Characterization of the Reduction of Oxygen at Anthraquinone-Modified Glassy Carbon and Highly Oriented Pyrolytic Graphite Electrodes

1-(N-Boc-aminomethyl)-4-(aminomethyl)benzene, bearing a protected amine group, was electrochemically grafted to glassy carbon and edge plane and basal plane highly oriented pyrolytic graphite electrodes by the oxidation of the corresponding linker. Following the removal of tert-butyloxycarbonyl protecting group, anthraquinone-2-carboxylic acid was coupled to the amine-terminated linker using solid-phase synthesis. The surface coverage of the immobilized anthraquinone redox centers was investigated by cyclic voltammetry and found to be the highest at edge plane and the lowest at the basal plane electrodes. The electrocatalytic activity of the anthraquinone-modified electrodes toward oxygen reduction was explored by cyclic voltammetry, chronoamperometry, and chronocoulometry at the unmodified and modified graphite electrodes. The immobilized anthraquinone was shown to catalyze the reduction of oxygen to hydrogen peroxide and the number of electrons transferred was two for all modified electrodes.     

Nickel Coated Graphite Microparticle Based Electrodes for Carbon Dioxide Reduction in MonoethanolamineMedium

A composite electrode that contains home-made nickel coated carbon micro-particles as active materials and epoxy binder has been prepared. The surface morphology, elemental composition and size distribution of microparticles were investigated using SEM, EDS, AAS, micro Raman spectroscopy and appropriate seizer apparatus. The prepared micro-particles appeared monodispers with 33 μm most numerous particle size diameter and with 10.1 w/w % Ni content. Conventional electrochemical methods like impedance spectroscopy and voltammetry as well as scanning electrochemical microscopy (SECM) were used for investigation the properties of the composite electrodes. It has been proved that the electrode can be well used for electro-catalytic reduction of CO₂ directly in aqueous mono-ethanol amine (MEA) solution that frequently are applied for capturing it from power plant flue gases. SECM measurements showed that presence of dissolved CO₂ hinders the hydrogen evolution in aqueous MEA solution.     

MOF-Conductive Polymer Composite Film as Electrocatalyst for Oxygen Reduction in Acidic Media

A metal-organic framework（MOF）-conductive polymer composite film was constructed from PCN-222（Fe） nanoparticles and PEDOT:PSS solution by simple drop-casting approach. The composite film was tested as an electrocatalytic device for oxygen reduction reaction（ORR）. The combination of PCN-222（Fe） MOF particles and conductive PEDOT matrix facilitates electron transfer in the composite material and improves the ORR performance of PCN-222（Fe）. Levich plot and H₂O₂ quantification ...     

Edge Plane Pyrolytic Graphite Electrodes for Halide Detection in Aqueous Solutions

The behavior of chloride, bromide and iodide at edge plane pyrolytic graphite electrodes has been explored in aqueous acid solutions. The voltammetric response in each case has been compared with that of basal plane pyrolytic graphite, glassy carbon and boron‐doped diamond. The electrochemical oxidation of chloride is found to only occur on boron‐doped diamond while the electrochemical reversibility for the oxidation of bromide on edge plane pyrolytic graphite is similar to that seen at glassy carbon whilst being superior to basal plane pyrolytic graphite and boron‐doped diamond. In the case of iodide oxidation, edge plane and basal plane pyrolytic graphite and glassy carbon display similar electrode kinetics but are all superior to boron‐doped diamond. The analytical possibilities were examined using the edge plane pyrolytic graphite electrode for both iodide and bromine where is was found that, based on cyclic voltammetry, detection limits in the order of 10^?6 M are possible.     

