The electrochemical behavior of diamond coated molybdenum

Natishan, Paul M.; Morrish, A. A.

doi:10.1016/0167-577x(89)90164-x

Cited by 27 publications

(12 citation statements)

References 4 publications

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“…Second, there is a negligible coverage of electroactive or ionizable surface carbon−oxygen functionalities. Thus, the capacitance for diamond is largely independent of the electrolyte composition and pH. ,,,, Similar capacitance data for these four electrodes have been reported previously. ,,,, It is clear from these data that HGC most resembles GC and diamond most resembles the basal plane of HOPG in terms of the surface electronic properties.…”

Section: Resultssupporting

confidence: 84%

“…Diamond thin films are sp 3 carbon-based electrode materials that have only recently begun receiving investigation. − Diamond is one of nature's best insulators, but, when doped with boron, the films can possess electronic properties ranging from semiconducting to semimetallic. For example, boron doping levels as high as 10 21 cm -3 can be achieved, resulting in resistivities lower than 0.01 Ω-cm .…”

mentioning

confidence: 99%

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Anthraquinonedisulfonate Electrochemistry: A Comparison of Glassy Carbon, Hydrogenated Glassy Carbon, Highly Oriented Pyrolytic Graphite, and Diamond Electrodes

1998

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The electrochemistry of anthraquinone-2,6-disulfonate (2,6-AQDS) at glassy carbon (GC), hydrogenated glassy carbon (HGC), the basal plane of highly oriented pyrolytic graphite (HOPG), and boron-doped diamond was investigated by cyclic voltammetry and chronocoulometry. Quantitative determination of the surface coverage and qualitative assessment of the physisorption strength of 2,6-AQDS adsorption on each of these electrodes were done. The diamond and HGC surfaces are nonpolar and relatively oxygen-free, with the surface carbon atoms terminated by hydrogen. The polar 2,6-AQDS does not adsorb on these surfaces, and the electrolysis proceeds by a diffusion-controlled reaction. Conversely, the GC and HOPG surfaces are polar, with the exposed defect sites terminated by carbon-oxygen functionalities. 2,6-AQDS strongly physisorbs on both of these surfaces at near monolayer or greater coverages, such that the electrolysis proceeds through a surface-confined state. Less than 40% of the initial surface coverage can be removed by rinsing and solution replacement, reflective of strong physisorption. The results show the important role of the surface carbon-oxygen functionalities in promoting strong dipole-dipole and ion-dipole interactions with polar and ionic molecules such as 2,6-AQDS. The results also support the theory that diamond electrodes may be less subject to fouling by polar adsorbates, as compared to GC, leading to improved response stability in electroanalytical measurements. The relationship between the 2,6-AQDS surface coverage, the double-layer capacitance, and the heterogeneous electron-transfer rate constant for Fe(CN)(6)(3)(-)(/4)(-) for these four carbon electrodes is presented.

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Section: Resultssupporting

confidence: 84%

mentioning

confidence: 99%

Anthraquinonedisulfonate Electrochemistry: A Comparison of Glassy Carbon, Hydrogenated Glassy Carbon, Highly Oriented Pyrolytic Graphite, and Diamond Electrodes

1998

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“…Our research group has been actively involved in the study of conductive and semiconductive diamond thin film electrodes. − The use of diamond in electrochemistry has only recently been demonstrated, so very little research has been conducted thus far. − Most of our work, to date, has involved using diamond films grown on Si(111 and 100) substrates. These results have indicated that diamond films exhibit lower voltammetric background currents and larger S/B ratios for Fe(CN) 6 4-/3- and IrCl 6 2-/3- than freshly polished GC; reasonably good activity for these redox analytes without any conventional surface pretreatment; and good response stability for periods up to weeks. − These are all desirable qualities of advanced electrode materials for use in electroanalysis.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical and Surface Structural Characterization of Hydrogen Plasma Treated Glassy Carbon Electrodes

