DOI: 10.1002/cphc.200500589 level is increased.

This trend allows us to choose an arbitrary

frequency and to set the trigger level accordingly, as demon-
strated in the inset. To implement this for a study of the effect
Ultrafast Chronoamperometry of of applied potential, it is necessary to determine the trigger
Single Impact Events in Acoustically level separately at each potential by producing similar plots.
For the potential-dependent experiments conducted, a fre-
Agitated Solid Particulate quency of 0.15 Hz was chosen to set the trigger level.
Suspensions First, 30 mg of graphite and 20 cm3 0.1 m HClO4 electrolyte
solution were added to the cell shown in Figure 1. Upon soni-
Antony D. Clegg,[a] Neil V. Rees,[b] Craig E. Banks,[a] and cation, a suspension was formed. With continued sonication,
Richard G. Compton*[a] the selected potential was applied to the working electrode.

The direct detection of interactions between single particles

and electrode surfaces is a relatively recent phenomenon.[1–10]
Most of the work conducted in this area has concentrated on
adhesion events of colloidal particles on mercury electro-
des.[1–7, 10] The focus herein is the study of time-resolved chro-
noamperometric signals of single impact events of various
solid particles on a polycrystalline platinum electrode under
conditions of acoustic streaming. Several important advances
are presented that have been made since this type of process
was first studied in 2004 by Rees et al.[8] Chief among these,
are experiments that demonstrate the potential to determine
the number and size of particles suspended in solution using
this technique.
The interaction of rigid particles with the electrode surface
during acoustic streaming occurs on a drastically shorter time-
scale than for systems involving nonrigid particles under silent
conditions, on the order of 1–5 ms. In order to record a chro-
noamperometric signal that is fully time-resolved, it is necessa-
ry to employ an ultrafast potentiostat to monitor the current
response of the electrode on the sub-microsecond level. Our
potentiostat was built in-house, has an upper scan rate limit of
about 2.2 MV
1, and is based on the design of Amatore Figure 1. Schematic experimental set-up.
et al.[11, 12]
In order to record a current spike, it is necessary to set a
trigger level on the oscilloscope which, when crossed, signals
the scope to store and display the current output from the po-
tentiostat a short time before and after the triggering event.
Ideally, the trigger level would be set at zero so that all spikes
can be recorded. However, this is rendered impossible by elec-
trical noise, which can be reduced, but never eliminated com-
pletely. So, a systematic method must be devised to set the
trigger level in such a way that experiments can be directly
compared.
The inset in Figure 2 shows the experimentally measured de-
pendency of the spike frequency on the trigger level. The
spike frequency decays in a predictable fashion as the trigger

[a] A. D. Clegg, Dr. C. E. Banks, Prof. Dr. R. G. Compton

Physical and Theoretical Chemistry Laboratory
University of Oxford, South Parks Road
Oxford, OX1 3QZ (UK)
Fax: (+ 44) 1865-275410
E-mail: richard.compton@chem.ox.ac.uk Figure 2. Potential dependence of the average spike areas for graphite
[b] Dr. N. V. Rees powder (bottom curve) and DPPD modified graphite powder (upper curve).
Department of Chemistry, Cardiff University, P.O. Box 912 The inset shows the effect of the trigger level on the observed spike fre-
Cardiff CF10 3TB (UK) quency.

