Kinetic Study of the Electro-Catalytic Oxidation of Hydrazine on Cobalt Hydroxide Modified Glassy Carbon Electrode

Electrocatalytic oxidation of hydrazine was investigated on a cobalt hydroxide modified glassy carbon (CHM-GC) electrode in alkaline solution. The process of oxidation involved and its kinetics were established by using cyclic voltammetry, chronoamperometry techniques as well as steady state polarization measurements. In cyclic voltammetry (CV) studies, in the presence of hydrazine the peak current increase of the oxidation of cobalt hydroxide is followed by a decrease in the corresponding cathodic current. This indicates that hydrazine is oxidized on the redox mediator that is immobilized on the electrode surface via an electrocatalytic mechanism. A mechanism based on the electrochemical generation of Co(IV) active sites and their subsequent consumption by the hydrazine in question was also investigated.     

Electrochemical Oxidation of Chlorimuron-ethyl on Ti/SnO2-Sb2O5/PbO2 Anode for Waste Water Treatment

<正>The electrochemical oxidation of chlorimuron-ethyl on Ti/SnO_2-Sb_2O_5/PbO_2 electrode was studied by cyclic voltammetry. The electrochemical behaviour of the electrode in a sodium sulfate solution and in the mixture solution of sodium sulfate and chlorimuron-ethyl was studied.The experimental results of cyclic voltammetry show that the acidic medium was suitable for the efficient electrochemical oxidation of chlorimuron-ethyl.Some electro-generated reagent was formed in the electrolysis process and chlorimuron-ethyl could be oxidized by the electro-generated reagent.A Ti/SnO_2-Sb_2O_5/PbO_2 electrode was used as the anode and the electrolysis experiment was carried out under the optimized conditions.The electrolysis process was monitored by UV-Vis spectrometry and high performance liquid chromatography(HPLC),and the chemical oxygen demand(COD) was determined by the potassium dichromate method.The mechanism of chlorimuron-ethyl to be oxided was studied primarily by the cyclic voltammetry and UV-Vis spectrometry.The results of electrolysis experiment demonstrate the possibility of the electrode to be used as an anode for the electrochemical treatment of chlorimuron-ethyl contained in waste water.     

方波伏安法测定新型修饰多壁碳纳米管糊电极对肼的电催化氧化(英文)

The application of p-aminophenol as a suitable mediator, as a sensitive and selective voltammetric sensor for the determination of hydrazine using square wave voltammetric method were described. The modified multiwall carbon nanotubes paste electrode exhibited a good electrocatalytic activity for the oxidation of hydrazine at pH = 7.0. The catalytic oxidation peak currents showed a linear dependence of the peaks current to the hydrazine concentrations in the range of 0.5–175 μmol/L with a correlation coefficient of 0.9975. The detection limit (S/N = 3) was estimated to be 0.3 μmol/L of hydrazine. The relative standard deviations for 0.7 and 5.0 μmol/L hydrazine were 1.7 and 1.1%, respectively. The modified electrode showed good sensitivity and selectivity. The diffusion coefficient (D = 9.5 × 10–4 cm2/s) and the kinetic parameters such as the electron transfer coefficient (α = 0.7) of hydrazine at the surface of the modified electrode were determined using electrochemical approaches. The electrode was successfully applied for the determination of hydrazine in real samples with satisfactory results.     

Plastic supported platinum modified nickel electrode and its high electrocatalytic activity for sodium borohydride electrooxidation

A novel plastic/multi-walled carbon nanotube(MWNTs)-nickel(Ni)-platinum(Pt) electrode(PMNP) is prepared by chemical-reducing Pt onto the surface of Ni film covered plastic/MWNTs(PM) substrate. The MWNTs are adhered by a piece of commercial double faced adhesive tape on the surface of plastic paper and the Ni film is prepared by a simple electrodeposition method. The morphology and phase structure of the PMNP electrode are characterized by scanning electron microscopy,transmission electron microscope and X-ray diffractometer. The catalytic activity of the PMNP electrode for Na BH4 electrooxidation is investigated by means of cyclic voltammetry and chronoamperometry. The catalyst combines tightly with the plastic paper and exhibits a good stability. MWNTs serve as both conductive material and hydrogen storage material and the Ni film and Pt are employed as electrochemical catalysts. The PMNP electrode exhibits a high electrocatalytic performance and the oxidation current density reaches to 10.76 A/(mg·cm) in 0.1 mol/dm3 Na BH4at0 V,which is much higher than those in the previous reports. The using of waste plastic reduces the discarding of white pollution and consumption of metal resources.     

