J Solid State Electrochem (2000) 4: 383389

Springer-Verlag 2000

ORIGINAL PAPER

Andrew J. Saterlay Shelley J. Wilkins

Christiaan H. Goeting John S. Foord
Richard G. Compton Frank Marken

Sonoelectrochemistry at highly boron-doped diamond electrodes:

silver oxide deposition and electrocatalysis
in the presence of ultrasound
Received: 17 March 2000 / Accepted: 10 April 2000

Abstract The use of boron-doped diamond has a considerable impact in electrochemistry owing to the wide
potential range accessible, low background currents,
extreme hardness, and the ease of chemical modication
of diamond surfaces. It is shown here that, although the
electrodeposition of silver metal is known to yield very
poorly adhering lms with a poor electrical contact, a
silver oxysalt deposit formed on anodically pre-treated
diamond surfaces adheres strongly with good electrical
contact. The deposit is stable even in the presence of
ultrasound. Voltammetric and XPS studies reveal that
the silver oxide deposit, in contrast to the silver metal
deposit, is eciently stripped from the diamond surface
by applying a suciently negative potential. The silver
oxysalt Ag7O8NO3, deposited onto two types of borondoped diamond electrodes, a 50 lm thick polycrystalline
thin lm deposited on a tungsten substrate and a polished free standing diamond plate, is shown to act as an
electrocatalyst for oxygen evolution and for the oxidation of toluene. This development opens up the possibility of boron-doped diamond being applied as an inert
and conducting substrate material for a wide range of
oxidic materials, which can then be utilised as active
electrocatalysts at high applied potentials.
Key words Electrocatalysis Diamond
Ultrasound Voltammetry Silver oxide

Introduction
Boron-doped diamond electrode materials can be grown
in a gas phase chemical vapour deposition (CVD) procedure and are available from industrial suppliers. The
A.J. Saterlay S.J. Wilkins C.H. Goeting J.S. Foord
R.G. Compton F. Marken (&)
Physical and Theoretical Chemistry Laboratory,
Oxford University, Oxford OX1 3QZ, UK
e-mail: [email protected]

unusual properties of diamond such as extreme hardness

and chemical inertness oer considerable potential for
exploitation in a multitude of demanding electrochemical applications. The reversible deposition of lithium
without intercalation [1], the selective analytical detection of serotonin and dopamine [26], waste water
treatment [7], the reduction of nitrate [8], and the electrouorination of diuorobenzene [9] are examples of
interesting developments based on boron-doped diamond electrodes. Recent reviews give further details on
the progress in this eld [1013].
Sonoelectrochemical methodology [14, 15] has been
introduced to allow electrode processes to proceed under
very fast mass transport conditions, with continuous
electrode cleaning, and with further more subtle eects
on nucleation and deposition processes. Applying power
ultrasound has been shown to be very benecial or even
essential in several electroanalytical [1618] and electrosynthetic [1921] processes. However, owing to cavitation erosion and the considerable mechanical strain
induced by the near-eld high intensity ultrasonic waves,
there are limitations for the type of electrode material
employed and the power applied. With highly borondoped diamond a novel type of electrode material is
available with both a high mechanical hardness and a
wide potential window ideal for applications of sonoelectrochemistry [22].
Both the boron-doping level [23] and the treatment of
the diamond surface [24] have been shown to result in
major changes in the rate and pathway of redox processes occurring at the diamond|solution interface. For a
number of more complex electrode processes, very slow
kinetics at bare diamond surfaces have been reported (for
example, see [25]). On the other hand, some forms of
deposit on boron-doped diamond allow very fast electron transfer with a good electrical contact to the electrode [26]. Under favourable conditions the modication
of the diamond surface with a catalyst may allow a reaction pathway to be ``selected'' and the boron-doped
diamond substrate may act as a versatile support with
good electrical conductivity. A rst report on the use of

384

boron-doped diamond for an anodic electrocatalytic

processs by Angus et al. [27] has appeared recently.
In the present study the oxidation of Ag+ in aqueous
media at boron-doped diamond electrodes and in the
presence of power ultrasound is investigated. Under these
conditions the formation of silver oxysalt deposits [28] on
anodically pretreated boron-doped diamond electrodes is
shown to result in a surface modication with strongly
adhering and catalytically active characteristics. It is
shown that in the presence of organic materials such as
toluene, preferential oxidation of the organic substrate at
the catalyst occurs. The combination of boron-doped
diamond as highly conducting but inert substrate material with an electrocatalytically active metal oxide deposit
is proposed as a new approach to ecient and selective
electrocatalysis at high applied potentials.