ChemPhysChem 2006, 7, 807 – 811 > 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 807
As reported previously,[8, 9] current spikes of duration 1–5 ms
were observed. 16 individual spikes were then recorded and
averaged using the oscilloscope to determine a “mean spike”.
The potential was then varied between
0.5 V and + 0.7 V (vs.
SCE). At more negative potentials, any trend was obscured by
hydrogen evolution. The polarity of the current spikes was
found to invert at a potential of
0.16 V (vs. SCE). Previous in-
vestigations have established that the inversion potential cor-
responds to the potential of zero charge (PZC) for the metal/
electrolyte interface.[8, 9] The charge transfer involved during
the impact event corresponds to the areas of the spikes which
are determined by integration in Microcal OriginG 7.0. The
measured areas are shown in Figure 2. It can be seen that the
magnitude of the charge increases linearly as the potential is
moved away from the inversion point. At  + 0.4 V however, it
appears as if a plateau is reached. A reasonable explanation for
this plateau is that it represents the maximum charge that can
be held by the average particle observed, which according to
the data, is about 7 H 10
11 C. Note that the solution in the ex-
periments discussed above does not contain materials which
are electroactive at the potentials employed; the spikes repre-
sent interactions of the particles with the electrode rather than
perturbation of any diffusional current.
For comparison, exactly the same procedure was performed
using 30 mg of diphenyl-1,4-phenylenediamine (DPPD) modi-
fied graphite powder instead of unmodified graphite. The
modification was performed according to a literature proce-
dure.[13] Figure 2 compares the resulting spike areas to the un-
modified graphite powder. It is clear that in the region where
any oxidative processes would occur, the two analyses virtually
overlay each other.
To confirm that the modification of the graphite was suc-
cessful, the synthesised powder was abrasively immobilised
onto a basal plane pyrolytic graphite electrode. The electrode
was then introduced into a standard electrochemical cell con-
taining 0.1 m HClO4 electrolyte and a cyclic voltammetric ex-
periment was conducted. The resulting voltammogram is
shown in Figure 3. From this, we can clearly see that the
Figure 3. Cyclic voltammogram of DPPD-modified graphite powder abrasive-
ly immobilised onto a basal plane pyrolytic graphite electrode.
808 www.chemphyschem.org > 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
powder is indeed modified as intended, with two oxidative
processes visible. The conclusion must be therefore that on
the timescale of an impact, NO processes occur which result in
the oxidation of functional groups attached to the graphite
particles. This is in disagreement with a previous study,[8] but
the cause of the different results is almost certainly the rigor-
ous treatment of the trigger level used here.
The potential dependence of the spike characteristics were
also investigated for glassy carbon spheres of diameter distri-
bution 10–20 mm using the same method as before. The result-
ing spike areas are shown in Figure 4. The same features that
were observed for the graphite powders are again visible—the
same inversion potential and a plateau at potentials more pos-
itive than + 0.4 V (vs. SCE).
Figure 4. Potential dependence of the average spike areas for 10–20 mm
glassy carbon powder.
Interpretation of all of the experimental data obtained up to
this point has been based on the fundamental assumption
that it is the particles impacting with the electrode surface
that are responsible for the current spikes. This assumption is
justified by the observation that in the absence of any added
particles, the spike frequency is negligible. However, a full
study of how the number of particles in the solution affects
the current spikes has never been conducted. To do this ex-
periment, the trigger level was set at an arbitrary fixed value of
5.5 mA, which is high enough to avoid any electrical noise. The
experiment was then set up in the same way as described pre-
viously, and the applied potential set to + 0.7 V (in the plateau
region), without the addition of any powder. The time taken to
record 512 spikes was then recorded for 10 mg additions of
graphite powder. The experiment was repeated for glassy
carbon spheres of sizes 20–50 mm and 80–200 mm. From
Figure 5, we can see that for a given powder, the impact fre-
quency is a linear function of the number of particles in solu-
tion. This technique could potentially be used as an analytical
tool for the determination of particle concentration.
When the same procedure is followed using alumina
powder, the results are very different. Not only is the trend
more complicated, but the impact frequencies are about
20 times lower than for the carbon based materials. The cause
ChemPhysChem 2006, 7, 807 – 811
 mina powder of varying sizes. With new data suggesting that
conductivity is important, an experiment could be designed to
re-examine that deduction. The experiment was set up as ex-
plained previously with 30 mg of 10–20 mm glassy carbon
spherical powder. The trigger level was set to a constant
5.5 mA and the applied potential to + 0.7 V. 512 spikes were
then recorded and averaged. This was repeated with glassy
carbon powders of sizes 20–50 mm, 40–80 mm and 80–200 mm.
The averaged spikes are shown in Figure 6, together with the

