Electrochemically oxidized carbon anode in direct l-ascorbic acid fuel cells

The activity of electrochemically oxidized carbon electrode was investigated in the operation of a direct l-ascorbic acid fuel cell anode. The surface oxygen species placed on electrochemically oxidized carbon electrode were analyzed by X-ray photoelectron spectroscopy and cyclic voltammetry. The electrochemical oxidation process of carbon electrode can facilitate the pore-filling process (i.e., wetting) of the electrolyte into the microstructure of the carbon electrode by increasing the number of more polar functional groups on the electrode surface. The electrochemically oxidized carbon electrode exhibited significantly enhanced electro-catalytic oxidation activity of l-ascorbic acid compared to an unmodified carbon electrode. Moreover, the simplified electrode structure using carbon paper without an additional powder-based precious catalyst layer is very favorable in creating percolation network and generates power density of 18 mW/cm² at 60 °C.     

The underlying electrode causes the reported ‘electro-catalysis’ observed at C60-modified glassy carbon electrodes in the case of N-(4-hydroxyphenyl)ethanamide and salbutamol

The reported ‘electro-catalysis’ of C₆₀-film-modified electrodes for the electrochemical oxidation of N-(4-hydroxyphenyl)ethanamide and salbutamol has been explored at boron-doped diamond and glassy carbon electrodes. Using both C₆₀-film-modified boron-doped diamond and glassy carbon as underlying electrode substrates no electro-catalytic response is observed using the target analytes but rather the C₆₀ serves to block the electrode surface.A common experimental protocol used by researchers in this field is to electrochemically pre-treat the C₆₀-film-modified electrode. The response of employing this electrochemical pre-treatment at both bare glassy carbon and boron-doped diamond electrodes using the target analytes reveals that no effect on the electrochemical responses obtained at the boron-doped diamond electrode whereas a slight but significant effect occurs on glassy carbon which is attributed to the likely introduction of surface oxygenated species.Consequently the previously reported ‘electro-catalysis’ using C₆₀-film-modified electrode is not due to C₆₀ itself being catalytic, but rather that substrate activation through electrode pre-treatment is responsible for the observed ‘electro-catalysis’ likely through the introduction of surface oxygenated species.This work clearly shows that substrate activation is an important parameter which researchers studying C₆₀-film-modified electrodes, especially in electro-analysis needs to be considered.     

Review on carbon-derived,solid-state,micro and nano sensors for electrochemical sensing applications

The aim of this review is to summarize the most relevant contributions in the development of electrochemical sensors based on carbon materials in the recent years. There have been increasing numbers of reports on the first application of carbon derived materials for the preparation of an electrochemical sensor. These include carbon nanotubes, diamond like carbon films and diamond film-based sensors demonstrating that the particular structure of these carbon material and their unique properties make them a very attractive material for the design of electrochemical biosensors and gas sensors.Carbon nanotubes (CNT) have become one of the most extensively studied nanostructures because of their unique properties. CNT can enhance the electrochemical reactivity of important biomolecules and can promote the electron-transfer reactions of proteins (including those where the redox center is embedded deep within the glycoprotein shell). In addition to enhanced electrochemical reactivity, CNT-modified electrodes have been shown useful to be coated with biomolecules (e.g., nucleic acids) and to alleviate surface fouling effects (such as those involved in the NADH oxidation process). The remarkable sensitivity of CNT conductivity with the surface adsorbates permits the use of CNT as highly sensitive nanoscale sensors. These properties make CNT extremely attractive for a wide range of electrochemical sensors ranging from amperometric enzyme electrodes to DNA hybridization biosensors. Recently, a CNT sensor based fast diagnosis method using non-treated blood assay has been developed for specific detection of hepatitis B virus (HBV) (human liver diseases, such as chronic hepatitis, cirrhosis, and hepatocellular carcinoma caused by hepatitis B virus). The linear detection limits for HBV plasma is in the range 0.5–3.0 µL^? 1 and for anti-HBVs 0.035–0.242 mg/mL in a 0.1 M NH₄H₂PO₄ electrolyte solution. These detection limits enables early detection of HBV infection in suspected serum samples. Therefore, non-treated blood serum can be directly applied for real-time sensitive detection in medical diagnosis as well as in direct in vivo monitoring.Synthetic diamond has been recognized as an extremely attractive material for both (bio-) chemical sensing and as an interface to biological systems. Synthetic diamond have outstanding electrochemical properties, superior chemical inertness and biocompatibility. Recent advances in the synthesis of highly conducting nanocrystalline-diamond thin films and nano wires have lead to an entirely new class of electrochemical biosensors and bio-inorganic interfaces. In addition, it also combines with development of new chemical approaches to covalently attach biomolecules on the diamond surface also contributed to the advancement of diamond-based biosensors. The feasibility of a capacitive field-effect EDIS (electrolyte-diamond-insulator-semiconductor) platform for multi-parameter sensing is demonstrated with an O-terminated nanocrystalline-diamond (NCD) film as transducer material for the detection of pH and penicillin concentration. This has also been extended for the label-free electrical monitoring of adsorption and binding of charged macromolecules. One more recent study demonstrated a novel bio-sensing platform, which is introduced by combination of a) geometrically controlled DNA bonding using vertically aligned diamond nano-wires and b) the superior electrochemical sensing properties of diamond as transducer material. Diamond nano-wires can be a new approach towards next generation electrochemical gene sensor platforms.This review highlights the advantages of these carbon materials to promote different electron transfer reactions specially those related to biomolecules. Different strategies have been applied for constructing carbon material-based electrochemical sensors, their analytical performance and future prospects are discussed.     

