Nitric acid oxidation of vapor grown carbon nanofibers

Vapor grown carbon nanofibers (Pyrograf III™) with 100–300 nm diameters and ∼10–100 μm lengths were oxidized in 69–71 wt.% nitric acid (115 °C) for various times (10 min to 24 h). These fibers were remarkably oxidation-resistant. XPS (O_1s) showed that the surface atomic oxygen percent increased from 6.3 to 18.3–22.5% for 10–90 min oxidations followed by a drop to 14–15% after 10–24 h oxidations. No damage was observed by TEM. Little change in surface area was observed by N₂ BET but CO₂-DR measurements exhibited an increase from 20–25 m²/g to 41–73 m²/g after 10–90 min of oxidation followed by a decrease to 35–22 m²/g after 10 h, consistent with the XPS findings. Shallow ultramicropore formation could account for the surface area increase. NaOH titrations showed ∼3-fold increase in surface acidic functions (∼27 to 76 μmol/g) occurring after 10 min of oxidation. Then this level remained constant through 24 h of oxidation. XPS (C_1s), O_1s) confirmed that carboxyl groups were removed and ester, anhydride, quinoid and phenolic hydroxyls appeared upon HNO₃ oxidation. Oxidized fibers dispersed when shaken in water, demonstrating wettability had increased. A model for this oxidation behavior is proposed.     

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 oxidation of carbon fibres in aqueous solutions and analysis of the surface oxides

Carbon fibres with notably different surface oxides can be prepared by varying the electrochemical oxidation conditions. Through correlation of voltammetric analysis and mass spectroscopy, interpretation of the reduction peaks of the surface oxides on the basis of their potential and width is possible. Narrow voltammetric reduction peaks at strongly negative potential are indicative of the predominance of –COOH type groups, while wide peaks at more positive potential are indicative of the presence of an excess of type groups. A quantitative determination of the surface acidic groups (–COOH and) is achieved by combination of Ag⁺ ion exchange and esterification of groups with 3,5-dinitrobenzoyl chloride. All results are confirmed by the independent method of –COOH group determination via their electrocatalytic behaviour in the reduction of azobenzene in methanol. The amounts of the –COOH and groups formed depend notably on the conditions of the electrochemical oxidation of the carbon fibres. The ratio between –COOH and groups coincides in all cases with that obtained by the mass spectrosopic data.     

The influence of oxidation on the texture and the number of oxygen-containing surface groups of carbon nanofibers

The effect of liquid-phase oxidation on the texture and surface properties of carbon nanofibers has been studied using XRD, TEM, SEM, N₂-physisorption, TGA-MS, XPS and acid-base titrations. Oxidation was performed by refluxing the nanofibers in HNO₃ and mixtures of HNO₃/H₂SO₄ for different times. The graphite-like structure of the treated fibers remained intact, however, the specific surface area and the pore volume increased with the severity of oxidation treatment. For the first time it is shown that the most predominant effect that gives rise to these textural modifications is the opening of the inner tubes of the fibers. Moreover, it is demonstrated that both the total oxygen content (O/C=0.02-0.07 at/at) as well as the number of acidic groups (1-3 nm⁻²) are a function of the type of oxidizing agent used and the treatment time. The total oxygen content of the oxidized samples turns out to be substantially higher than can be accommodated in the form of oxygen-containing groups at the exterior surface.     

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.     

Electrochemical oxidation of benzene at a glassy carbon electrode

Benzene oxidation in sulfuric acid at a glassy carbon electrode was investigated using voltammetric, chronoamperometric, and spectroscopic methods. The results are compared with those at a Pt electrode. Benzene was observed to be oxidized to benzoquinone presumably by active oxygen that was adsorbed on the GC electrode in the oxygen evolution region. It is concluded that oxidation at glassy carbon can produce benzoquinone or quinone-like compounds from an aqueous benzene solution. The applied potential for benzene oxidation should be less than 2.1 V vs RHE in order to prevent glassy carbon electrode damage by oxidation during long operation.     

