Adsorption of n-alkanes on plasma-oxidized high-strength carbon fibers

The objective of this work was to characterize the degree of heterogeneity brought about by oxygen plasma treatment of carbon fibers by studying its effects on the adsorption of n-alkanes. Untreated and unsized high-strength carbon fibers were subjected to oxygen plasma treatments with different degrees of severity. A sample of the same material oxidized following a standard industrial method was also studied for comparison. Adsorption of C5-C10n-alkanes at 303-353 K was measured by inverse gas chromatography (IGC). Elution peaks were symmetrical for the fresh and industrially oxidized samples; however, a large extent of asymmetry was observed for the plasma-treated fibers. Differences in surface heterogeneity were quantified in terms of several adsorption thermodynamic magnitudes. Differential heats of adsorption exhibited values similar to those corresponding to the probe-basal plane interaction. The dispersive component of the surface tension of the solids increased clearly upon plasma oxidation, the increase being systematic according to the severity of plasma treatment. It can be concluded that plasma oxidation generates high-surface-energy sites responsible for trapping of n-alkane molecules, this effect being more marked as the chain length increases. The possibility of this effect being associated to creation of micropores was ruled out on the basis of volumetric CO2 adsorption experiments and IGC measurements at finite dilution. Scanning tunneling microscopy observations allowed us to establish a possible connection between fiber surface nanostructure and IGC results. The sites accessible to n-alkane molecules in the industrially oxidized sample seem to be highly disordered, thus leading to a weaker interaction with the adsorbate.     

Tuning of texture and surface chemistry of carbon xerogels

The influence of different activation processes on the textural and surface chemical properties of carbon xerogels was studied. Carbon xerogels were prepared by the conventional sol-gel approach using resorcinol and formaldehyde; two different pHs of sol-gel processing led to carbon materials with distinct pore size distributions. The materials were subjected to controlled activation by three different methods: activation by oxygen plasma, activation by HNO(3), and activation by diluted air. Treatments with HNO(3) and diluted air created oxygen groups on the external surface as well as inside the pore channels, whereas plasma is more suitable for introducing oxygen groups selectively on the external surface. Nevertheless, it was shown that samples with wider pores can be oxidized to some extent on the pore interiors by plasma. Significant changes in total surface area by air activation were observed.     

Surface reactions of molecular and atomic oxygen with carbon phosphide films

The surface reactions of atomic and molecular oxygen with carbon phosphide films have been studied using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Carbon phosphide films were produced by ion implantation of trimethylphosphine into polyethylene. Atmospheric oxidation of carbon phosphide films was dominated by phosphorus oxidation and generated a carbon-containing phosphate surface film. This oxidized surface layer acted as an effective diffusion barrier, limiting the depth of phosphorus oxidation within the carbon phosphide film to < 3 nm. The effect of atomic oxygen (AO) exposure on this oxidized carbon phosphide layer was subsequently probed in situ using XPS. Initially AO exposure resulted in a loss of carbon atoms from the surface, but increased the surface concentration of phosphorus atoms as well as the degree of phosphorus oxidation. For more prolonged AO exposures, a highly oxidized phosphate surface layer formed that appeared to be inert toward further AO-mediated erosion. By utilizing phosphorus-containing hydrocarbon thin films, the phosphorus oxides produced during exposure to AO were found to desorb at temperatures >500 K under vacuum conditions. Results from this study suggest that carbon phosphide films can be used as AO-resistant surface coatings on polymers.     

Anchoring of a [Mn(salen)Cl] complex onto mesoporous carbon xerogels

Carbon xerogels were synthesized by the conventional sol-gel approach using formaldehyde and resorcinol. The wet gel was dried by two different procedures followed by carbonization, leading to mesoporous carbon xerogels with considerably different pore size distributions. The materials were subsequently oxidized with air, in order to introduce functional groups on the surface, in particular phenols, anhydrides and carbonyls. The capacity of the carbon xerogels for direct immobilization of metal complexes was tested with a manganese(III) salen complex which possesses an extended ligand pi system and two reactive hydroxyl groups on the aldehyde fragment. The manganese loadings of the various samples indicate that larger amounts of Mn(III) complex were immobilized in the oxidized carbon xerogels when compared with the parent unactivated materials, suggesting that complex immobilization took place preferably by covalent bond between the surface oxygen functional groups and the ligand reactive groups, rather than by pi-pi interactions. The size and shape of the carbon xerogel pores were also shown to play an important role in the final loading of the manganese(III) salen complex.     

