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 electroche...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.展开更多
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 p...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.展开更多
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 characterize...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.展开更多
Electrochemicaldegradation of2,4-dichlorophenol (2,4-DCP) in aqueous solutionwas investigated over Ti/SnO2-Sb anode. The factors influencing thedegradation rate, such as applied currentdensity (2-40 mA/cm2 ), pH ...Electrochemicaldegradation of2,4-dichlorophenol (2,4-DCP) in aqueous solutionwas investigated over Ti/SnO2-Sb anode. The factors influencing thedegradation rate, such as applied currentdensity (2-40 mA/cm2 ), pH (3-11) and initial concentration (5-200 mg/L)were evaluated. Thedegradation of2,4-DCP followed apparent pseudo first-order kinetics. Thedegradation ratio on Ti/SnO2 -Sb anode attained 〉 99.9% after 20 min of electrolysis at initial 5-200 mg/L concentrations at a constant currentdensity of 30 mA/cm2 with a 10 mmol/L sodium sulphate (Na2SO4 ) supporting electrolyte solution. The results showed that 2,4-DCP (100 mg/L)degradation and total organic carbon (TOC) removal ratio achieved 99.9% and 92.8%, respectively, at the optimal conditions after 30 min electrolysis. Under this condition, thedegradation rate constant (k) and thedegradation half-life (t1/2 )were 0.21 min1 and (2.8 ± 0.2) min, respectively. Mainly carboxylic acids (propanoic acid, maleic acid, propanedioic acid, acetic acid and oxalic acid) weredetected as intermediates. The energy efficiencies for2,4-DCPdegradation (5-200 mg/L)with Ti/SnO2-Sb anode ranged from 0.672 to 1.602 g/kWh. The Ti/SnO2-Sb anodewith a high activity to rapid organic oxidation could be employed todegrade chlorophenols, particularly2,4-DCP inwastewater.展开更多
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...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.展开更多
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 wi...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.展开更多
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(EC...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.展开更多
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)como...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).展开更多
Ti/SnO2–Sb electrode has a good effect on the removal of organic pollutants. But its short service life limits its large-scale application in industry. Electro-catalytic degradation performances and service life of t...Ti/SnO2–Sb electrode has a good effect on the removal of organic pollutants. But its short service life limits its large-scale application in industry. Electro-catalytic degradation performances and service life of the electrode can be significantly improved by doping rare earth(RE) ions into the oxide coating of Ti/SnO2–Sb electrode. Ti/SnO2–Sb electrodes doped with different RE elements(Ce, Dy, La, and Eu) were prepared by the thermal decomposition method at 550 ℃. Electro-catalytic degradation performances of electrodes doped with different RE elements were evaluated by linear sweep voltammetry(LSV) and Tafel curves. During the electrolysis,the conversion of p-nitrophenol was performed with these electrodes as anodes under galvanostatic control. The structures and morphologies of the surface coating of the electrodes were characterized by scanning electron microscope(SEM). The results demonstrate that the electro-catalytic degradation performances of Ti/SnO2–Sb electrodes are improved to different levels by doping different RE ions. Improved Ti/SnO2–Sb electrodes by the introduction of different RE have higher oxygen evolution potential, better electro-catalysis ability, better coverage,and longer electrode life.展开更多
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 electr...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.展开更多
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...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.展开更多
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(...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.展开更多
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...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.展开更多