Electrochemical impedance spectroscopy of oxidized and hydrogen-terminated nitrogen-induced conductive ultrananocrystalline diamond

We have studied the electrochemical impedance spectroscopy of conductive ultrananocrystalline diamond (UNCD) modified by either oxidation or hydrogenation surface treatments. The impedance was measured in the frequency range from 0.1 Hz to 40 kHz at different DC voltages and the results fitted to an equivalent electrical circuit. Despite the complexity of the conductive UNCD surface, composed of sp³-bonded grains and grain boundaries with a high content of sp²-bonded carbon atoms, a Randles circuit with a constant phase element (CPE) for the capacitive element provided a reasonable model for both terminations. However, the parameters of the CPE were very different for each termination. Taking into account the results obtained, we propose that the interfacial impedance of oxidized UNCD is dominated by the oxidized sp²-bonded carbon atoms present at the grain boundaries, and the interfacial impedance of hydrogen-terminated UNCD is governed by both the grain boundaries and the grains.     

Chemical and electrochemical characterization of porous carbon materials

Chemical and electrochemical techniques have been used in order to asses surface functionalities of porous carbon materials. An anthracite has been chemically activated using both KOH and NaOH as activating agents. As a result, activated carbons with high micropore volume (higher than 1 cm³/g) have been obtained. These samples were oxidized with HNO₃ and thermally treated in N₂ flow at different temperatures in order to obtain porous carbon materials with different amounts of surface oxygen complexes. Thermal treatment in H₂ was also carried out. The sample treated with H₂ was subsequently treated in air flow at 450 °C. Thus, materials with very similar porous texture and widely different surface chemistry have been compared. The surface chemistry of the resulting materials was systematically characterized by TPD experiments and XPS measurements. Galvanostatic and voltammetric techniques were used to deepen into the characterization of the surface oxygen complexes. The combination of both, chemical and electrochemical methods provide unique information, regarding the key role of surface chemistry in improving carbon wettability in aqueous solution and the redox processes undergone by the surface oxygen groups. Both contributions are of relevance to understand the use of porous carbons as electrochemical capacitors.     

掺硼金刚石纳米棒电极的制备及电化学性质

Boron-doped diamond nanorods with 300—400nm in diameters and several μm in lengths were successfully fabricated by deposited diamond film onto silicon nanowires using HFCVD methodElectrochemical analysis of glucose at the boron-doped diamond nanorods electrode was studiedCompared with normal flat boron-doped diamond electrode, some unique electrochemical properties were found on the nanorods electrode due to its large surface area and special nanostructuresThe nanorods electrode, as a new type of carbon material electrode, may serve as enabling technology for potential applications in electrochemical analysis     

Early stages of the HFCVD process on multi-vicinal silicon surfaces studied by electron microscopy probes (SEM,TEM)