A facile preparation and electrochemical properties of nickel based compound-graphene sheet composites for supercapacitors

Composites of a nickel based compound incorporated with graphene sheets(NiBC-GS) are prepared by a simple flocculation,using hydrazine hydrate as flocculant and reductant,from a homogeneous intermixture of nickel dichloride and graphene oxide dispersed in N,N-dimethylformamide.Morphology,microstructure and thermal stability of the obtained products were characterized by field-emission scanning electron microscopy,X-ray diffraction and thermal gravimetric analysis.Furthermore,the electrochemical properties of NiBC-GS,as electrode materials for supercapacitors,were studied by cyclic voUammetry and galvanostatic charge/discharge in 2 mol L~(-1) KOH solution.It was determined that for NiBC-GS annealed at 250 ℃.a high specific capacitance of 2394 Fg~(-1) was achieved at a current density of 1 Ag~(-1),with 78%of the value(i.e.,1864 Fg~(-1)) retained after 5000 times of repeated galvanostatic charge/discharge cycling.The high specific capacitance and available charge/discharge stability indicate the synthesized NiBC-GS250 composite is a good candidate as a novel electrode material for supercapacitors.     

以方沸石负载Ni(Ⅱ)催化剂修饰的电极电氧化甲醇(英文)

There is a high overvoltage in the oxidation of methanol in fuel cells,and so modified electrodes are used to decrease it.A modified electrode that used Ni(II) loaded analcime zeolite to catalyze the electrooxidation of methanol in alkaline solution was proposed.Analcime zeolite was synthesized by hydrothermal synthesis,and Ni(II) ions were incorporated into the analcime structure,which was then mixed with carbon paste to prepare modified electrode.The electrocatalytic oxidation of methanol on the surface of the modified electrode in alkaline solution was investigated by cyclic voltammetry and chronoamperometry.The effects of the scan rate of the potential,concentration of methanol,and amount of zeolite were investigated.The rate constant for the catalytic reaction of methanol was 6 × 103 cm3 mol-1 s-1 from measurements using chronoamperometry.The proposed electrode significantly improved the electron transfer rate and decreased the overpotential for methanol oxidation.     

A Novel Amperometric Nitric Oxide Sensor Based on Polythionine / Nation Modified Glassy Carbon Electrode

A novel amperometric sensor for the determination of nitric oxide was developed by coating polythionine / nafion on a glassy carbon electrode. This sensor exhibited a great enhancement to the oxidation of nitric oxide. The oxidation peak currents were linear to the concentration of nitric oxide over the wide range from 3.6×10-7 to 6.8×10-5 mol.L-1, and the detection limit was 7.2×10-8 mol.L-1. Experimental results showed that this nitric oxide sensor possessed excellent selectivity and longer stability. NO releasing from rat kidney was monitored by this sensor.     

在3,4-二羟基肉桂酸介质中以多壁碳纳米管为传感器电催化检测L-半胱氨酸(英文)

A highly sensitive electrochemical sensor was prepared for the determination of L-cysteine using a modified multiwall carbon nanotubes paste electrode in the presence of 3,4-dihydroxycinnamic acid(3,4-DHCA) as a mediator, based on an electrocatalytic process. The results indicate that the electrode is electrocatalytically efficient for the oxidation of L-cysteine in the presence of 3,4-DHCA. The interaction between the mediator and L-cysteine can be used for its sensitive and selective determination. Using chronoamperometry, the catalytic reaction rate constant was calculated to be 2.37 × 102 mol–1 L s–1. The catalytic peak current was linearly dependent on the L-cysteine concentration in the range of 0.4–115 μmol/L. The detection limit obtained by linear sweep voltammetry was 0.25 μmol/L. Finally, the modified electrode was examined as a selective, simple, and precise new electrochemical sensor for the determination of L-cysteine in real samples.     

Hydrogen evolution kinetics on Ni cathodes modified by spontaneous deposition of Ag or Cu

Nickel modification by spontaneous deposition of transition metals such as Ag and Cu is shown as an economic and simple alternative for the activation of hydrogen evolution reaction(HER) on cathodes in alkaline media. The kinetics of HER is studied on Ni/Ag and Ni/Cu catalysts by cyclic voltammetry and electrochemical impedance spectroscopy(EIS) using a rotating disk electrode(RDE). Freshly synthesized catalysts, as well as catalysts subjected to a short chronoamperometric ageing procedure, are analyzed and the kinetic and thermodynamic parameters of the HER are obtained. The nickel surface modified with transition metals with an outer shell electronic configuration [xd~(10)(x+1)s~1], such as Cu(3d~(10)4s~1)and Ag(4d~(10)5s~1), shows an improved activity for the HER compared to bare nickel. Furthermore, the Ni/Cu catalyst presents a decreased onset potential. The hydrogen evolution rate, measured as current density at –1.5 V(vs. SCE), is similar on Ni/Cu and Ni/Ag electrodes.     