Electrocatalysis of Nitrate Reduction at Copper‐Nickel Alloy Electrodes in Acidic Media

The cathodic reduction of NO in 1.0 M HClO₄ is investigated by voltammetry at pure Ni and Cu electrodes, and three Cu‐Ni alloy electrodes of varying composition, all configured as rotated disks. Voltammetric data obtained using these hydrodynamic electrodes demonstrate significantly improved activity for NO reduction at Cu‐Ni alloy electrodes as compared to the pure Ni and Cu electrodes. This observation is explained on the basis of the synergistic benefit of different surface sites for adsorption of H‐atoms, generated by cathodic discharge of H⁺ at Ni‐sites, and adsorption of NO at Cu‐sites on these binary alloy electrodes. Koutecky‐Levich plots indicate that the cathodic response for NO at a Cu₇₅Ni₂₅ electrode corresponds to an 8‐electron reduction, which is consistent with production of NH₃. In comparison, the cathodic response at Cu₅₀Ni₅₀ and Cu₂₅Ni₇₅ electrodes corresponds to a 6‐electron reduction, which is consistent with production of NH₂OH. Flow injection data obtained using Cu₅₀Ni₅₀ and Cu₂₅Ni₇₅ electrodes with 100‐μL injections exhibit detection limits for NO of ca. 0.95 μM (ca. 95 pmol) and 0.60 μM (ca. 60 pmol), respectively.     

酞菁钴及其衍生物修饰电极对分子氧的电催化还原

在玻碳电极上采用吸附法制备了四溴代酞菁钴(CoPcBr₄)、酞菁钴(CoPc)和四-α-(2,2,4-三甲基-3-戊氧基)酞菁钴(CoPc(OC₈H₁₇)₄)修饰电极。利用循环伏安法和线性扫描伏安法研究了修饰电极在酸性介质中对分子氧的电催化还原,比较了不同取代基的酞菁钴对电催化性质的影响。结果表明,它们对分子氧还原均具有良好的电催化活性,其中酞菁钴和四-α-(2,2,4-三甲基-3-戊氧基)酞菁钴对O₂的催化是2电子还原生成H₂O₂,与裸电极相比,O₂的还原峰电位分别向正方向移动了0.33和0.48 V。而四溴代酞菁钴修饰电极在-0.1和-0.7 V附近产生的2个还原峰,说明它催化O₂到H₂O₂的还原以后还可以促进H₂O₂继续还原到H₂O,最终实现O₂的4电子还原。     

Oxygen Reduction on Amalgamated Platinum Electrodes Coated with Monolayers of Cetyl Alcohol and Stearic Acid

Oxygen reduction on an amalgamated platinum electrode with a monolayer of cetyl alcohol or stearic acid is studied. It is shown that the process proceeds inside the monolayer, most probably, at a certain distance from the metal; an electron is transferred to the reagent by the superexchange mechanism. The process characteristics depend on competition between several factors: the electron transfer distance, the potential drop between the electrode and the reagent in a given site in the monolayer, and the hydrogen ion concentration distribution across the film. The penetration of H⁺ inside the film appears to be responsive to the monolayer structure.     

石墨炉原子吸收法中热解涂层石墨管在无标准分析法测定环境样品中铬的应用

本文探讨了热解涂层石墨管测定铬的最佳实验条件,研究了各种酸和干扰物质的基体效应,提出用浓氨水为基体改进剂克服高氯酸的干扰。比较了各原子化温度时的理论和实验特征量。使热解涂层石墨管有可能用于无标准分析法测定各种环境样品中的铬。     

酸性喷淋石墨屑电极氧还原为过氧化氢研究

酸性喷淋石墨屑电极氧还原为过氧化氢研究①陆兆锷＊张关永钟天耕方国女（华东理工大学化学系,上海２００２３７）石墨在碱液中对氧还原为过氧化氢根ＨＯ－２有良好的电催化作用．碱液喷淋的石墨屑床阴极已应用于氧还原制备ＨＯ－２［１～５］．Ｓａｂｕｐｏｖ［６］研究...     