The direct detection of clenbuterol(CL) in pig liver without any extraction separation at a pyrrole-DNA modified boron-doped diamond(BDD) electrode is reported. The pyrrole-DNA modified BDD electrode has a strong ...The direct detection of clenbuterol(CL) in pig liver without any extraction separation at a pyrrole-DNA modified boron-doped diamond(BDD) electrode is reported. The pyrrole-DNA modified BDD electrode has a strong electrocatalytic effect on the redox reaction of CL. One oxidization and two reduction peaks of CL appear at 340. 2, 299. 8 and 166. 6 mV( versus SCE), respectively. The pyrrole polymer alone cannot electrocatalyze the above reaction at a BDD electrode ; the electrocatalytic effect of a BDD electrode modified with DNA membrane is unsufficient for the analytical detection of CL; the replacement of boron-doped diamond by glass carbon makes the electrocatalytic reaction impossible ; the redox process is pH dependent. The influences of various experimental parameters on the pyrrole-DNA modified BDD electrode were investigated. A sensitive cyclic vohammetric response for CL was obtained in a linear range from 3.4 × 10^-6 to 5 × 10^ -4 mol/L with a detection limit of 8.5 × 10^-7 mol/L. A mean recovery of 102. 7% of CL in the pig liver sample solution and a reproducibility of 3.2% were obtained.展开更多
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, HPL...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.展开更多
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...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.展开更多
The electrochemical process of Ti-Ni alloy electrode was studied by using cyclic voltammetry. The hydrogen-absorbing electrode could be approximately regarded as a reversible hydrogen elecrede. The con- trolling steps...The electrochemical process of Ti-Ni alloy electrode was studied by using cyclic voltammetry. The hydrogen-absorbing electrode could be approximately regarded as a reversible hydrogen elecrede. The con- trolling steps of the discharging process varying with the anodic overpotentials were investigated and the effect ofelecrode constituent modification or Zr adulteation on the electrochemical behavior was also studied.展开更多
采用微波等离子体技术在CH4-H2-C2H6气体条件下制备了钛基掺硼金刚石薄膜。四点探针法测得薄膜电阻率在零掺杂时为1×1012Ω·cm,当反应气源中B/C上升为5×10-3时电阻率降至5×10-3Ω·cm。扫描电镜显示掺硼金刚石...采用微波等离子体技术在CH4-H2-C2H6气体条件下制备了钛基掺硼金刚石薄膜。四点探针法测得薄膜电阻率在零掺杂时为1×1012Ω·cm,当反应气源中B/C上升为5×10-3时电阻率降至5×10-3Ω·cm。扫描电镜显示掺硼金刚石具有完整晶型和致密结构。拉曼光谱观察到金刚石结构在掺杂前后发生明显改变。采用循环伏安测试了Ti/BDD电极的电化学参量,并与PbO2,Sn-Sb and PbO2-Er三种电极进行阳极氧化对-硝基酚的对比实验。结果表明,在Ti/BDD电极上,对-硝基酚的总有机碳去除率接近100%,远高于其它三种电极。展开更多
基金supported by the National Natural Science Foundation of China(21507104)the Fundamental Research Funds for the Central Universities of China
文摘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.
基金Project supported by the Institute of Environmental Engineering,Peking University and China Postdoctoral Science Foundation(No.2005037032)
文摘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.
基金the Fund of the Natural Science of Guangxi (0731015)
文摘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.
基金supported by the National Science Foundation for Innovative Research Group of China(No.51121003)the Specialized Research Fund for the Doctoral Program of Higher Education of China(No.20110003110023)the special fund of State Key Joint Laboratory of Environment Simulation and Pollution Control of China
文摘Electrochemicaldegradation of2,4-dichlorophenol (2,4-DCP) in aqueous solutionwas investigated over Ti/SnO2-Sb anode. The factors influencing thedegradation rate, such as applied currentdensity (2-40 mA/cm2 ), pH (3-11) and initial concentration (5-200 mg/L)were evaluated. Thedegradation of2,4-DCP followed apparent pseudo first-order kinetics. Thedegradation ratio on Ti/SnO2 -Sb anode attained 〉 99.9% after 20 min of electrolysis at initial 5-200 mg/L concentrations at a constant currentdensity of 30 mA/cm2 with a 10 mmol/L sodium sulphate (Na2SO4 ) supporting electrolyte solution. The results showed that 2,4-DCP (100 mg/L)degradation and total organic carbon (TOC) removal ratio achieved 99.9% and 92.8%, respectively, at the optimal conditions after 30 min electrolysis. Under this condition, thedegradation rate constant (k) and thedegradation half-life (t1/2 )were 0.21 min1 and (2.8 ± 0.2) min, respectively. Mainly carboxylic acids (propanoic acid, maleic acid, propanedioic acid, acetic acid and oxalic acid) weredetected as intermediates. The energy efficiencies for2,4-DCPdegradation (5-200 mg/L)with Ti/SnO2-Sb anode ranged from 0.672 to 1.602 g/kWh. The Ti/SnO2-Sb anodewith a high activity to rapid organic oxidation could be employed todegrade chlorophenols, particularly2,4-DCP inwastewater.
基金National Natural Science Foundation of China with Grant No.21905304Natural Science Foundation of Shandong Province(No.ZR2019BEM031)the Fundamental Research Funds for the Central Universities(Nos.18CX02158A and 19CX05001A).
文摘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.
文摘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.