and¹,

Swain²,

and³

et al. 1996

Langmuir

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Electrochemical and structural characterization of glassy carbon (GC) electrodes exposed to the plasma conditions necessary to nucleate and grow diamond have been performed for the first time. The electrodes are referred to as diamond-coated (DGC) if the surface was exposed to a CH4/H2 plasma and as hydrogenated (HGC) if the surface was exposed to only an H2 plasma. Continuous diamond films were formed on the surfaces exposed to both plasma conditions, but due to poor adhesion, the films were easily lifted, exposing a modified GC surface. The results presented demonstrate that these modified surfaces exhibit lower voltammetric background currents and higher faradaic currents for Fe(CN)6 4-/3than does freshly polished GC. The enhanced signal-to-background (S/B) ratios lead to lower limits of detection for this redox analyte. The electrodes exhibited near-Nernstian behavior (∆Ep ∼ 70-85 mV) for this redox analyte without any conventional surface pretreatment, and the response remained stable for long periods of time up to several weeks. The nucleation and growth mechanism of diamond on GC appears to first involve hydrogenation of the unsaturated edge plane sites on the surface, producing an sp 3 bonded "diamond-like" phase. These surfaces are relatively oxygen-free, as hydrogen chemisorbs at the edge plane sites, replacing the oxygen functional groups. Formation of this surface phase is followed by subsequent nucleation and growth of a diamond film. Voltammetric data for Fe(CN)6 4-/3-, Ru(NH3)6 2+/3+ , Fe 2+/3+ , and ascorbic acid at these surfaces are presented as are structural characterization data by scanning electron microscopy, atomic force microscopy, Raman spectroscopy, and auger electron spectroscopy.

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“…Advantageous utilization of these unique properties has been the motivation of our group's efforts to investigate boron-doped diamond as a new electrode material for electroanalysis. Unlike the more extensively studied carbonaceous electrodes (e.g., highly oriented pyrolytic graphite, glassy carbon, and carbon fibers), the use of diamond in electrochemistry has only recently been reported. − …”

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confidence: 99%

Oxidation of Azide Anion at Boron-Doped Diamond Thin-Film Electrodes

1998

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The oxidation of dissolved inorganic azide anion in aqueous media was investigated using high-quality, boron-doped diamond thin-film electrodes. Linear sweep and differential pulse voltammetry, along with flow injection analysis in the amperometric detection mode, were used to study the reaction at neutral pH as a function of the potential sweep rate, analyte concentration, and electrolyte composition. Comparison experiments were performed using polished glassy carbon. Azide undergoes an irreversible oxidation (1 e-/equiv) at both of these carbon electrodes, presumably with nitrogen as the primary product. A linear dynamic range of 3−4 orders of magnitude and a detection limit as low as 0.1 μM (4.3 ppb) at a S/N = 3 were observed for diamond in the voltammetric measurements. The flow injection analysis results for diamond indicated a linear dynamic range of 5 orders of magnitude and a detection limit of 8 nM (0.3 ppb) at a S/N = 3. The diamond response was generally reproducible from film to film, and the background signal and signal-to-background ratio were extremely stable for up to 12 h of continuous use. The results demonstrate that this new electrode material serves as an analytically useful substrate for the detection of azide anion and exhibits superior performance characteristics compared with glassy carbon.

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The electrochemical behavior of diamond coated molybdenum

Cited by 27 publications

References 4 publications

Anthraquinonedisulfonate Electrochemistry: A Comparison of Glassy Carbon, Hydrogenated Glassy Carbon, Highly Oriented Pyrolytic Graphite, and Diamond Electrodes

Anthraquinonedisulfonate Electrochemistry: A Comparison of Glassy Carbon, Hydrogenated Glassy Carbon, Highly Oriented Pyrolytic Graphite, and Diamond Electrodes

Electrochemical and Surface Structural Characterization of Hydrogen Plasma Treated Glassy Carbon Electrodes

Oxidation of Azide Anion at Boron-Doped Diamond Thin-Film Electrodes

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