Influence of the surface chemistry of modified activated carbon on its electrochemical behaviour in the presence of lead(II) ions

Cyclic voltammetric studies of the influence of surface chemistry on the electrochemical behaviour of granulated and powdered activated carbon samples in the presence of lead(II) ions both in bulk solution and pre-adsorbed on carbon were carried out. Variety in surface chemical character was achieved through modification of carbon samples by heat treatment in vacuum, ammonia and ammonia-oxygen atmospheres, as well as by oxidation in moist air and with concentrated nitric acid. For the samples obtained, the surface area (BET), acid–base neutralization capacities and sorption capacity towards Pb²⁺ ions were estimated. The states of the deposited Pb species were assessed by means of FTIR and XPS spectra as well as cyclic voltammetry. The importance of the surface chemistry of the carbon electrode materials are discussed in terms of their electrochemical properties and the mechanism of adsorption processes. The Cπ-metal and heteroatom-metal interaction are dominant in amphoteric and basic carbons, but in oxidized samples adsorption take place mainly by ion-exchange. Other forms of adsorption, such as the formation metal hydroxide species, are also covered buy this paper. Various forms of adsorbed lead species exhibit different electrochemical activities.     

Electrochemical stability of carbon nanofibers in proton exchange membrane fuel cells

This fundamental study deals with the electrochemical stability of several non-conventional carbon based catalyst supports, intended for low temperature proton exchange membrane fuel cell (PEMFC) cathodes. Electrochemical surface oxidation of raw and functionalized carbon nanofibers, and carbon black for comparison, was studied following a potential step treatment at 25.0 °C in acid electrolyte, which mimics the operating conditions of low temperature PEMFCs. Surface oxidation was characterized using cyclic voltammetry, X-ray photoelectron spectroscopy (XPS), and contact angle measurements. Cyclic voltammograms clearly showed the presence of the hydroquinone/quinone couple. Furthermore, identification of carbonyl, ether, hydroxyl and carboxyl surface functional groups were made by deconvolution of the XPS spectra. The relative increase in surface oxides on carbon nanofibers during the electrochemical oxidation treatment is significantly smaller than that on carbon black. This suggests that carbon nanofibers are more resistant to the electrochemical corrosion than carbon black under the experimental conditions used in this work. This behaviour could be attributed to the differences found in the microstructure of both kinds of carbons. According to these results, carbon nanofibers possess a high potential as catalyst support to increase the durability of catalysts used in low temperature PEMFC applications.     

Effect of carbon surface oxidation on platinum supported carbon particles on the performance of gas diffusion electrodes for the oxygen reduction reaction

The effect of carbon surface oxidation on platinum supported carbon particles (Pt/C) with nitric acid was investigated by cyclic voltammetry, electrochemical impedance spectroscopy, polarization experiments and chronoamperometry. Cyclic voltammograms, polarization curves and electrochemical impedance spectra showed that the treated catalyst had much larger active surface area and higher ionic conductivity than the untreated catalyst, and provided enhanced performance for oxygen reduction. The formation of acidic groups was examined by IR spectra. The Pt/C surface oxidation had a large effect on the performance of a gas diffusion electrode for oxygen reduction reaction.     

整形和表面改性对人造石墨负极材料性能的影响

在对不同来源人造石墨原料进行理化性能分析的基础上,按照相同的工艺条件制成负极材料,比较了原料来源不同的人造石墨用作锂离子电池负极材料的性能。再以同一来源人造石墨为原料,采用不同设备、不同工艺、不同含量沥青进行整形、炭包覆及表面氧化改性处理,探讨了不同工艺处理对所制备的人造石墨负极材料的粒度分布、振实密度、比表面积和电化学性能的影响。结果表明,整形工艺与设备、炭包覆和表面氧化改性处理对提高负极材料的性能具有重要的作用。     