In this paper, we show that silicon dimples are suitable samples to study diamond nucleation on a controlled distribution of defects by SEM FEG and HRTEM observations. Indeed, multi-vicinal surfaces generated by a UHV thermal treatment have been characterised by STM experiments. On these terraces, we observed a strong increase of the nucleation density higher than two orders of magnitude compared to pristine silicon samples. Moreover, a preferential location of diamond nuclei along the steps is reported. This result is explained by the large surface diffusion length of carbon species compared to the terrace's width. Indeed, during the early stages of growth, oriented silicon carbide nano-crystals are observed with the relationship SiC(220)//Si(220).     

Voltammetric and electrochemical impedance spectroscopy characterization of a cathodic and anodic pre-treated boron doped diamond electrode

The effect of boron doped diamond (BDD) surface termination, immediately after cathodic and anodic electrochemical pre-treatments, on the electrochemical response of a BDD electrode in aqueous media and the influence of the different supporting electrolytes utilized in these pre-treatments on the final surface termination was investigated with [Fe(CN)₆]^4−/3−, as redox probe, by cyclic and differential pulse voltammetry and electrochemical impedance spectroscopy. The cyclic voltammetry results indicate that the electrochemical behavior for the redox couple [Fe(CN)₆]^4−/3− is very dependent on the state of the BDD surface, and a reversible response was observed after the cathodic electrochemical pre-treatment, whereas a quasi-reversible response occurred after anodic electrochemical pre-treatment. Differential pulse voltammetry in acetate buffer also showed that the potential window is very much influenced by the electrochemical pre-treatment of the BDD surface. Electroactivity of non-diamond carbon surface species (sp² inclusions) incorporated into the diamond structure was observed after cathodic and anodic pre-treatments. Electrochemical impedance spectroscopy confirmed the cyclic voltammetry results and indicates that the BDD surface resistance and capacitance vary significantly with the electrolyte and with the electrochemical pre-treatment, caused by different surface terminations of the BDD electrode surface.     

Electrochemical behavior of amorphous carbon obtained from camphor

Amorphous carbon films were deposited on alumina plate by pyrolysing camphor at different temperatures with thermal chemical vapor deposition (CVD) technique. Carbon coated alumina plates were used as working electrode to ascertain their electrochemical behavior in different electrolytic media. Electrochemical windows of these carbon films were found to be suitable in the potential range of 1.05 to −0.30 V versus SCE in acid medium. In the presence of redox electrolyte, cathodic-anodic peak separation was found to be the same as that obtained with diamond. Raman spectra of carbon films were studied to explain some of their electrochemical behavior.     

The role of oxygen in the one step amination process of nanocrystalline diamond surface

Nanocrystalline diamond (NCD) thin films are ideal to realize platform for bio-chemical sensors. They interface in a very specific way with the environment and the surface termination controls their electrochemical behavior. Generally the as-deposited NCD diamond surface is hydrogen terminated and several techniques are reported to obtain covalent bonding of biological matter. Among others, amino-functional groups are very versatile linkers to biomolecules. Grafting of amino groups to the diamond surface includes: chlorination and exposure to ammonia gas under thermal conditions, radio-frequency plasma or a one step method consisting of UV irradiation in a pure ammonia atmosphere. This last technique is very promising, combining surface functionalization with the realization of SGFETs (Solution Gate FET), and thus being compatible with semiconductor technologies. Experimental data from literature show that ammonia functional groups are always accompanied by the presence of oxygen which degrades the NCD conductivity. In this work we report on XPS in situ study to understand the role of oxygen in the one step amination process. Five NCD samples with different surface terminations (hydrogenated, plasma oxidized, chemically oxidized and UV oxidized) were irradiated with UV photons in different atmospheres (pure NH₃ or NH₃ + O₂). XPS analysis shows that the presence of oxygen, both on the surface and in the gas mixture, strongly increases the efficiency of the UV surface amination.     