The efficiency of the oxidation of carbon nanofibers with various oxidizing agents

The oxidation of carbon nanofibers (CNFs) with various oxidizing agents; 6 M HNO₃, KMnO₄, RuO₄, and a mixture of concentrated H₂SO₄/HNO₃ is studied to determine the reaction conditions that optimizes yield and chemical functionalization. The oxidized nanofibers were examined by scanning electron microscopy, and Raman spectroscopy to characterize the defects caused by oxidation. The amount of acidic sites generated during oxidative treatment was quantified by reacting them with amine terminated octadecane and the subsequent quantification of the products of this grafting process by Fourier transform infrared spectroscopy. The concentrated H₂SO₄/HNO₃ mixture created the maximum number of carboxylic acid groups and the highest amount of defect sites, but had very low yield (∼12%). Six molar of HNO₃ generated fewer defect sites and a lower number of -COOH groups, but did exhibit a 70% yield. RuO₄ and KMnO₄ resulted in similar amounts of overall defect sites, however the yield and amount of -COOH groups for KMnO₄ treated CNF were significantly lower than the RuO₄ treatment. Overall, oxidation of these CNF with RuO₄ provides the best balance of yield and carboxylation.     

Influence of wet oxidation of herringbone carbon nanofibers on the pseudocapacitance effect

Herringbone carbon nanofibers (CNFs) were treated with concentrated HNO₃ and a mixture of diluted HNO₃/H₂SO₄ to obtain a series of oxygen enriched CNF with different oxygen group distribution, but with a similar porous texture. Oxygen functional groups were determined by X-ray photoelectron spectroscopy. CNFs with a very high relative concentration of carbonyl and/or quinone groups and hydroxyl groups were obtained by adjusting the suitable temperature and time of oxidation with HNO₃ and HNO₃/H₂SO₄, respectively. The electrochemical behavior of the samples was studied in three- and two-electrode cells. The performance of oxidized CNFs-based supercapacitors working in 1 mol L⁻¹ H₂SO₄ and 6 mol L⁻¹ KOH was analyzed using cyclic voltammetry and galvanostatic charging/discharging. The specific capacitance of the oxidized CNFs was more than twice enhanced in acidic and alkaline media compared to the pristine CNFs due to the pseudocapacitance effect. It was revealed that not only quinone groups but also hydroxyl groups contribute into the overall capacitance through the pseudocapacitance effect. With increasing surface concentration of the CO and C–OH groups, the capacitance values increase for the capacitors operating in both media.     

Electrochemical properties of electrospun PAN/MWCNT carbon nanofibers electrodes coated with polypyrrole

The multi-walled carbon nanotube (CNT)-embedded activated carbon nanofibers (ACNF/CNT) and activated carbon nanofibers (ACNF) were prepared by stabilizing and activating the non-woven web of polyacrilonitrile (PAN) or PAN/CNT prepared by electrospinning. Both ACNF and ACNF/CNT were partially aligned along the winding direction of the drum winder. The average diameter of ACNF was 330 nm, while that of ACNF/CNT was lowered to 230 nm with rough surface. This was attributed to the CNT-added polymer solution in the electrospinning process providing finer fibers by increasing the electrical conductivity compared with the CNT-free one. The specific surface area and electrical conductivity of ACNF were 984 m²/g and 0.42 S/cm, respectively, while those of ACNF/CNT were 1170 m²/g and 0.98 S/cm, respectively. PPy was coated on the electrospun ACNF/CNT (PPy/ACNF/CNT) by in situ chemical polymerization in order to improve the electrochemical performance. The capacitances of the ACNF and PPy/ACNF electrodes were 141 and 261 F/g at 1 mA/cm², respectively, whereas that of PPy/ACNF/CNT was 333 F/g. This improvement in capacitance was attributed to the following: (i) the preparation of aligned nano-sized ACNF/CNT by electrospinning and the addition of CNT and (ii) the formation of a good charge-transfer complex by the PPy coating on the surface of the aligned nano-sized ACNF/CNT. The former leads to a good morphology and superior properties, such as a higher surface area, the formation of mesopores and an increase in electrical conductivity. The latter offers a refined three-dimensional network due to the highly porous structure between ACNF/CNT and PPy.     

Direct synthesis of carbon nanofibers on the surface of copper powder

A novel approach to synthesize carbon nanofibers (CNFs) directly on the surface of metal μm-sized particles to evenly disperse the carbon nanomaterials in a composite material was proposed. As a metal matrix, 5–10 μm copper particles were utilized. As a carbon source, C₂H₂, CH₄ and CO were examined. The best conditions were found to be in C₂H₂ (30 cm³/min) and H₂ (260 cm³/min) atmosphere at the temperature of 750 °C. The composites based on copper and CNFs prepared by vacuum hot pressing showed the increase in hardness from 35 to 60 kg/mm² almost retaining pure copper electrical properties.     