Immobilization of amines at carbon fiber surfaces

The reaction between amines acting as nucleophiles and the C=C bonds on the carbon fiber surface acting as electrophilic vinyl groups has not yet been explored. In this contribution it is demonstrated that both thermal reactions and electrochemical oxidation of amines at carbon fibers allow the covalent bonding of these molecules directly to the carbon fiber surface, presumably via nucleophilic attack of the amine at electrophilic C=C sites at the surface and subsequent formation of C–N bonds between the surface and the amine. A novel strategy for a quantitative assay of the number of amines attached to the surface is developed in which Fe(CN)₆³⁻ is electrostatically bound to the protonated, cationic amine sites, followed by electrochemical determination of the amount of bound Fe(CN)₆³⁻ as a function of its concentration in solution. Analysis of the isotherm for this electrostatic binding process then provides a measure of the number of interfacially immobilized amines. The composition of the amine layer is also probed using X-ray photoelectron spectroscopy (XPS). Mechanisms are discussed by which attachment of amines at the electrophilic vinyl groups of the carbon fibers can occur. The likely influence that this type of reaction has on the interfacial shear strength in carbon fiber/epoxy composite materials is also discussed.     

锂离子电容器硬碳负极材料的表面改性及其电化学性能研究

以浓硫酸和浓硝酸为氧化剂,采用超声氧化法对硬碳进行表面氧化处理,并研究其作为锂离子超级电容器负极材料的电化学性能。采用扫描电镜、X射线衍射和X射线光电子能谱等表征手段研究了超声氧化处理对硬碳形貌、结构以及表面含氧官能团相对含量的影响。采用恒电流充放电、循环伏安法及交流阻抗法等电化学测试手段对处理前后硬碳的电化学性能进行研究。结果表明:超声氧化处理能在硬碳表面引入适量的含氧官能团,添加额外的活性中心,提高电子迁移率,进而提高硬碳材料的电化学性能。半电池测试中,在2 A·g-1的高电流密度下,氧化硬碳的比容量是未处理硬碳的2倍,具有优秀的倍率性能。以氧化硬碳负极和活性炭正极制备出锂离子电容器,能量密度为37.6 W·h·kg-1,功率密度可达9415 W·kg-1,在1.0 A·g-1电流密度下,经过4000次充放电循环后,容量保持率为99.1%,具有良好的循环稳定性。     

阳极氧化对碳纤维及其复合材料性能影响的研究

对聚丙烯腈基碳纤维表面进行电化学氧化处理,用SEM扫描电镜、力学分析研究了阳极氧化对碳纤维表面形貌及力学性能的变化过程.结果表明：随着阳极氧化电流的增大,碳纤维表面沟槽缺陷逐渐消失,碳纤维力学性能先上升后下降,80 A氧化电流使碳纤维层间剪切强度提高变化15.3％、拉伸强度提高l2.1％;阳极氧化有利于提高碳纤维在热塑性材料中的粒径尺寸.     

Synergies between electrochemical oxidation and activated carbon adsorption in three-dimensional boron-doped diamond anode system

In order to enhance the performance of boron-doped diamond (BDD) anode system, activated carbon is added into BDD anode system to construct a three-dimensional electrode system. The degradation rates of p-nitrophenol and COD were significantly improved by 2–7 times compared to two-dimensional BDD anode system. More importantly, the synergy between electrochemical oxidation and activated carbon adsorption was observed. Investigations revealed that the synergy was not only resulted from direct electrochemical oxidation at activated carbon, but also from electro-catalysis of activated carbon to indirect electrochemical oxidation mediated by hydroxyl radicals. Although oxygen was reduced to hydrogen peroxide at the activated carbon surface, but the oxidation of hydrogen peroxide was not the main reason for the improvement of three-dimensional electrode system due to its relative weak oxidation capacity. Instead, the decomposition of hydrogen peroxide to hydroxyl radicals at catalysis of activated carbon played an important role on the enhancement of three-dimensional electrode system.     