Experimental
Reagents
Chemical reagents such as K4Fe(CN)6, K3Fe(CN)6, AgNO3, KCl,
KNO3, and HNO3 (all Aldrich) were obtained commercially in analytical or the highest available purity and used without further purication. Water was taken from an Elgastat lter system (Elga, High
Wycombe, Bucks, UK) with a resistivity of not less than 18 Ohm cm.
Argon (BOC, Pureshield) used as an inert atmosphere and hydrogen,
methane, and diborane (BOC) used for CVD synthesis were used as
supplied. Tungsten substrates (5 mm diameter rod, Goodfellows)
were employed for the synthesis of boron-doped diamond lms.
Instrumentation
The electrochemical cell [29] (volume 250 ml) employed for sonoelectrochemical measurements consisted of a glass cooling coil
connected to a thermostatted bath, a platinum counter electrode, a
saturated Calomel reference electrode (SCE, Radiometer Kopenhagen, REF 401), the diamond working electrode tted into a
Teon holder and placed at the bottom of the cell facing the
transducer horn tip, and an argon inlet. The ultrasonic processor, a
Sonics & Materials VXC400 (20 kHz, 400 W) with 13 mm diameter titanium tip or a Hielscher UP200G system (24 kHz, 200 W)
tted with a 13 mm diameter glass horn (Dr. Hielscher, Stuttgart,
Germany), were both electrically insulated from the electrochemical system and suitable for strongly acidic environments. The
ultrasound intensity was determined calorimetrically [30, 31].
Electrochemical measurements were performed with a PGSTAT 20
AUTOLAB system (Eco Chemie, Netherlands) at a temperature of
25 2 C. The synthetic diamond lms were characterised by
scanning electron microscopy (SEM) with a JEOL JSM-5200 system, atomic force microscopy (AFM) with a Topometrix 2010
Discoverer system (Thermo Microscopes, Bicester, UK), and by
Raman spectroscopy (Dilor Labram spectrometer with 20 mW
He-Ne laser). The X-ray photoelectron spectra (XPS) were recorded at approximately 10)9 mbar with an ESCA300 using
monochromatised Al Ka (1486.6 eV) X-ray radiation with 0.25 eV
electron energy resolution.
Diamond electrodes
Two dierent types of boron-doped diamond electrodes were used.
The rst type consisted of a polycrystalline thin lm deposit of
diamond (50 lm thickness) grown on a 5 mm diameter tungsten

support via a CVD procedure as described previously [32]. The

Raman study of the lm deposit indicates the presence of high
quality diamond with a boron doping level of 10201021 cm)3.
The surface of this polycrystalline diamond deposit is shown in
Fig. 1a. The crystals size is typically 1020 lm. In order to oxidise
the surface of the diamond electrode, a potential cycling procedure
employing 10 potential cycles over a potential range from 0 to 3 V
vs. SCE in 0.2 M phosphate buer at pH 2 was employed [32].
Further, a free-standing plate of boron-doped diamond (De
Beers Industrial Diamond Division, Ascot, UK) of 5 5 0.6 mm
dimensions [24] was employed, mounted in a Teon housing using
Araldite (Ciba Polymers, CY219), with an electrical connection to
the rear side via a brass rod, attached using silver epoxy resin (RS).
Raman spectra of this diamond material also are consistent with
high quality diamond with a boron-doping level of 10191020 cm)3.
The surface of this diamond electrode, which was obtained in a
polished state (see Fig. 1b), is smooth to a nanometer scale with
only small imperfections between crystal boundaries.

Results and discussion

Sonovoltammetric oxidation of Fe(CN)46
at a boron-doped diamond thin lm electrode
Cyclic voltammetric experiments with boron-doped
3 =4
diamond electrodes employing the Fe(CN)6
redox
couple (Eq. 1) in aqueous KCl provided a suitable redox
system for the characterisation of the diamond electrode
surface properties [33] and the mass transport under
diusion limiting conditions:
Fe(CN)36 e