Electrochemical oxidation of glutathione at well-aligned carbon nanotube array electrode

Electrochemical oxidation and determination of glutathione (GSH) were investigated with well-aligned carbon nanotube (CNT) arrays. Square wave voltammetric and amperometric results suggest that aligned-CNT electrode exhibits excellent electrochemical activity and good anti-fouling property for direct electrochemical oxidation of glutathione. Also, the preliminary application of the aligned-CNT electrode for amperometric determination of glutathione was evaluated.     

Electrochemical study of surface oxidation and collectorless flotation of arsenopyrite

The surface oxidation of arsenopyrite in alkaline solutions has been studied by cyclic voltammetry. The initial oxidation of arsenopyrite surface produces ferric hydroxide and a realgar-like compound according to the following rection: At higher potentials, the oxidation of arsenopyrite results in elemental sulphur and arsenate according to the following overall reaction:

Preparation of graphene/carbon hybrid nanofibers and their performance for NO oxidation

A series of novel microdomain-graphitized polyacrylonitrile (PAN)-based nanofibers were prepared by adding varied amounts of graphene oxide into the precursor via the electrospinning method. These hybrid electrospun nanofibers with were stabilized in ambient atmosphere, carbonized in nitrogen atmosphere and treated in NH₃ atmosphere for NO oxidation with low concentration (50 ppm) at room temperature. The samples were characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, and nitrogen adsorption at 77 K. Oxidation of NO into NO₂ at room temperature was investigated in a fiber fixed-bed. The results demonstrated that the reduced graphene oxide sheets provide catalytic active sites embedded in the PAN-based nanofibers. In addition it was determined that nitrogen-containing functional groups played important roles in the enhancement of the catalytic oxidation of NO to NO₂. The samples with 5 wt.% GO exhibit the most catalytic oxidation of NO into NO₂.     

Electrochemical oxidation of divalent iron mixed oxides using carbon paste electrodes

The electrochemical behaviours of several iron(II) mixed oxides, Fe(II)M₂O₄ [where M = Fe(III), Al(III) and Cr(III)], and Fe(II) Ti(IV)O₃ were investigated using a carbon paste electrode with 1 M HCl binder. Solids containing Fe(III), Al(III) and Ti(IV) are not oxidized when the potential varies from +0.2 to + 1.1 V/sce whereas FeCr₂O₄ exhibits two oxidation peaks. The first one at about +0.4 V/sce, is due to iron(II) ions because the finest particles (< 100 nm) are immediately chemically solubilized. The second peak occurring at more positive potential is larger and corresponds to the oxidation of the biggest particles. This behaviour is similar to that of the reduction of Fe₂O₃ described elsewhere. So the oxidation phenomenon is the addition of two consecutive steps: a chemical solubilization followed by an oxidation and the shape of the second peak is influenced by the morphology of the oxide under study. Influences of the nature of the binder, of the synthesis procedure and of the grinding are reviewed.     

Consolidation of carbon nanofibers with pyrolytic carbon

A strategy of industrial-scale manufacture for a wide range of carbon materials based on carbon nanofibers is proposed. It was shown that porous materials with a high sorption capacity can be obtained with the use of carbon nanofibers by means of conventional manufacturing operations. The results of studying of consolidation of carbon nanofibers with pyrolytic carbon are reported. It was found that the nature of carbon material has a substantial effect on the rate of deposition of pyrolytic carbon. The most appropriate temperature range in which carbon nanofibers should be consolidated for the preparation of materials with a high catalytic activity was determined.     

电化学耦合阴极二氧化碳还原与阳极氧化合成

电催化二氧化碳还原（CO₂RR）利用电场作用在温和的条件下将二氧化碳转化为高值化学品。将CO₂RR与热力学电势较低的阳极反应耦合,可以降低槽电压,在阳极和阴极同时生成高值化学品,提高能量效率。本文介绍了CO₂RR与氧化合成反应耦合策略,探究了电解池、离子交换膜等电解装置对CO₂RR耦合电催化性能的影响,归纳了常用于CO₂RR耦合氧化合成体系中阴阳极电催化剂的种类,重点综述了CO₂RR与氯碱过程、醇类和含氮有机物氧化等典型阳极氧化合成反应耦合的最新进展。最后,针对目前存在的阳极催化剂成本高、全电解阳极产物的分离检测困难、反应物转化率低等问题,提出开发更加高效、稳定和低成本的阳极电催化剂、升级电极结构和电解装置以及拓展新型CO₂RR耦合体系等是未来的研究方向。