Analysis of functional groups on the surface of plasma-treated carbon nanofibers

Plasma chemically modified carbon nanofibers were characterized by X-ray photoelectron spectroscopy with regard to the content of carbon, oxygen, and nitrogen and the contribution of carboxylic groups or ester, carbonyl and hydroxylic groups or ether on the surface. Unfortunately, X-ray photoelectron spectroscopy only provides an average value of the first 10 to 15 molecular layers. For comparison, depth profiles were measured and wet chemical methods were applied to estimate the thickness of the functionalized layer and the distribution of oxygen-containing functional groups within the near-surface layers. The results indicate that the fiber surface is covered by a monomolecular oxygen-containing layer and that plasma treatment allows a complete oxygen functionalization of the uppermost surface layer. The best conditions for plasma treatment found within the set of parameters applied to generate complete functionalization are: plasma gas O(2)/Ar ratio 1:1, gas pressure 1-1.5 hPa, plasma power 80 W, treatment time >or= 5 min. Additionally, three quick and easy methods are presented to estimate the efficiency of plasma treatment with regard to surface functionalization: pyrolysis, contact angle measurements, and light permeability measurements of aqueous carbon nanofiber suspensions.     

STUDY ON THE OXIDIZED GRAPHITE MATERIAL COATED WITH N-DOPED PHENOLIC RESIN FOR LITHIUM ION BATTERIES

Carbon-coated oxidized graphite has been prepared by a liquid-state deposition method. Oxidized graphite wasprepared by wet chemical oxidation. Oxidation increases the reversible capacity of graphite, but its initial charge anddischarge efficiency was reduced. Phenolic resin was applied to form the disordered carbon layer on the oxidized graphite.The efficiency and reversible charge capacity were obviously increased. The morphology of carbon materials wasinvestigated by SEM.     

Electronic and adsorption properties of Ce‐Ag layers

Silver has rarely been considered as the catalyst for CO oxidation, although it has been recognized to be very active in several partial oxidation reactions such as ethylene epoxidation and formaldehyde synthesis. It is generally believed that a metal support interaction plays an important role in catalytic processes. Therefore in our study, we examined electronic and adsorption properties of cerium deposited onto a polycrystalline silver substrate. Layers of approximately one monolayer of cerium deposited on a clean silver substrate were examined in situ using surface‐sensitive techniques—by XPS, ultraviolet photoelectron spectroscopy (UPS) and low energy ion scattering (LEIS). CO molecular adsorption was observed by UPS and LEIS; experimental results exhibited CO adsorption on Ce atoms sites. Oxygen adsorption on deposited layers led to a strong oxidation; stoichiometry of oxidized layers was given by amount of adsorbed oxygen and by temperature. Copyright © 2011 John Wiley & Sons, Ltd.     

Local electron transfer rate measurements on modified and unmodified glassy carbon electrodes

A natural and artificial distribution of electron transfer activity on glassy carbon electrodes can be observed and quantified by the use of scanning electrochemical microscopy (SECM). A large (sevenfold) spread in rate constant is found for randomly sampled sites on polished, untreated glassy carbon surfaces. Direct-mode oxidation with the SECM tip was used to produce small regions of oxidized carbon on a polished surface. A large increase in electron transfer rate for the Fe(II/III) ion is observed on the locally oxidized carbon surface in comparison to the unoxidized region. Rate constant measurements made along a line profiles the transition from unoxidized to oxidized surfaces. SECM images of defect sites show reaction–rate variations. Rate constants measured at several locations of the defective surface allows discrimination between the kinetic and topographic components of the SECM image. Dedicated to the 80th birthday of Keith B. Oldham     

HREELS investigation of the surfaces of nanocrystalline diamond films oxidized by different processes

