrocatalytic system) was evaluated. Hence, HPLC/UV analysis shows that EE (at 0.34 mmol) is totally consumed after 30 minutes of exposure to the photoelectrocatalytic system in the presence of Na2SO4 (0.1 mol·L-1) and with an applied bias potential of +1.0 V versus the Ag/AgCl reference electrode. Moreover, monitoring by direct infusion electrospray ionization mass spectrometry (ESI-MS) and SPME-GC/ MS (solid phase microextraction coupled with gas chromatography-mass spectrometry) reveals that apparently no degradation products are formed under these conditions. Hence, this study demonstrates that the photoelectrocatalytic system can be efficiently used to promote the complete degradation (and likely mineralization) of this hormone under these conditions.

A STUDY ON Ti ELECTRODE MODIFIED BY NICKEL ION BEANS

The reduction of H^+ on Ti electrodes which were treated by implanting nickel ions and thermodiffusing in vacuum has been studied.The calytic activity of the afore- mentioned electroes for H^+ reduction is much higher than that of the untreated Ti electrodes.