Preparation, Electrochemical Behavior and Electrocatalytic Activity of a Copper Hexacyanoferrate Modified Ceramic Carbon Electrode

A copper hexacyanoferrate modified ceramic carbon electrode （CuHCF/CCE） had been prepared by two-step sol-gel technique and characterized using electrochemical methods. The resulting modified electrode showed a pair of well-defined surface waves in the potential range of 0.40 to 1.0 V with the formal potential of 0.682 V （vs. SCE） in 0.050 mol·dm^-3 HOAc-NaOAc buffer containing 0.30 mol·dm^-3 KCl. The charge transfer coefficient （a） and charge transfer rate constant （ks） for the modified electrode were calculated. The electrocatalytic activity of this modified electrode to hydrazine was also investigated, and chronoamperometry was exploited to conveniently determine the diffusion coefficient （D） of hydrazine in solution and the catalytic rate constant （kcat）. Finally, hydrazine was determined with amperometry using the resulting modified electrode. The calibration plot for hydrazine determination was linear in 3.0 × 10^-6--7.5 × 10^-4 mol·dm^-3 with the detection limit of 8.0 × 10^-7 molodm^-3. This modified electrode had some advantages over the modified film electrodes constructed by the conventional methods, such as renewable surface, good long-term stability, excellent catalytic activity and short response time to hydrazine.     

Nanoporous Pt Catalyst Modified by Sn Electrodeposition for Electrochemical Oxidation of Formaldehyde

A nanoporous Pt particles‐modified Ti (nanoPt/Ti) electrode was prepared through a simple hydrothermal method using aqueous H₂PtCl₆ as a precursor and formaldehyde as a reduction agent. The nanoPt/Ti electrode was then modified with limited amounts of tin particles generated by cyclic potential scans in the range of ?0.20 to 0.50 V in a 0.01 mol·L^?1 SnCl₂ solution, to synthesize a Sn‐modified nanoporous Pt catalyst (Sn/nanoPt/Ti). Electroactivity of the nanoPt/Ti and Sn/nanoPt/Ti electrodes towards formaldehyde oxidation in a 0.5 mol·L^?1 H₂SO₄ solution was evaluated by cyclic voltammetry and chronoamperometry. Electrooxidation of formaldehyde on the nanoPt/Ti electrode takes place at a potential of 0.45 V and then presents high anodic current densities due to the large real surface area of the nanoPt/Ti electrode. The formaldehyde oxidation rate is dramatically increased on the Sn/nanoPt/Ti electrode at the most negative potentials, where anodic formaldehyde oxidation is completely suppressed on the nanoPt/Ti electrode. Chronoamperogramms (CA) of the Sn/nanoPt/Ti electrode display stable and large quasi‐steady state current densities at more negative potential steps. Amperometric data obtained at a potential step of 100 mV show a linear dependence of the current density for formaldehyde oxidation upon formaldehyde concentration in the range of 0.003 to 0.1 mol·L^?1 with a sensitivity of 59.29 mA·cm^?2 (mol·L^?1)^?1. A detection limit of 0.506 mmol·L^?1 formaldehyde was found. The superior electroactivity of the Sn/nanoPt/Ti electrode for formaldehyde oxidation can be illustrated by a so‐called bifunctional mechanism which is involved in the oxidation of poisoning adsorbed CO species via the surface reaction with OH adsorbed on neighboring Sn sites.     

A novel titanium-supported nickel electrocatalyst for cyclohexanol oxidation in alkaline solutions

A novel titanium-supported nickel electrode (Ni/Ti) is fabricated by a simple hydrothermal process using hydrazine hydrate as a reduction agent. Its electrocatalytic activity towards cyclohexanol oxidation has been investigated by cyclic voltammetry (CV), chronoamperometry (CA), quasi-steady state polarization and electrochemical impedance spectroscopy (EIS). Effects of various parameters such as potential scan rate and cyclohexanol concentration on the electro-oxidation of cyclohexanol are investigated. Results show that the Ni/Ti electrode behaves as an efficient catalyst for the electro-oxidation of cyclohexanol in basic media and its electrocatalytic activity towards cyclohexanol oxidation is higher than a nickel oxyhydroxide modified nickel electrode (NOMN). It is confirmed that during the anodic potential sweep the electro-oxidation of cyclohexanol follows the formation of NiOOH on the electrode surface and is then catalysed by NiOOH. The rate-determining step for cyclohexanol oxidation is the reaction between the high oxidation state nickel (Ni³⁺) and the adsorbed cyclohexanol on the surface of the Ni/Ti.     