This article reports on the use of high-resolution electron energy loss spectroscopy (HREELS) for the investigation of as-grown (hydrogen-terminated) and oxidized nanocrystalline diamond films (NCD) using chemical, physical, and electrochemical approaches. The results indicate that the nature and number of oxygen-related chemical groups generated on the NCD surface depend strongly on the oxidation process. A high concentration of C-O functions has been obtained on the NCD surface oxidized by rf (radio frequency) oxygen plasma, whereas the highest C═O/C-O ratio has been achieved by electrochemical oxidation. The NCD surface oxidized by rf plasma was totally free of C═O groups. Traces of surface hydroxyl groups (C-OH) have been detected upon annealing in air or through UV/ozone oxidation.     

In situ extended X-ray absorption fine structure study during selective alcohol oxidation over Pd/Al2O3 in supercritical carbon dioxide

High-pressure in situ X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data are reported during the selective oxidation of benzyl alcohol to benzaldehyde in supercritical carbon dioxide over a Pd/Al(2)O(3) catalyst (shell impregnated). For this purpose, a continuous-flow system with a spectroscopic cell suitable for in situ X-ray absorption studies on heterogeneous catalysts up to 200 degrees C and 200 bar has been developed. Due to the high contribution of the dense fluid to the overall X-ray absorption, high stability of the process pressure is mandatory, particularly when recording EXAFS spectra. According to EXAFS and XANES results, the palladium particles were fully reduced after exposure to benzyl alcohol in scCO(2). In contrast to Pd-catalyzed liquid-phase oxidation, a higher oxygen tolerance of the catalyst was observed. Palladium was partially oxidized on the surface under typical reaction conditions (0.9 mol % benzyl alcohol/0.5 mol % O(2) in carbon dioxide), which gradually increased when the concentration of oxygen in the feed was raised. Both XANES and EXAFS data uncovered that palladium is mainly oxidized on the surface or within the outermost layers. These results are in accordance with simulations of the XANES data using the FEFF8.20 code (program for ab initio calculations on multiple scattering XAS) and EXAFS data fitting/simulation.     

Improving ORR activity of carbon nanotubes by hydrothermal carbon deposition method

Nitrogen doped carbons are an important family of materials with ideal activity for oxygen reduction reaction(ORR). It is always interesting to search functional carbons with high heteroatom contents and desirable structure for ORR. Within this study, the surface modification of carbon nanotubes(CNTs) via hydrothermal carbonization(HTC) technique in the presence of glucose and urea was reported, where the surface of CNTs is successfully coated by nitrogen containing hydrothermal carbon layers. The resulting composite combines both advantages of the outstanding electrical conductivity of CNTs and the effective ORR active sites provided by doped nitrogen in the HTC carbon layers. By controlling the ratio of glucose and urea, the nitrogen contents coated on the surface of CNTs can reach up to 1.7 wt%. The resulting materials show outstanding electrochemical activity towards ORR in alkaline electrolyte, making it one of the valuable metal-free electrode materials and a competent alternative to the state-of-the-art Pt/C catalyst.     

Atomic-scale scanning tunneling microscopy study of plasma-oxidized ultrahigh-modulus carbon fiber surfaces

In the present work, scanning tunneling microscopy (STM) was employed to study the surface modification of ultrahigh modulus carbon fibers at the atomic level by oxygen plasma. As detected by STM, the distinctive feature of the fresh, untreated surface was the general presence of atomic-scale arrangements in different degrees of order (from atomic-sized spots without a clearly ordered disposition to triangular patterns identical to those typical of perfect graphite). Following fiber exposure to the plasma, the STM images showed evidence of the abstraction of carbon atoms from random locations on the fiber surface, giving rise to the development of defects (i.e., structural disorder), which in turn were the places where oxygen could be introduced during and after the plasma etching. It was observed that the most effective treatments in terms of extent of surface structural modification (disordering) and uniform introduction of oxygen were those carried out for just a few ( approximately 3) minutes. Considerably shorter exposures failed to provide a homogeneous modification and many locations on the fiber surface remained unaltered, retaining their original atomic-scale order, whereas longer treatments did not bring about further structural changes to the surface and only led to fiber consumption. These results are consistent with previous X-ray photoelectron spectroscopy measurements on these fibers and provide an atomic-level understanding of the saturation effect observed in the surface oxygen concentration of this and other types of carbon fibers with plasma oxidation. Such understanding may also prove helpful for the accurate control and optimization of fiber-matrix interaction in composite materials.     

