Abstract
We investigated water interfaces of boron-doped diamond (BDD) terminated by hydrogen, oxygen, and hydroxyl groups by using density functional theory (DFT)-based molecular dynamics to elucidate the electrochemical behaviors of the as-grown and oxidized BDD electrodes. The reversible outer-sphere electron transfer on the as-grown electrode and the irreversibility on the oxidized electrode, observed in the experiment, are well explained by the BDD band position and subsurface band bending, which depend on the termination and interfacial dipoles. The reductive character of the H-terminated BDD is found, while the interface covered by the carbonyl oxygen is clearly oxidative. The redox character of the hydroxyl termination depends on the lateral hydrogen bonding network among the termination groups and is rather oxidative at the water interface. We also examined the preference of the boron position in the diamond and the stability of boron pairs and clusters. It is suggested that the wide distribution of the single boron dopants is crucial to the BDD conductivity, against the tendency of clustering. These results give novel atomistic aspects of the termination and the boron doping effects on the BDD electrodes, which is useful for further exploration of the efficient electrochemical applications of BDD.
| Original language | English |
|---|---|
| Pages (from-to) | 22040-22052 |
| Number of pages | 13 |
| Journal | Journal of Physical Chemistry C |
| Volume | 118 |
| Issue number | 38 |
| DOIs | |
| Publication status | Published - 2014 Sep 25 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Electronic, Optical and Magnetic Materials
- Surfaces, Coatings and Films
- Energy(all)
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First principles calculation study on surfaces and water interfaces of boron-doped diamond. / Futera, Zdenek; Watanabe, Takeshi; Einaga, Yasuaki; Tateyama, Yoshitaka.
In: Journal of Physical Chemistry C, Vol. 118, No. 38, 25.09.2014, p. 22040-22052.Research output: Contribution to journal › Article
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TY - JOUR
T1 - First principles calculation study on surfaces and water interfaces of boron-doped diamond
AU - Futera, Zdenek
AU - Watanabe, Takeshi
AU - Einaga, Yasuaki
AU - Tateyama, Yoshitaka
PY - 2014/9/25
Y1 - 2014/9/25
N2 - We investigated water interfaces of boron-doped diamond (BDD) terminated by hydrogen, oxygen, and hydroxyl groups by using density functional theory (DFT)-based molecular dynamics to elucidate the electrochemical behaviors of the as-grown and oxidized BDD electrodes. The reversible outer-sphere electron transfer on the as-grown electrode and the irreversibility on the oxidized electrode, observed in the experiment, are well explained by the BDD band position and subsurface band bending, which depend on the termination and interfacial dipoles. The reductive character of the H-terminated BDD is found, while the interface covered by the carbonyl oxygen is clearly oxidative. The redox character of the hydroxyl termination depends on the lateral hydrogen bonding network among the termination groups and is rather oxidative at the water interface. We also examined the preference of the boron position in the diamond and the stability of boron pairs and clusters. It is suggested that the wide distribution of the single boron dopants is crucial to the BDD conductivity, against the tendency of clustering. These results give novel atomistic aspects of the termination and the boron doping effects on the BDD electrodes, which is useful for further exploration of the efficient electrochemical applications of BDD.
AB - We investigated water interfaces of boron-doped diamond (BDD) terminated by hydrogen, oxygen, and hydroxyl groups by using density functional theory (DFT)-based molecular dynamics to elucidate the electrochemical behaviors of the as-grown and oxidized BDD electrodes. The reversible outer-sphere electron transfer on the as-grown electrode and the irreversibility on the oxidized electrode, observed in the experiment, are well explained by the BDD band position and subsurface band bending, which depend on the termination and interfacial dipoles. The reductive character of the H-terminated BDD is found, while the interface covered by the carbonyl oxygen is clearly oxidative. The redox character of the hydroxyl termination depends on the lateral hydrogen bonding network among the termination groups and is rather oxidative at the water interface. We also examined the preference of the boron position in the diamond and the stability of boron pairs and clusters. It is suggested that the wide distribution of the single boron dopants is crucial to the BDD conductivity, against the tendency of clustering. These results give novel atomistic aspects of the termination and the boron doping effects on the BDD electrodes, which is useful for further exploration of the efficient electrochemical applications of BDD.
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U2 - 10.1021/jp506046m
DO - 10.1021/jp506046m
M3 - Article
VL - 118
SP - 22040
EP - 22052
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
SN - 1932-7447
IS - 38
ER -