Electrocatalytic Reduction of Oxygen at Glassy Carbon Electrodes Coated with Diazonium‐derived Porphyrin/Metalloporphyrin Films

In this study, the influence of the film structure was investigated on the electrocatalytic oxygen reduction at GC electrodes covered with porphyrin and metalloporphyrin rings via the diazonium modification method. For that purpose, primarily, tetraphenylporphyrin (TPP) films on GC electrode surfaces were prepared by electroreduction of in situ generated diazonium salts of 5‐(4‐aminophenyl)‐10,15,20‐triphenylporphyrin (APP) and 5,10,15,20‐tetrakis(4‐aminophenyl)porphyrin (TAPP) molecules. Next, the formation of metalloporphyrin films on the modified surfaces was accomplished through the complexation reactions of surface porphyrin rings with metal ions in the salt solutions containing Mn(II), Fe(III) and Co(II) ions. The resulting porphyrin and metalloporphyrin layers were identified with XPS and ICP‐MS. The electrochemical barrier properties of the films on GC surfaces were examined by cyclic voltammetry in K₃Fe(CN)₆ aqueous solution. The electrocatalytic abilities of the resulting films were also investigated for the oxygen electrochemical reduction by employing cyclic voltammetry in PBS solutions saturated with oxygen. The results showed that the oxygen reduction potentials on modified GC electrodes were shifted to less negative potentials compared to that of bare GC electrode. Also, it was obtained that the oxygen reduction reaction was more effective on the GC electrodes modified with TPP rings by using TAPP molecules than those prepared by using APP molecules.     

Direct Electrochemistry of Hemoglobin in Layer-by-layer {PDDA/Hb}_n Films Assembled on Pyrolytic Graphite Electrodes

The principle of alternate adsorption can be used to design and control specific molecular architectures1. Protein-polyion layer-by-layer assembly opens a possibility of organizing proteins with specific molecular architectural plan1 and studying redox proteins with electrochemical methods2. Recently, we reported electrochemistry of layer-by-layer {PSS/Mb}n films grown on PG electrodes1. In this work, layer-by-layer {PDDA/Hb}n films were fabricated on PG electrodes. Electrochemistry and …     

Enhanced Electron Transfer for Hemoglobin in 2C_(12)N~ PVS-Composite Films Modified on Pyrolytic Graphite Electrodes

Some water-insoluble surfactants can be introduced onto surface of electrodes and formordered bilayer structure by self-assembling* The films provide a biomembrane-likemicroenvironment which is favorable to electron transfer for some redox proteins onelectrodesl. Surfactant-polymer multibilayer composite films show similarbiomembrane-mimetic bilayer structure to surfactant films alone, but demonstrateadvantages over the latter for their physically stronger solidity and stability because ofintr…     

Highly Active Electrocatalyst Derived from ZIF-8 Decorated with Iron(III) and Cobalt(III) Porphyrin Toward Efficient Oxygen Reduction in Both Alkaline and Acidic Media

Zeolite imidazole frameworks 8(ZIF-8) and modified ones after pyrolysis are highly promising toward oxygen reduction reaction(ORR). Especially, the compositional modification of ZIF-8 is crucial to the enhancement of ORR performance, yet limited to the substitution of skeletal Zn(II) with other cations or simple physical adsorption of cations. Herein, we report the decoration of ZIF-8 with ORR active hemin(FeP) and Co(III) protoporphyrin(CoP) via the coordination between the peripheral carboxylic group of FeP and CoP with skeletal Zn(II). This allows well control over the quantity of loaded FeP and CoP, critical to the synthesis of advanced electrocatalysts. Subsequent pyrolysis of FeP and CoP co-decorated ZIF-8 leads to highly active ORR electrocatalysts with a half-wave potential(E_1/2) of 0. 913 V(vs. RHE) in 0.1 mol/L KOH aq. and an E_1/2 of 0.803 V(vs. RHE) in 0.1 mol/L HClO₄ aq. Moreover, our electrocatalyst shows much more improved and comparable durability in alkaline and acidic media, respectively, during 3000 cycles of cyclic voltammetry(CV) scanning relative to commercial Pt/C.     