新型的钛基Ni-Sn/Ti电极的制备及对甲醇氧化反应的电催化活性

利用电热法,一步制备出新型的钛基Ni-Sn/Ti电极(Ni8Sn/Ti, Ni7Sn3/Ti 和 Ni/Ti)。扫描电镜（SEM）图像表明,催化剂以片状的纳米颗粒形式沉积于钛基体上。利用电化学伏安技术、电位阶跃法和电化学交流阻抗谱（EIS）,研究了这些电极在1mol.L�1NaOH溶液中对甲醇氧化反应的电催化活性。研究表明,与Ni7Sn3/Ti,Ni/Ti以及多晶镍电极相比,Ni8Sn/Ti电极对甲醇氧化反应表现出更高的阳极氧化电流和更低的起始电位。EIS分析表明,在本文所考察的阳极电位和甲醇浓度下,Ni8Sn/Ti电极对甲醇氧化反应显示出极低的电荷传递电阻。结果表明,这种新型的钛基Ni8Sn/Ti电极对甲醇氧化反应具有极高的电催化活性。     

多孔枝晶镍铜合金的制备及其电催化析氢、肼氧化性能

以镍网(NM)为基体,采用氢气泡模板法合成了独立分相金属Ni、Cu为主晶相、具有四级复合微纳结构的镍铜合金电催化剂(NiCu/NM)。在电催化析氢(HER)及肼氧化(HzOR)反应中,NiCu/NM表现出优良的催化活性,在1.0 mol·L^-1KOH(含0.5 mol·L^-1N2H4·H2O)溶液中,电流密度为10 mA·cm^-2时,其需要的HER及HzOR过电势分别为104和41 mV;在双电极体系中,电流密度为100 mA·cm^-2时,NiCu/NM的分解槽压仅为0.536 V,远低于全水分解过程所需的1.921 V,大大提高了电池的产氢效率。无论三电极体系还是双电极体系,NiCu/NM均表现出优异的催化活性及稳定性。分析认为,镍铜合金薄膜的多级复合结构使其展现出增大了近14倍的电化学活性面积(ECSA),为电催化反应提供了大量催化活性位点,也为电极表面的电荷传输、物质传递提供了充足的通道;Cu的掺入提高了材料的本征HER活性,两者协同促进了电催化活性的提升,其中NiCu/NM的结构优势对其优良的催化性能起主导作用。     

镍/生物质衍生氮掺杂多孔碳纳米复合材料的制备及对甲醇氧化反应的电催化

以Ni （Ac）₂·4H₂O和生物质材料丝瓜络为原料,通过先浸渍后热解的方法制备了低成本的镍纳米颗粒/丝瓜络衍生氮掺杂多孔碳纳米复合材料（Ni/T-dNPCN）。研究复合材料对甲醇的电催化性能,并讨论热解温度对复合材料结构和性能的影响。结果表明,Ni/T-dNPCN修饰玻碳电极（GCE）在碱性条件下对甲醇氧化反应（MOR）具有良好的电催化活性。其中,800℃煅烧得到的Ni/T-dNPCN₈₀₀/GCE对1 mol·L^-1甲醇具有最低的起始电位（0.344 V （vs Ag/AgCl））、最高的催化电流密度（质量活性：1 902 mA·mg_Ni^-1;比活性：1.61 mA·cm^-2）和最快的动力学反应过程（Tafel斜率：50.23 mV·dec^-1）,其催化活性约为商业化Pt/C/GCE的3.92倍。且计时电流测试表明,Ni/T-dNPCN₈₀₀/GCE具有良好的稳定性。     

不同Ni含量NiCoAl LDH的制备及CNT/Ni0.3CoAl LDH材料的电化学性能

利用水热法一步合成了不同镍、钴元素比例的镍钴铝层状氢氧化物(NiCoAl LDH),并探究了不同Ni元素含量的NiCoAl LDH的电化学性能,在Ni和Co的物质的量之比为3:7时,Ni_(0.3)CoAl LDH具有最优电化学性能。晶格中部分Ni元素被Co元素代替有利于降低氧化电势,提高材料的化学可逆性。然后通过水热法将CNT与Ni_(0.3)CoAl LDH复合,CNT的复合提高了材料的导电性。CNT/Ni_(0.3)CoAl LDH在1 A·g~(-1)的电流密度下比容量为1 332 F·g~(-1),电流密度为10 A·g~(-1)时比容量保持率为60.4%。在5A·g~(-1)的电流密度下循环3 000圈容量保持率为87.6%。     