Electrochemical generation of oxygen-containing groups in an ordered microporous zeolite-templated carbon

Zeolite templated carbon (ZTC) was electrochemically oxidized under various conditions, and its chemistry and structural evolution were compared to those produced by conventional chemical oxidation. In both oxidation methods, a general loss of the original structure regularity and high surface area was observed with increasing amount of oxidation. However, the electrochemical method showed much better controllability and enabled the generation of a large number of oxygen functional groups while retaining the original structure of the ZTC. Unlike chemical treatments, highly microporous carbons with an ordered 3-D structure, high surface area (ranging between 1900 and 3500 m²/g) and a large number of oxygen groups (O = 11,000–3300 μmol/g), have been prepared by the electrochemical method. Some insights into the electrooxidation mechanism of carbon materials are proposed from the obtained polarization curves, using ZTC as a model carbon material.     

Simultaneous growth of well-aligned diamond and graphitic carbon nanostructures through graphite etching

A hot filament chemical vapor deposition process based on hydrogen etching of graphite has been developed to synthesize diamond and graphitic carbon nanostructures. Well-aligned diamond and graphitic carbon nanostructured thin films have been synthesized simultaneously on differently pretreated silicon substrates in a pure hydrogen plasma. Graphitic nanocones, diamond nanocones and carbon nanotubes were selectively grown on uncoated, diamond and nickel pre-coated silicon substrates, respectively, in a single deposition process. The nanocones are solid cones with submicron scale roots and nanometer-size sharp tips. The nanotubes are hollow tubes with outer diameter of approximately 50 nm. The orientation of the well-aligned carbon nanostructures depends on the direction of the electric field at the samples surface. Nucleation and growth of diamond on the nanocones were further investigated under similar conditions without plasma. Diamond nanocomposite films have been obtained by depositing a nanocrystalline diamond film on the layer of diamond nanocones.     

Carbon nanofibres and activated carbon nanofibres as electrodes in supercapacitors

Carbon nanofibres have been prepared by a floating catalyst procedure at industrial scale in a metallic furnace. The nanofibres (50-500 nm diameter and 5-200 μm length) are grown from the Fe particles used as catalyst. Soot appears together with the carbon nanofibres. The sample has been chemically activated using KOH as activating agent. Scanning electron microscopy has shown a smooth surface for the as-prepared carbon nanofibres but a rough surface for the activated ones. The specific surface area increases from 13 to 212 m²/g due to the activation. The volume of the micropores (in the 1-2 nm range) and the mesopores (2-5 nm range), as deduced by density functional theory methods, also increases after the activation. Electrochemical behaviour of the as-prepared and activated carbon nanofibres has been tested in a supercapacitor at laboratory scale using 6 M KOH aqueous solution as electrolyte. The specific capacitance, which is less than 1 F/g for the as-prepared sample, increase up to ≈60 F/g for the activated sample. Only a slight decrease in capacitance has been observed as the current density increases. Specific power of ≈100 W/kg at specific energy of 1 Wh/kg has been found in some particular cases. We have compared the electrochemical parameters of our activated carbon nanofibres with those of activated carbon nanofibres coming from a commercial sample; the latter was activated by the same way as our sample.     

Nucleation and Initial Growth Stages of Chemical Vapor Deposition (CVD) Diamond

Nucleation of diamond on non-diamond virgin substrates is characterized by low nucleation densities and long incubation times. Various methods have been developed to enhance nucleation densities and reduce the duration of incubation. This report describes a number of different but related studies of diamond nucleation on silicon and chemically modified silicon surfaces. The effect on the initial stages of deposition of mechanical abrasion with slurries and in-situ sample biasing are especially discussed. Substrate abrasion with diamond results in the embeddying of diamond debris into its surface. Destructive ion implantation into this diamond debris is found to prevent subsequent diamond growth, therefore leading to the conclusion that the diamond debris serves as growth centers. Abrasion of the substrate with mixed metal/diamond slurries is reported to further enhance nucleation relative solely to diamond abrasion. It is suggested that during the chemical vapor deposition (CVD) process some metals alter the composition of the gas phase above the growing surface. Also, the role of surface reactions is emphasized. We also introduce the dc-glow discharge process as a novel, in situ surface pretreatment method for the formation of a precursor for diamond nucleation. Our results show that the promotion of diamond growth by this method is primarily due to formation of nano-size diamond particles during the pretreatment process. It is suggested that, to some extent, graphitic carbon with a high degree of defects may serve as a diamond nucleation center as well.     