Fe(CN)46

In Fig. 2 a cyclic voltammogram together with a sonovoltammogram are shown. The 5 mm diameter polycrystalline boron-doped diamond electrode has been
activated prior to the experiment by anodising in 0.2 M
phosphate buer at pH 2 by cycling the potential up to
+3.0 V vs. SCE in phosphate buer (see Experimental).
Well-dened cyclic voltammetric responses for the
3 =4
Fe(CN)6
redox system can be observed.
In the presence of ultrasound the current increases
considerably (Fig. 2b). The high limiting current, Ilim
0.53 mA, is predominantly due to the ow of liquid close
to the electrode surface induced by the high intensity
ultrasound on macro and micro scales [34]. The limiting
current for the oxidation of 1 mM Fe(CN)46 in aqueous
0.1 M KCl induced by the 24 kHz insonation with the
glass horn may be used to estimate the diusion layer
thickness, d, a parameter describing the rate of mass
transport (Eq. 2):
Ilim

nF DAc
d

In this equation the limiting current, Ilim, is determined

by n, the number of electrons transferred per molecule in
the redox process, F, the Faraday constant, D, the diffusion coecient, A, the area of the electrode, c, the
concentration, and the diusion layer thickness, d. For
the conditions used in Fig. 2 and a diusion coecient
[35] of D(Fe(CN)46 ) 0.65 10)9 m2 s)1, a typical

385
Fig. 1a,b AFM images of boron-doped diamond electrodes:
a surface of an ``as grown''
diamond lm on a tungsten
substrate and b a polished
boron-doped diamond surface
(De Beers)

diusion layer thickness of 9 lm can be determined. By

varying the distance between horn emitter and working
electrode, diusion layer thicknesses of less than 1 lm
are accessible [34]. More detailed models for the mass
transport induced by ultrasound in aqueous media have
been proposed [36] but are not essential in the context of
the present study.
Sonovoltammetric oxidation of Ag+
at boron-doped diamond electrodes
The voltammetric reduction and oxidation of Ag+ dissolved in aqueous solution at a boron-doped diamond
electrode in the absence of ultrasound has been studied by
several authors [37, 38]. Recent work by Vinokur et al.

[28] gives a detailed account of the mechanism of the

electrochemical deposition of both silver metal and silver
oxysalts onto boron-doped diamond surfaces. The oxidation of Ag+ to Ag2+ is a commercially important process for the detoxication of wastes [39, 40] and more
specically the degradation of toxic organic compounds
[41]. This process has to be conducted in the presence of
high concentrations of nitric acid to solubilise the Ag2+
cation.
Voltammetric responses for the reduction and oxidation of 1 mM Ag+ at a 5 mm diameter polycrystalline
boron-doped diamond electrode in the presence of an
acidic supporting electrolyte, HNO3, are shown in
Fig. 3. The onset of the reduction process (Eq. 3) can be
seen to lead to the slow increase of the cathodic current
until a limiting current, Ilim 0.48 mA, is reached:

386

Fig. 2 a Cyclic voltammogram for the oxidation of 1 mM Fe(CN)46

obtained in 0.1 M KCl solution at a 5 mm diameter boron-doped
diamond lm electrode with a scan rate of 0.1 V s)1. b Cyclic
sonovoltammogram obtained under the same conditions (30 W cm)2,
24 kHz ultrasound, 10 mm electrode to horn distance)

Ag (aq) e

Ag(solid)

This diusion-controlled limiting current is consistent

with a diusion layer thickness of d 23 lm based on a
diusion coecient of DAg 1.5 10)9 m2 s)1 [42]
(Eq. 2). The diusion-controlled limiting current associated with the deposition of silver metal remains constant until at a potential of 0.25 V vs. SCE, when anodic
stripping of the metal deposit commences.
The current uctuation superimposed on the sonovoltammetric limiting current is in agreement with mass
transport control [14, 15]. It is interesting to note the
eect of increasing the supporting electrolyte concentration. On the polycrystalline thin lm diamond electrode, both the reduction and the ``stripping'' process
become substantially less well-dened in the presence of
a higher concentration of supporting electrolyte (Fig. 3).
The metal stripping process has been shown to be incomplete, with silver metal deposit left behind on the
surface of the diamond electrode after the potential has
been scanned positive of the stripping process [28]. An
SEM and XPS study on the state of the polycrystalline
boron-doped diamond electrode surface immersed in
1 mM Ag+ in 1 M HNO3 after cycling the potential to
)0.25 V vs. SCE and back to 0.75 V vs. SCE with a scan
rate of 0.1 V s)1 revealed that, even after stripping the
silver metal deposit, the electrode surface remained
partially covered with silver metal. SEM images in
backscatter mode indicate approximately 0.4% surface
area covered with silver.
The oxidation of aqueous Ag+ in the presence of
NO3 is known to yield a deposit of a silver oxysalt [43]
with a composition Ag7O8NO3 (Eq. 4). Only in the
presence of high concentrations of acid is the Ag2+
cation suciently soluble to be formed directly.