Mössbauer investigation of Fe doped La4Ni3O10±y phases

⁵⁷Fe doped La₄Ni_2.97Fe_0.03O_9.95 was synthesized by a citrate method and, afterwards, successfully oxidized and reduced by electrochemical methods. The compounds obtained were investigated by X-ray diffraction, electrical measurements and Mössbauer spectroscopy. The study allowed to follow the variation of the two nickel sites environment with the oxygen stoichiometry and a deeper understanding of the electrical behavior versus oxygen non-stoichiometry was achieved. The Mössbauer study revealed that after both oxidation and reduction treatments, the major modifications were observed on the octahedra adjacent to the La₂O₂ layers, while the middle octahedra of the triple perovskite block remained almost unchanged. The oxygen intercalation (oxidized treatment) takes place essentially in the La₂O₂ layers and the oxygen desintercalation (reduction treatment) occurs in the octahedral sites adjacent to those layers.     

Opening mechanism of internal nanoporosity of single-wall carbon nanohorn

Single-wall carbon nanohorn (SWNH), which is a tubular particle with a cone cap, was oxidized in an oxygen flow at various temperatures. N(2) adsorption at 77 K, thermogravimetry (TG), differential thermal analysis (DTA), transmission electron microscopy, and Raman spectroscopy measurements were carried out on the oxidized SWNHs. The specific surface area of the oxidized SWNHs can be controlled by oxidation temperature, giving the maximum value of 1420 m(2)/g. The pore size distribution by the BJH method and the comparison plot of the N(2) adsorption isotherms of SWNH oxidized at different temperatures against that of as-grown SWNH revealed the minimum oxidation temperature for opening internal nanopores. TG-DTA analyses determined the components of as-grown SWNH: amorphous carbon 2.5 wt %, defective carbon at the cone part 15 wt %, tubular carbon 70 wt %, and graphitic carbon 12 wt %. These systematic analyses provided the exact internal nanopore volume of 0.49 mL/g for pure SWNH particles.     

Analysis of the Electrochemical Oxidation of Multiwalled Carbon Nanotube Tower Electrodes in Sodium Hydroxide

Towers of aligned multiwalled carbon nanotubes (MWCNTs) were electrochemically oxidized in aqueous 1 M NaOH. An oxidation current that decayed with time was monitored using amperometry at a fixed potential. Cyclic voltammetry showed that the background current and electrode capacitance increased after oxidation without significantly affecting the faradaic current from the reduction of ferricyanide. Oxidation in NaOH caused morphological changes and increased hydrophilicity of the MWCNT tower electrodes. XPS spectra indicated increased oxygen on the surface after oxidation, while Raman spectra indicated that a large amount of amorphous carbon was present before and after oxidation.     

Removal of copper from aqueous solutions by adsorption on activated carbons

The adsorption isotherms of Cu(II) ions from aqueous solutions in the concentration range 40–1000 mg l⁻¹ on two samples of granulated and two samples of activated carbon fibres containing varying amounts of associated oxygen have been reported. The adsorption isotherms are type I of BET classification showing initially a rapid adsorption tending to be asymptotic at higher concentrations. The amounts of oxygen associated with the carbon surface has been enhanced by oxidation with nitric acid and ammonium persulphate in the solution phase and with oxygen gas at 350°C and decreased by degassing of the oxidized carbon samples at 400, 650 and 950°C. The adsorption of Cu(II) ions increases on oxidation and decreases on degassing. The increase in adsorption on oxidation depends on the nature of the oxidative treatment while the decrease in adsorption on degassing depends on the temperature of degassing. This has been attributed to the increase in the carbon–oxygen acidic surface groups on oxidation and their decrease on degassing. Suitable mechanisms consistent with the results have been proposed.     