基金Supported by the National Natural Science Foundation of China(21676200,21576208)the Program for Innovative Research Team in University of Ministry of Education of China(IRT-17R80)+2 种基金the Science and Technology Plans of Tianjin(17JCYBJC19800)111 Project(B12015)College Students' Innovation and Entrepreneurship Project(201510058083)
文摘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.
基金Thanks to the financial support from the Science and technology project of Shaanxi Province(2017ZDXM-GY-041).
文摘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).
基金financially supported by the National Natural Science Foundation of China (No. 51364024 and 51404124)Gansu Province Department of Education Fund (No. 2013A-029)the Foundation of State Key Laboratory of Gansu Advanced Nonferrous Metal Materials (Nos. SKL 1316 and SKL 1314)
文摘Ti/SnO2–Sb electrode has a good effect on the removal of organic pollutants. But its short service life limits its large-scale application in industry. Electro-catalytic degradation performances and service life of the electrode can be significantly improved by doping rare earth(RE) ions into the oxide coating of Ti/SnO2–Sb electrode. Ti/SnO2–Sb electrodes doped with different RE elements(Ce, Dy, La, and Eu) were prepared by the thermal decomposition method at 550 ℃. Electro-catalytic degradation performances of electrodes doped with different RE elements were evaluated by linear sweep voltammetry(LSV) and Tafel curves. During the electrolysis,the conversion of p-nitrophenol was performed with these electrodes as anodes under galvanostatic control. The structures and morphologies of the surface coating of the electrodes were characterized by scanning electron microscope(SEM). The results demonstrate that the electro-catalytic degradation performances of Ti/SnO2–Sb electrodes are improved to different levels by doping different RE ions. Improved Ti/SnO2–Sb electrodes by the introduction of different RE have higher oxygen evolution potential, better electro-catalysis ability, better coverage,and longer electrode life.
文摘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.
文摘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.
文摘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.
基金Supported by the Project of the Development and Reform Commission in Jilin Province,China(No.2009-633)the New Century Excellent Talents in Universities of China(No.NCET-06-0303)the National Natural Science Foundation of China(No.20873051)
文摘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.
基金Supported by the National Natural Science Foundation of China(Nos. 20435010, 20375012, 20205005 and 20475014).
文摘The direct detection of clenbuterol(CL) in pig liver without any extraction separation at a pyrrole-DNA modified boron-doped diamond(BDD) electrode is reported. The pyrrole-DNA modified BDD electrode has a strong electrocatalytic effect on the redox reaction of CL. One oxidization and two reduction peaks of CL appear at 340. 2, 299. 8 and 166. 6 mV( versus SCE), respectively. The pyrrole polymer alone cannot electrocatalyze the above reaction at a BDD electrode ; the electrocatalytic effect of a BDD electrode modified with DNA membrane is unsufficient for the analytical detection of CL; the replacement of boron-doped diamond by glass carbon makes the electrocatalytic reaction impossible ; the redox process is pH dependent. The influences of various experimental parameters on the pyrrole-DNA modified BDD electrode were investigated. A sensitive cyclic vohammetric response for CL was obtained in a linear range from 3.4 × 10^-6 to 5 × 10^ -4 mol/L with a detection limit of 8.5 × 10^-7 mol/L. A mean recovery of 102. 7% of CL in the pig liver sample solution and a reproducibility of 3.2% were obtained.
文摘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.
文摘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.
文摘The electrochemical process of Ti-Ni alloy electrode was studied by using cyclic voltammetry. The hydrogen-absorbing electrode could be approximately regarded as a reversible hydrogen elecrede. The con- trolling steps of the discharging process varying with the anodic overpotentials were investigated and the effect ofelecrode constituent modification or Zr adulteation on the electrochemical behavior was also studied.
文摘采用微波等离子体技术在CH4-H2-C2H6气体条件下制备了钛基掺硼金刚石薄膜。四点探针法测得薄膜电阻率在零掺杂时为1×1012Ω·cm,当反应气源中B/C上升为5×10-3时电阻率降至5×10-3Ω·cm。扫描电镜显示掺硼金刚石具有完整晶型和致密结构。拉曼光谱观察到金刚石结构在掺杂前后发生明显改变。采用循环伏安测试了Ti/BDD电极的电化学参量,并与PbO2,Sn-Sb and PbO2-Er三种电极进行阳极氧化对-硝基酚的对比实验。结果表明,在Ti/BDD电极上,对-硝基酚的总有机碳去除率接近100%,远高于其它三种电极。