Fig. 3 Cyclic sonovoltammograms for the reduction and oxidation of

1 mM Ag+ obtained in HNO3 solution (concentration a 0.02 M,
b 0.04 M, c 0.08 M, d 0.16 M) at a 5 mm diameter boron-doped
diamond lm electrode with a scan rate of 0.1 V s)1, 30 W cm)2,
24 kHz ultrasound and 12 mm electrode to horn distance

7Ag (aq) 8H2 O NO3 (aq)

Ag7 O8 NO3 (solid) 10e 16H (aq)

In Fig. 3 it can be seen that the oxidation process is

followed by a characteristic stripping peak upon reversal
of the scan direction. Both the onset of the deposition
process and the potential for the stripping process are
aected by the concentration of nitric acid. In Fig. 4a
voltammograms obtained for the oxidation of 1 mM
Ag+ in aqueous HNO3 at a polished boron-doped diamond electrode are shown. At this type of diamond
surface, very similar voltammetric characteristics are
observed. The onset of silver oxysalt deposition as well
as the stripping response shift to more positive potentials
as the concentration of protons is increased. The onset
potentials of the stripping peaks exhibit a characteristic
shift of approximately 95 mV per unit pH change, in
agreement with the process described by Eq. 4. In

387

Fig. 4 a Cyclic voltammograms for the oxidation of 1 mM Ag+

obtained in 0.1 M HNO3 at pH i 1.09, ii 1.14, iii 1.31, iv 1.62, v 2.15,
and vi 3.14 (pH adjusted by addition of 10 M NaOH). b Cyclic
voltammograms for the oxidation of 1 mM Ag+ obtained in 1 mM
HNO3 i under continuous ultrasonic irradiation (38 W cm)2, 10 mm
horn to electrode separation), ii ultrasound during oxidation, potential
held at 1.375 V vs. SCE for 120 s (silent), silent reduction, and iii as in
i except held at 1.375 V vs. SCE for 60 s during negative sweep.
c Cyclic voltammograms for the oxidation of Ag+ i 12 lM, ii
258 lM, iii 510 lM, and iv 1.96 mM in 0.1 M HNO3

Fig. 4b the eect of ultrasound on the silver oxysalt

deposit formation in a solution containing 1 mM Ag+
and 1 mM HNO3 is demonstrated. The response (i) has
been obtained by cycling the potential with 0.1 V s)1 in
the presence of 38 W cm)2 ultrasound. Switching the
ultrasound o at a potential of 1.375 V vs. SCE and
holding the potential for 120 s has only a minor eect
(response ii). Holding the potential scan at a potential at
which no further deposition occurs, E +1.375 V vs.
SCE, in the presence of ultrasound can be seen (response
iii) to lead to a virtually identical voltammetric trace.
Therefore both further deposition at a potential of
+1.375 V vs. SCE and the removal of the silver oxysalt
deposit by ultrasound-induced interfacial cavitation can

be ruled out. The deposit appears to remain rigidly attached. Aside from the electrosynthetic possibilities
discussed here, the silver oxysalt deposition and stripping procedure oers scope for development into a
quantitative analytical method (Saterlay AJ, Marken F,
Foord JS, Compton RG, submitted).
The cathodic stripping process in which the silver
oxysalt is reduced back to Ag+(aq) is relatively fast, in
contrast to the stripping of metal deposits (vide supra).
An SEM and XPS study of a polycrystalline borondoped diamond electrode on a tungsten substrate immersed in 1 mM Ag+ (1 M HNO3) after cycling the
potential from 0.5 V vs. SCE to 1.75 V vs. SCE and
back with a scan rate of 0.1 V s)1 revealed that, in this
case, no silver deposit remains on the electrode surface
at 0.5 V vs. SCE. That is, the electrical contact between
electrode and deposit is good and the stripping process
essentially complete. The considerable mismatch between anodic and cathodic current can be explained via
a catalytic process in which water is oxidised to oxygen.
In Fig. 3 it can be seen that, at the potential at which the
silver oxysalt deposition commences, there is an immediate increase in anodic current. This current is considerably higher than that expected for the mass transport
controlled deposition process.
The eect of the concentration of Ag+ on the voltammetric response for the formation and stripping of
Ag7O8NO3 in the absence of ultrasound is shown in
Fig. 4c. The catalytic current associated with the water
oxidation develops even at a very low concentration of
12 lM Ag+ in 0.1 M aqueous HNO3 (response i).
However, the rapid increase in current is much more
pronounced at higher concentration. The peak-shaped
feature is probably associated with the depletion of silver
from the solution during the deposition process and/or
the formation of gas bubbles on the electrode surface in
the absence of ultrasound.
By increasing the concentration of acid to 6 M HNO3
the formation of the silver oxysalt deposit ceases (not
shown); however, the anticipated formation of soluble
Ag2+ at the boron-doped diamond electrode surface still
cannot be detected even up to potentials of 2.5 V vs.
SCE. It appears likely that the heterogeneous electron transfer for the Ag2+/+ redox couple is associated
with slow kinetics at diamond electrodes in the presence
of a high concentration of HNO3.
At lower concentration of HNO3, silver oxysalt is
formed which is acting as catalyst for the formation of
oxygen. After the onset of silver oxysalt deposition the
dramatic rise in anodic current (Fig. 3) suggests a high
catalytic activity and a good electrical contact between
oxide deposit and diamond surface. The nding may be
interpreted in terms of highly boron-doped diamond
being a very good conductor for electrical charges and a
very good substrate for carrying active catalyst materials. Recent work on the anodic deposition of other types
of metal oxides, such as PbO2 and MnO2, on borondoped diamond surfaces [44, 45] demonstrates the
general applicability of the method.