Electroless oxidation of boron-doped diamond surfaces: comparison between four oxidizing agents; Ce, MnO4, H2O2 and S2O8

The electrochemical properties of diamond are very sensitive to the surface terminations. It is still a challenge to successfully produce well-defined “C-O” functions. In this paper, we describe and compare the oxidation of as-grown polycrystalline boron-doped diamond (BDD) films using four different oxidizing agents in aqueous media: Ce⁴⁺, MnO₄⁻, H₂O₂ and S₂O₈²⁻. The different treatments lead to the formation of oxygenated functions at the diamond surface, mainly singly oxidized “C-O” groups such as “C-OH” or “C-O-C”. Processes with Ce⁴⁺ and MnO₄⁻ seem to be particularly interesting as they both lead to the creation of a high amount of oxygenated functions and an improvement of the charge transfer at BDD surfaces.     

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.     

Thermal conductance calculations of silicon nanowires: comparison with diamond nanowires

We present phonon thermal conductance calculations for silicon nanowires (SiNWs) with diameters ranging from 1 to 5 nm with and without vacancy defects by the non-equilibrium Green’s function technique using the interatomic Tersoff-Brenner potentials. For the comparison, we also present phonon thermal conductance calculations for diamond nanowires. For two types of vacancy defects in the SiNW, a ‘center defect’ and a ‘surface defect’, we found that a center-defect reduces thermal conductance much more than a surface defect. We also found that the thermal conductance changes its character from the usual behavior, in proportion to the square of diameter (the cross-sectional area) for over 100 and 300 K, to the unusual one, not dependent on its diameter at all at low temperature. The crossover is attributed to the quantization of thermal conductance.     

Pulsed laser surface modifications of diamond thin films

In view of practical applications requiring diamond films, plates and membranes with very smooth surfaces, ArF excimer laser polishing treatments were applied to thin (30 μm) diamond films grown by CVD on silicon substrates. The as-prepared diamond surfaces and the laser-treated parts of the samples were characterised by SEM analysis, Raman and micro-Raman spectroscopy. The presence on the laser-treated surface of a thin amorphous carbon layer responsible for the higher surface electrical conductivity and for the different optical reflectivity properties was evidenced. Using confocal micro-Raman spectroscopy a comparative depth profile analysis of the phase quality, below the surface in different regions of the films, was carried out. After short (10 min) treatment by H₂ plasma etching in the CVD chamber the graphitic top layer was completely removed from the samples.     

In situ FTIR characterization of the electrooxidation of glassy carbon electrodes

The electrooxidation of glassy carbon electrodes in acid and neutral solution has been investigated using in situ FTIR spectroelectrochemical techniques. The formation and transformation of intermediate oxide species in different potential regions has been observed. The results show that in the lower anodic potential region (i.e., < +1.2 V vs SCE), the main reaction is the transformation of oxide species (i.e. phenol-like species) initially on the carbon electrode surface. But in the high anodic potential region (i.e., > + 1.65 V vs SCE), the electrooxidation of carbon is a combination of electrochemical and chemical oxidation. A more detailed electrooxidation mechanism is proposed based on the experimental results.     

Oxidation behavior and protection of carbon/carbon composites prepared using rapid directional diffused CVI techniques

The oxidation kinetics of carbon/carbon (C/C) composites prepared using a rapid directional diffused (RDD) CVI process were studied. The results showed that the Arrhenius curve for the RDD CVI C/C composites consists of two straight lines, the intercept of which is at about 700 °C at the linear oxidation stage. The oxidation rates are controlled by the surface reaction at 600-700 °C, and the corresponding activation energy is 121 kJ/mol. Between 700 and 800 °C, the oxidation rates are dominated by chemical reaction and diffusion, and the relevant activation energy is 80 kJ/mol. SEM investigation showed that the oxidation starts with original pores on the C/C composite surface with the carbon fiber and matrix oxidized simultaneously. An inexpensive and easily pasted coating containing epoxy organic silicon resin, borates, refractory particulates, etc. was developed. After isothermal temperature, thermal cycle and immersion water oxidation tests, the coating was demonstrated to exhibit good oxidation-resistance properties. The oxidation-resistant mechanism of the coating is discussed.