Electrochemical oxidation behavior of titanium nitride based electrocatalysts under PEM fuel cell conditions

Titanium nitride (TiN) is attracting attention as a promising material for low temperature proton exchange membrane fuel cells. With its high electrical conductivity and resistance to oxidation, TiN has a potential to act as a durable electrocatalyst material. Using electrochemical and spectroscopic techniques, the electrochemical oxidation properties of TiN nanoparticles (NP) are studied under PEM fuel cell conditions and compared with conventional carbon black supports. It is observed that TiN NP has a significantly lower rate of electrochemical oxidation than carbon black due to its inert nature and the presence of a native oxide/oxynitride layer on its surface. Depending on the temperature and the acidic media used in the electrochemical conditions, the open circuit potential (OCP) curves shows the overlayer dissolved in the acidic solution leading to the passivation of the exposed nitride surface. It is shown that TiN NP displays passive behavior under the tested conditions. The XPS characterization further supports the dissolution argument and shows that the surface becomes passivated with the O-H groups reducing the electrical conductivity of TiN NP. The long-term stability of the Pt/TiN electrocatalysts is tested under PEM fuel cell conditions and the trends of the measured electrochemical surface area at different temperatures is shown to agree with the proposed passivation model.     

粘胶基碳纤维连续式电化学氧化表面处理（1）：碳纤维表面的物理 …

本文报道了用连续式电化学氧化表面处理粘胶基碳纤维表面,并测定了处理后碳纤维的单丝强度,表面浸润性,表面活性官能团含量及表面形貌等表面物理化学性能。结果表明：粘胶基碳纤维经电化学氧化表面处理可以有效地在表面主生活性官能团和提高表面粗糙度,从而有效地提高表面润湿性,但经处理后单丝强度较易下降,因此需精确控制处理的条件。     

A novel hydrazine electrochemical sensor based on a zirconium hexacyanoferrate film-bimetallic Au–Pt inorganic–organic hybrid nanocomposite onto glassy carbon-modified electrode

This work describes the electrochemical behavior of zirconium hexacyanoferrate (ZrHCF) film immobilized on the surface of bimetallic Au–Pt inorganic–organic hybrid nanocomposite glassy carbon electrode and its electrocatalytic activity toward the oxidation of hydrazine. The electrode possesses a three-dimensional (3D) porous network nano architecture (NFs). The surface structure and composition of the sensor was characterized by scanning electron microscopy (SEM). Electrocatalytic oxidation of hydrazine on the surface of modified electrode was investigated with cyclic voltammetry and chronoamperometry methods and the results showed that the ZrHCF film displays excellent electrochemical catalytic activities toward hydrazine oxidation. The modified electrode indicated reproducible behavior and high level of stability during the electrochemical experiments.     

Comparative investigation of the resistance to electrochemical oxidation of carbon black and carbon nanotubes in aqueous sulfuric acid solution

The resistance to electrochemical oxidation of carbon black (Vulcan XC-72) and chemical vapor deposited multiwalled carbon nanotubes (CVD-MWNTs), both widely-used as catalyst supports for low temperature fuel cells, is investigated with potentiostatic oxidation in 0.5 mol L⁻¹ H₂SO_4, which mimics the working conditions of low temperature fuel cells. The surface oxygen of oxidized carbon black and MWNTs are analyzed with cyclic voltammetry and X-ray photoelectron spectroscopy (XPS). The increase in surface oxygen on MWNTs during 120 h holding at 1.2 V (versus Reversible Hydrogen Electrode, RHE) is much less than that on carbon black. The conclusion can be reached that CVD-MWNTs are more resistant to electrochemical oxidation than carbon black under the condition in the report. CVD-MWNTs therefore possess a higher potential for low temperature fuel cell applications.     

