Effect of sp2-bonded nondiamond carbon impurity on the response of boron-doped polycrystalline diamond thin-film electrodes

Jason Alan Bennett, Jian Wang, Yoshiyuki Show, Greg M. Swain

Research output: Contribution to journalArticle

123 Citations (Scopus)

Abstract

The physical and electrochemical properties of boron-doped polycrystalline diamond thin-film electrodes, prepared with varying levels of sp 2-bonded nondiamond carbon impurity, were systematically investigated. This impurity was introduced through adjustment of the methane-to-hydrogen (C/H) source gas ratio used for the deposition. Volumetric gas ratios of 0.3, 0.5, 1, 2, 3, and 5% were employed. Proportional increases in the fraction of grain boundary, the extent of secondary nucleation, and the sp2-bonded carbon impurity content resulted in increasing C/H ratio. Variations in the morphology and microstructure were monitored using atomic force microscopy (AFM) and Raman spectroscopy, respectively. The electrode response was assessed using Fe(CN)63-/4-, Ru(NH 3)63+/2+, Fe3+/2+, and 4-tert-butylcatechol (4-tBC). All were 1 mM in concentration and dissolved in either l M KCl or 0.1 M HClO4. While increased sp2-bonded carbon content had little effect on the cyclic voltammetric peak separation (ΔEp) and peak current for the first two redox systems, the impurity had a significant impact on the latter two, as ΔEp decreased proportionally with increased sp2-bonded carbon content. The effect of the impurity on the reduction of oxygen in 0.1 M HClO4 and 0.1 M NaOH was also investigated. A direct correlation was found between the relative amount of the impurity, as estimated from Raman spectroscopy, and the overpotential for oxygen reduction. The greater the nondiamond content, the lower the kinetic overpotential for the reduction reaction. Tafel plots yielded an apparent exchange current density that increased and a transfer coefficient that decreased with the increased nondiamond carbon content. The results demonstrate that the grain boundaries, and the sp2 carbon impurity presumably residing there, can have a significant impact on the electrode reaction kinetics for certain redox systems and little influence for others.

Original languageEnglish (US)
JournalJournal of the Electrochemical Society
Volume151
Issue number9
DOIs
StatePublished - Oct 18 2004

Fingerprint

Boron
Diamond films
Carbon
Impurities
Thin films
Electrodes
Raman spectroscopy
Grain boundaries
Gases
Oxygen
Hydrogen
Methane
Electrochemical properties
Reaction kinetics
Atomic force microscopy
Ion exchange
Nucleation
Current density
Physical properties
Microstructure

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Renewable Energy, Sustainability and the Environment
  • Surfaces, Coatings and Films
  • Electrochemistry
  • Materials Chemistry

Cite this

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title = "Effect of sp2-bonded nondiamond carbon impurity on the response of boron-doped polycrystalline diamond thin-film electrodes",
abstract = "The physical and electrochemical properties of boron-doped polycrystalline diamond thin-film electrodes, prepared with varying levels of sp 2-bonded nondiamond carbon impurity, were systematically investigated. This impurity was introduced through adjustment of the methane-to-hydrogen (C/H) source gas ratio used for the deposition. Volumetric gas ratios of 0.3, 0.5, 1, 2, 3, and 5{\%} were employed. Proportional increases in the fraction of grain boundary, the extent of secondary nucleation, and the sp2-bonded carbon impurity content resulted in increasing C/H ratio. Variations in the morphology and microstructure were monitored using atomic force microscopy (AFM) and Raman spectroscopy, respectively. The electrode response was assessed using Fe(CN)63-/4-, Ru(NH 3)63+/2+, Fe3+/2+, and 4-tert-butylcatechol (4-tBC). All were 1 mM in concentration and dissolved in either l M KCl or 0.1 M HClO4. While increased sp2-bonded carbon content had little effect on the cyclic voltammetric peak separation (ΔEp) and peak current for the first two redox systems, the impurity had a significant impact on the latter two, as ΔEp decreased proportionally with increased sp2-bonded carbon content. The effect of the impurity on the reduction of oxygen in 0.1 M HClO4 and 0.1 M NaOH was also investigated. A direct correlation was found between the relative amount of the impurity, as estimated from Raman spectroscopy, and the overpotential for oxygen reduction. The greater the nondiamond content, the lower the kinetic overpotential for the reduction reaction. Tafel plots yielded an apparent exchange current density that increased and a transfer coefficient that decreased with the increased nondiamond carbon content. The results demonstrate that the grain boundaries, and the sp2 carbon impurity presumably residing there, can have a significant impact on the electrode reaction kinetics for certain redox systems and little influence for others.",
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Effect of sp2-bonded nondiamond carbon impurity on the response of boron-doped polycrystalline diamond thin-film electrodes. / Bennett, Jason Alan; Wang, Jian; Show, Yoshiyuki; Swain, Greg M.

In: Journal of the Electrochemical Society, Vol. 151, No. 9, 18.10.2004.

Research output: Contribution to journalArticle

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T1 - Effect of sp2-bonded nondiamond carbon impurity on the response of boron-doped polycrystalline diamond thin-film electrodes

AU - Bennett, Jason Alan

AU - Wang, Jian

AU - Show, Yoshiyuki

AU - Swain, Greg M.

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AB - The physical and electrochemical properties of boron-doped polycrystalline diamond thin-film electrodes, prepared with varying levels of sp 2-bonded nondiamond carbon impurity, were systematically investigated. This impurity was introduced through adjustment of the methane-to-hydrogen (C/H) source gas ratio used for the deposition. Volumetric gas ratios of 0.3, 0.5, 1, 2, 3, and 5% were employed. Proportional increases in the fraction of grain boundary, the extent of secondary nucleation, and the sp2-bonded carbon impurity content resulted in increasing C/H ratio. Variations in the morphology and microstructure were monitored using atomic force microscopy (AFM) and Raman spectroscopy, respectively. The electrode response was assessed using Fe(CN)63-/4-, Ru(NH 3)63+/2+, Fe3+/2+, and 4-tert-butylcatechol (4-tBC). All were 1 mM in concentration and dissolved in either l M KCl or 0.1 M HClO4. While increased sp2-bonded carbon content had little effect on the cyclic voltammetric peak separation (ΔEp) and peak current for the first two redox systems, the impurity had a significant impact on the latter two, as ΔEp decreased proportionally with increased sp2-bonded carbon content. The effect of the impurity on the reduction of oxygen in 0.1 M HClO4 and 0.1 M NaOH was also investigated. A direct correlation was found between the relative amount of the impurity, as estimated from Raman spectroscopy, and the overpotential for oxygen reduction. The greater the nondiamond content, the lower the kinetic overpotential for the reduction reaction. Tafel plots yielded an apparent exchange current density that increased and a transfer coefficient that decreased with the increased nondiamond carbon content. The results demonstrate that the grain boundaries, and the sp2 carbon impurity presumably residing there, can have a significant impact on the electrode reaction kinetics for certain redox systems and little influence for others.

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