Hydrothermal Synthesis of Titanium‐Supported Nickel Nanoflakes for Electrochemical Oxidation of Glucose

Titanium‐supported nanoscale flaky nickel electrode (nanoNi/Ti) was prepared by a hydrothermal process using hydrazine hydrate as a reduction agent. Its electrocatalytic activity as an electrocatalyst for the electrooxidation of glucose was evaluated in alkaline solutions using cyclic voltammetry (CV), chronoamperometric responses (CA) and electrochemical impedance spectra (EIS). The nanoNi/Ti electrode exhibits significantly high current density of glucose oxidation. A high catalytic rate constant of 1.67×10⁶ cm³ mol^?1 s^?1 was calculated from amperometric responses on the nanoNi/Ti electrode. Low charge transfer resistances on the nanoNi/Ti in 0.5 M NaOH containing various concentrations of glucose were obtained according to the analysis for EIS. Furthermore, amperometric data show a linear dependence of the current density for glucose oxidation upon glucose concentration in the range of 0.05–0.6 mM with a sensitivity of 7.32 mA cm^?2 mM^?1. A detection limit of 0.0012 mM (1.2 μM) M glucose was found. Results show that the prepared nanoNi/Ti electrode presents high electrocatalytic activity for glucose oxidation.     

Ni(II)-baicalein complex modified multi-wall carbon nanotube paste electrode toward electrocatalytic oxidation of hydrazine

A modified electrode Ni(II)-BA-MWCNT-PE has been fabricated by electrodepositing nickel(II)-baicalein [Ni(II)-BA] complex on the surface of multi-wall carbon nanotube paste electrode (MWCNT-PE) in alkaline solution. The Ni(II)-BA-MWCNT-PE exhibits the characteristic of improved reversibility and enhanced current responses of the Ni(III)/Ni(II) couple compared with Ni(II)-BA-CPE. It also shows good electrocatalytic activity toward the oxidation of hydrazine. Kinetic parameters such as the electron transfer coefficient α, rate constant k_s of the electrode reaction, the diffusion coefficient D of hydrazine and the catalytic rate constant k_cat of the catalytic reaction are determined. Moreover, the catalytic currents present linear dependence on the concentration of hydrazine from 2.5 μM to 0.2 mM by amperometry. The detection limit and sensitivity are 0.8 μM and 69.9 μA mM⁻¹, respectively. The modified electrode for hydrazine determination is of the property of simple preparation, good stability, fast response and high sensitivity.     

聚3,4-乙烯二氧噻吩/石墨烯/钛电极的制备及其电化学性能

采用直流电弧等离子体喷射化学气相沉积法把石墨烯生长在钛(Ti)基底上,并采用电化学氧化聚合法在石墨烯表面沉积聚3,4-乙烯二氧噻吩(PEDOT),由此构造PEDOT/石墨烯/Ti电极。形貌及结构表征结果表明,电聚合200圈以上的PEDOT呈线状或泡沫状且均匀分布于石墨烯表面。电化学性能测试结果表明,PEDOT/石墨烯/Ti电极具有高的比电容和库伦效率;其电聚合次数为400圈时,与PEDOT/Ti电极相比,比电容提高42倍,其最大电势窗口可达1.4 V,而在0～1.2 V电势窗口范围内,扫描速度为10 mV·s-1时,比电容可达到269.6 mF·cm-2。     

Voltammetric Study and Detection of Methane on Nickel Hydroxide–Modified Nickel Electrode

Abstract

The nickel hydroxide–modified nickel (NMN) electrode was prepared by cyclic voltammetry. The modified electrode exhibited better catalytic effect toward electrochemical oxidation of methane in 1.0 mol · L^?1 NaOH solution. The catalytic activation of nickel hydroxide on the nickel electrode surface was investigated in different supporting electrolyte solutions by the cyclic voltammetry method in detail, and the related electrochemical oxidation of methane at the NMN electrode was first proposed by amperometric i‐t curve method under the experiment conditions. The results indicated that in the 1.0 mol · L^?1 NaOH solution, the anodic peak current increased with the increased concentration of methane.