钯基氧还原反应电极的构筑及其在水处理领域的研究进展

发展氧气还原反应(ORR)的二电子高效电催化剂一直是燃料电池领域的研究热点,但针对具有二电子还原特征且可应用于水处理领域电极材料的研究还处在起步阶段。本综述介绍了近年来二电子还原特征的贵金属电极材料及其在电催化处理水中污染物的研究进展。在Fe~(2+)存在下,Pd基电极材料催化氧气还原合成H_2O_2,间接催化氧化水中有机污染物,实现有机物的矿化降解和水质的净化;Pd基电极催化还原水中有机污染物、无机盐等,将其转化为低毒性、易处理产物并彻底去除;Pd基催化电极的高效电子传导性能增强了水中重金属离子的氧化/还原转化,实现重金属去除。本综述展望了纳米电极材料在水处理应用的机遇与发展方向。     

Bioelectrocatalytic Reduction of Oxygen in the Presence of Laccase Adsorbed on Carbon Electrodes

The kinetics of electroreduction of molecular oxygen on isotropic pyrocarbon with adsorbed laccase or a laccase–Nafion composite is studied. Kinetic parameters thus obtained are compared with those determined previously for electrodes of carbon black with adsorbed laccase. The closeness of kinetic parameters of the reaction of bioelectrocatalytic reduction of oxygen by laccase adsorbed on smooth (pyrocarbon) and disperse (carbon black) carbon materials led to a refined reaction mechanism. The slow stage of the reaction of bioelectrocatalytic reduction of oxygen is a synchronous transfer of two first electrons onto the oxygen molecule, similar to the mechanism of enzymatic catalysis by laccase.     

恒电位氧化改性石墨毡及其氧还原电极的电化学性能

分别采用循环伏安改性法和恒电位氧化法对石墨毡进行改性处理,并采用循环伏安法对其电化学性能进行研究,实验结果表明,恒电位氧化改性较循环伏安改性的石墨毡有较好的氧还原活性。通过XRD、FTIR、接触角和CV针对恒电位氧化处理石墨毡进行了进一步的测试。测试结果显示,随恒电位氧化时间的增加,石墨毡表面亲水性含氧官能团增加,润湿性增强。恒电位氧化改性处理25 min的石墨毡氧还原峰电位及电流密度分别为~-0.43 V和~0.003 4 mA·cm^-2,显示出很好的电化学催化性能。基于以上结果,恒电位氧化法改性处理能够极大提高石墨毡的氧阴极活性。     

氧在振动球磨石墨上阴极还原动力学的研究

石墨具有很好的导电性和化学稳定性而被广泛地用作电极材料,细粉状石墨对氧的电化学还原表现出相当好的催化活性^[1],氧在碳上的还原机理已经有许多人进行过研究[2,3],本工作中利用在真空条件下高速振动制备了超细振动球磨石墨,并运用旋转盘环电极技术研究了氧在这种石墨上的电化学还原机理。     

Oxygen Reduction Reaction on a Rotating Ag/GC Disk Electrode in Acidic Solution

Finding an appropriate mechanism of oxygen reduction reaction, without having kinetic parameters and intermediate species at hand, is an impossible task. In view of the fact that this reaction is one of the important reactions, it was tried to overcome this problem through computing the kinetic parameters by means of Ag/GC rotating disc electrode in an acidic solution. Using this electrode, two values were obtained for electron transfer coefficient and reaction order was calculated through relative equations. Based on this information, an ECE (electrochemical chemical electrochemical) mechanism has been proposed.     

Inhibition of Reduction Current of Oxygen by Cysteine and Glutathione at Smooth Platinum Electrodes

Abstract

The reduction of molecular oxygen is inhibited by the chemisorption of cysteine and glutathione on the smooth platinum electrode. The cathodic current of the molecular oxygen reduction is dependent on the concentration of both substances.