388

Sonovoltammetric oxidation of toluene

at modied boron-doped diamond electrodes
The voltammetric characteristics of the silver oxysalt
deposit suggest that a high catalytic activity of the deposit is responsible for the high anodic current observed
at a potential of approximately 1.6 V vs. SCE (Fig. 3).
The presence of organic materials in the aqueous solution phase can be shown to have a considerable eect on
the voltammetric response for the silver oxysalt formation and the catalytic current. Here, toluene is used as
a model system in order to explore the possibility of
diamond-based electrocatalysis. The oxidation of toluene in the presence of a homogeneous silver catalyst has
been studied [4648] and benzaldehyde has been identied as the main product. In Fig. 5a it can be seen that
the presence of toluene, employing a saturated solution
with 0.4 volume% toluene emulsied in 0.5 M HNO3,
causes the onset of the anodic current response to shift
to more positive potentials. That is, the deposition of the
silver oxysalt requires a higher overpotential in the
presence of toluene. However, once the catalytically
active deposit is formed the current increases considerably compared to the current observed in the absence of
toluene. Also the current response during the reverse
potential scan is increased. That is, the silver oxysalt
deposit is preferentially oxidising the organic material
even in the presence of a huge excess of water. In the
presence of ultrasound, very similar characteristics can
be observed (Fig. 5b). The formation of the silver oxysalt deposit occurs at a more positive potential in the
presence of ultrasound and the current associated with
the oxidation of toluene appears to be increased. However, the mass transport enhancement, which is known
to strongly aect kinetically fast processes, is rather
small and the process may therefore be considered to be

Fig. 5 a Cyclic voltammograms obtained for i 0.5 M HNO3, ii in the

presence of 3.64 mM Ag+, and iii in the presence of 3.64 mM Ag+ and
0.4 volume% toluene emulsion. b Cyclic voltammograms obtained for
the oxidation of 1.96 mM Ag+ in a 0.4 volume% toluene/0.5 M
HNO3 emulsion: i under silent conditions, ii under ultrasound
irradiation (38 W cm)2, 10 mm horn to electrode separation)

controlled by the kinetics of the heterogeneous process.

Mechanistic details, such as the ratio of oxygen evolution and toluene oxidation in the presence of ultrasound
and the distribution of products formed in this oxidation
process, are under further investigation.

Conclusions
Boron-doped diamond is a versatile electrode material
not only in bare or surface-modied form, but it may
also act as substrate material in electrocatalysis. In
particular, metal oxide deposits appear to form on
anodised diamond with good adhesion and good electrical conductivity. The wide potential window accessible with boron-doped diamond may therefore allow thin
layers of metal oxide deposits to be employed in electrocatalytic processes even in cases in which the oxide
itself is not suciently electrically conducting. Further,
the use of power ultrasound to enhance the rate of the
heterogeneous electrocatalytic process is possible and
may lead to higher eciencies, especially in the case of
reactions with low substrate concentrations.
Acknowledgements F.M. thanks the Royal Society for a University Research Fellowship and New College, Oxford, for the award
of a stipendiary Lectureship. S.J.W. thanks Glaxo Wellcome and
BBSRC for a CASE award. G. Scarsbrook, R.S. Sussmann, and
A.J. Whitehead (De Beers Industrial Diamond Division, UK) are
gratefully acknowledged for generous support of the diamond
project. A.J.S. thanks Alcan and the EPSRC for a CASE studentship and the EPSRC for nancial support.

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