Evidence from first principles calculations for a bent CO2 intermediate in the oxidation of carbon monoxide on the Cu (110) surface

We have carried out first principles plane wave density-functional theory calculations to study the adsorption of CO molecule on a clean and unreconstructed Cu (110) surface at 1/12 monolayer coverage and have investigated the subsequent oxidation by preadsorbed oxygen atoms. As found experimentally, the CO adsorbs perpendicular to the surface plane through the carbon atom; the top site was found to be the most favorable position for CO adsorption although the short-bridge site is only slightly less stable. Surprisingly, for a sparely oxidized surface with O atoms adsorbed in hollow sites the coadsorption energy is slightly negative for only the above two CO sites which have therefore been used as starting points to explore the energy surface of the oxidation reaction. We have confirmed the existence of bent CO(2) surface intermediate as previously suggested from experimental studies. Using the nudged elastic band method, we have characterized a two step reaction which involves the formation of this intermediate. The results suggest that the rate determining step of the oxidation reaction is the formation of the intermediate and the energy barrier (200 meV) is close to although smaller than experimentally estimated values.     

Electrooxidation of CO on Ru（0001） and RuO2（ 100） Electrode Surfaces

The electrooxidation of CO on Ru(0001) and RuO2(100) electrode surfaces were characterized by cyclic voltammetry,AES and RHEED,The CO adlayer was first partially oxidized at 0.8 V, which is controlled by the attack of oxygen species toward the Ru(0001) surface. The remaining CO aldayer oxidation at 0.55 V is related to the combination of CO molecules with oxygen species already located on the surface,In contrast,successive peaks on RuO2(100) at 0.4 V and 0.72 V are observed ,which shows that CO molecules can directly react with two different lattice-oxygen on the surface to carbon dioxide.     

Perchloric acid dissolution of graphite and pyrolytic carbon

Three procedures are described for the wet oxidation, with perchloric acid, of nuclear graphite, pyrocarbon-coated fuel particles, and other carbonaceous materials used in high-temperature gas-cooled nuclear reactors (HTGRs). The first procedure is for dissolution of graphite and pyrolytic carbon, the second for dissolution of milligram quantities of HTGR fuel particles, and the last for dissolution of more easily oxidized carbonaceous materials such as charcoal. These procedures were developed primarily for the dissolution of irradiated materials before fission-product or burn-up analyses, but they are also used for dissolution of unirradiated materials.     

Multi‐instrument characterization of poly(divinylbenzene) microspheres for use in liquid chromatography: as received,air oxidized,carbonized, and acid treated

We report a multi‐instrument characterization of the carbon particles in carbon/polymer/nanodiamond core‐shell materials used for high‐performance liquid chromatography. These particles are prepared by the carbonization/pyrolysis of poly(divinylbenzene) (PDVB) microspheres. Scanning electron microscopy showed that the particles (4.9 µm initially) decreased in size after air oxidation (to 4.4 µm) and again after carbonization (down to 3.5 µm) but remained highly spherical. Brunauer–Emmett–Teller measurements showed low surface areas initially (as received: 1.6 m²/g, after air oxidation: 2.6 m²/g) but high values after carbonization (445 m²/g). Fourier transform infrared spectroscopy revealed the changes in the functional groups after air oxidation (C = O and C–O stretches appear), carbonization (carbon‐oxygen containing moieties disappear), and acid treatment (reintroduction of carbon‐oxygen containing moieties). X‐ray photoelectron spectroscopy (XPS) and elemental analysis revealed the surface and bulk oxygen contents before and after treatments. By XPS, the atom percent oxygen for the as received, air oxidized, carbonized, and acid treated particles are 8.7, 16.6, 3.7, and 13.8, respectively, and by elemental analysis, the percent oxygen in the materials is 0.6, 8.1, 0.9, 16.9, respectively. A principal components analysis of time‐of‐flight secondary ion mass spectrometry data identified ions that were enhanced in the different materials, where almost 90% of the variation in the analyzed peak areas was captured by two principle components. X‐ray diffraction and Raman spectroscopy suggested that the carbonized PDVB was disordered. Thermogravimetric analysis showed significant differences between the differently treated PDVB microspheres. This work applies directly to a commercial product and the process for preparing it. Copyright © 2015 John Wiley & Sons, Ltd.