Preparation and characterization of epoxy/carbon fiber composite capacitors

Capacitors based on structural carbon fiber electrodes and epoxy‐based gel polymer electrolyte have been fabricated. The electrochemical properties of electrolytes and capacitors were evaluated by linear sweep voltammetry, cyclic voltammetry (CV), galvanostatic charge–discharge, and electrochemical impedance spectroscopy techniques. Surface modification of carbon fibers was carried out by oxidation, and the structural and surface characteristics of carbon fibers were investigated by scanning electron microscope, Brunauer–Emmet–Teller, and Boehm titration. The results showed that the electrochemical stability window of the electrolyte reached 2.75 V and the ionic conductivity reached the order of 10⁻⁵ S/cm at room temperature. Surface modification of carbon fiber by oxidation can enlarge fiber area and strengthen fiber chemical activity, as well as its energy storage ability. The specific capacitance of epoxy/carbon fiber composite capacitor was obtained as high as 3.0 F/g with good cycling performance. POLYM. COMPOS., 36:1447–1453, 2015. © 2014 Society of Plastics Engineers     

Exponential growth of electrochemical double layer capacitance in glassy carbon during thermal oxidation

The evolution of the electrochemical double layer capacitance of glassy carbon during thermochemical gas phase oxidation was studied with electrochemical impedance spectroscopy. Particular attention was paid to the initial oxidation stage, during which the capacitance grows exponentially. This stage could be experimentally assessed by lowering the reaction temperature and oxidant partial pressure. After a specific oxidation time the capacitance growth experiences a cross-over to a logistic growth.     

Enhanced electro-oxidation resistance of carbon electrodes induced by phosphorus surface groups

The electro-oxidation of carbon materials enormously degrades their performance and limits their wider utilization in multiple electrochemical applications. In this work, the positive influence of phosphorus functionalities on the overall electrochemical stability of carbon materials has been demonstrated under different conditions. We show that the extent and selectivity of electroxidation in P-containing carbons are completely different to those observed in conventional carbons without P. The electro-oxidation of P-containing carbons involves the active participation of phosphorus surface groups, which are gradually transformed at high potentials from less-to more-oxidized species to slow down the introduction of oxygen groups on the carbon surface (oxidation) and the subsequent generation of (C*OOH)-like unstable promoters of electro-gasification. The highest-oxidized P groups (–C–O–P-like species) seem to distribute the gained oxygen to neighboring carbon sites, which finally suffer oxidation and/or gasification. So it is thought that P-groups could act as mediators of carbon oxidation although including various steps and intermediates compared to electroxidation in P-free materials.     

Electrochemical oxidation of multi-wall carbon nanotubes

The electrochemical modification of carbon nanotube films (buckypapers) in three different electrolytes consisting of two acids and a basic solvent at very low concentrations was studied. The electrolysis was performed at 1 A up to a maximum of 12 h. Four different characterization techniques have been employed for assessing the effectiveness of the proposed process. The results presented are very encouraging for the development of electrochemical oxidation as the main surface modification method for carbon nanotubes. It was found that the use of nitric acid electrolyte leads to scalable and controllable oxidation as compared to the basic electrolyte which was also effective but appeared to damage the graphitic structure of nanotubes during longer treatments.     

Electrochemical responses from surface oxides present on HNO3-treated carbons

Carbons of different surface oxide compositions, which were prepared from HNO₃ oxidation of polyacrylonitrile-based carbon fabric followed by heat treatment at different temperatures, were subjected to electrochemical response analysis using a voltammetric method. Temperature programmed desorption was employed to analyze the surface oxide composition. A significant amount of unstable oxides that can be irreversibly removed with reduction using a cathodic potential sweep were found to be present on the oxidized carbons. About 2.6 electrons are required to remove one oxygen atom from the carbon surface, and this may be the first quantitative study ever reported. After the initial cathodic sweep, no irreversible reduction peak response was observed for the subsequent electrochemical measurements. The capacitive performance of the carbons is related to the population of stable CO-desorbing complexes that can be determined with thermal desorption after the cathodic sweep. The present work has shown that carbon capacitance increases from 170 to 190 F/g with an increase of the CO-desorbing oxides from 1.31 to 1.56 mmol/g. This means that each stable CO-desorbing oxide is able to store 0.8 electron charge per volt within the potential window employed, suggesting the effective role of CO-desorbing oxides in improving the capacitance.     

Electrocatalytic oxidation of hydrazine at a Co(II) complex multi-wall carbon nanotube modified carbon paste electrode

The catalytic oxidation of hydrazine was investigated by a cobalt(II) bis (benzoylacetone) ethylenediimino multi wall carbon nanotube-modified carbon paste electrode (Co(II)BBAEDI-MWCNT-MCPE) as a highly sensitive electrochemical sensor. The effect of variables such as pH and modifier percent on cyclic voltammograms peak current was optimized. The modified electrode showed very efficient electrocatalytic activity for anodic oxidation of hydrazine in 0.1 M phosphate buffer solution (pH 7.0). Anodic peak potential of hydrazine oxidation at the surface of modified electrode shifts by about 500 mV toward negative values compared with that on the bare electrode. The diffusion coefficient and electron transfer coefficient of hydrazine were obtained using electrochemical approaches. The Co(II)BBAEDI-MWCNT-MCPE showed good reproducibility (RSD < 3.3%). The electrocatalytic current increased linearly with the hydrazine concentration in the range of 0.3–70.0 μM and detection limit was 0.1 μM. The effect of various interferences on the hydrazine peak current was studied. This method was applied to determine hydrazine in water samples.     

Enhanced methanol electro-oxidation activity of PtRu catalysts supported on heteroatom-doped carbon

A typical heteroatom (nitrogen)-doped carbon materials were successfully synthesized through the carbonization of a hybrid containing traditional carbon black covered by in situ polymerized polyaniline. The nitrogen content onto carbon can be adjusted up to 5.1 at.% by changing the coverage of polyaniline. The effects of nitrogen doping on the surface physical and electrochemical properties of carbon were studied using XPS, XRD and HRTEM, as well as CV and EIS techniques. With increasing nitrogen doping, the carbon structure became more compact, showing curvatures and dislocations in the graphene stacking. The nitrogen-doped carbon also exhibited a higher accessible surface area in electrochemical reactions, and a lower charge transfer resistance at the carbon/electrolyte interface. Moreover, to investigate the influence of nitrogen doping on the electrocatalytic activity of the PtRu/C catalyst, comparisons in CO stripping and methanol oxidation were carried out on PtRu catalysts supported by non-doped and nitrogen-doped carbon. Since the promotional roles of nitrogen doping, including the high electrochemically accessible surface area, the richness of the disordered nanostructures and defects, and the high electron density on N-doped carbon supports, contribute to the synthesis of well-dispersed PtRu particles with high Pt utilization and stronger metal-support interactions, an enhanced catalytic activity for methanol oxidation was obtained in the case of the PtRu/N-C catalyst in comparison with the traditional PtRu/C catalyst.     

The effect of electrolytic oxidation on the electrochemical properties of multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWNTs) were electrochemically oxidized by a constant-potential electrolysis method and then investigated in detail using scanning electron microscope, transmission electron microscope, FT-IR, electrical impedance spectroscopy, and cyclic voltammetry. The FT-IR spectra showed that the amount of hydroxyl generated on the surface of MWNTs increased with increasing the electrochemical oxidation time of MWNTs. The CV results, being conducted in nitrobenzene solution, showed that the nitrobenzene reduction current increased with the increase in oxidation time of the MWNTs within the first 60 min of electrolysis. An electrical equivalent circuit model for electrical impedance spectroscopy was further established to analyze the surface capacitance and resistance of the MWNTs, and the model results showed that the capacitance of the oxidized MWNTs increased greatly while the charge transfer resistance decreased, suggesting electrochemical oxidized MWNTs modified pyrolytic carbon electrode being an effective electrochemical sensor for nitrobenzene determination.