Figure 6. Average spike areas as a function of particle radius for glassy

carbon spheres. The inset shows the recorded spikes which increase with
particle size.

calculated areas. The linear relationship between the transfer-

red charge and the particle radius is slightly unexpected—if
the charge depends on the surface area or volume of the
sphere, a squared or cubed dependence would be observed.
However, what if the charge that the particle can hold de-
pends on the contact region with the (unsmooth) electrode?
Over 512 averaged contacts, this region would probably repre-
sent something similar to a “spherical cap”. The surface area of
a spherical cap, A, is given by Equation (1):[14]

A ¼ 2phr ð1Þ

where r is the radius of the impacting particle and h is the

Figure 5. Impact frequency as a function of mass of a) 2–20 mm graphite height of the cap, which would be constant. Thus, this type of
powder, b) 20–50 mm spherical carbon powder and c) 80–200 mm spherical
interaction with the particle would explain the linear trend we
carbon powder.
observe experimentally.
Putting together all of the evidence we have obtained up to
of these effects could be the lower conductivity of alumina. To this point:
try and confirm this supposition, the experiment was repeated
using a very resistive powder: pure CaCO3. The electrolyte was * inversion at the PZC,
replaced with 0.1 m LiClO4 to stop the powder dissolving. In * unidirectional spikes,
this case, no spikes were observed at all, suggesting that con- * linear dependence of impact frequency on th enumber of
ductivity is indeed an important consideration. particles for a given powder,
Rees et al. concluded in their 2004 paper that the size of the * conductivity important and
impacting particle has little or no influence on the observed * linear relationship between charge transferred and particle
signal.[8] However, their experiments were conducted using alu- radius

ChemPhysChem 2006, 7, 807 – 811 > 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemphyschem.org 809
enables us to construct a probable mechanism for the process
occurring at the electrode, which is given in Scheme 1. This
mechanism is an idealised model for the process that occurs
Scheme 1. Proposed mechanism for a sonically induced impact of a spherical particle on
an electrode surface. Also shown is the effect on the measured current as a function of
time.
during the impact. After contact with the electrode, the parti-
cle is represented as a squashed sphere. This is to symbolise
contact with the unsmooth electrode after 512 averaged im-
pacts. Upon initial contact with the electrode, there is a rapid
increase in the magnitude of the current. This is an effect of
the large potential difference between the electrode and the
particle. As the charge on the particle increases, the potentials
become more similar and the magnitude of the current de-
creases accordingly. When the current has returned to its origi-
nal level, the particle has effectively become part of the elec-
trode and the electrical double layer extends over its surface.
From the data, it is difficult to say precisely what happens
next. However, it is well known that electrodes that are ex-
posed to ultrasound are much less likely to undergo adsorp-
tion process.[15] This principle could be extended to enable us
to say that the likely next step in the mechanism would be the
detachment of the charged particle into solution. The unidirec-
tionality of the spikes means that there must also be a counter
electrode process in order to maintain charge neutrality.
The study of current spikes caused by sonically induced im-
pacts of single particles on an electrode has been possible for
several years[9] and we note that charged suspension of con-
ducting particles can be used synthetically [16] However, never
before has such a wide range of variables been investigated.
The dependencies of spike characteristics such as area and fre-
quency on potential, particle number, particle conductivity and
particle size have all been examined. The experimental results
obtained have not only allowed us to construct a mechanism
for the process that occurs during a “sonoimpact”, but also
demonstrate the potential analytical power of the technique
for the determination of the number and size of particles in
solution.
Experimental Section
Chemical reagents used were graphite powder (Aldrich, 2–20 mm),
glassy carbon spherical powders of diameter distribution 10–
810 www.chemphyschem.org > 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
20 mm, 20–50 mm, 40–80 mm and 80–200 mm (Alfa Aesar), Alumina
powder (Buehler Ltd), calcium carbonate (Alfa Aesar, puratronic
grade), N,N’-diphenyl-1,4-phenylenediamine (DPPD, Aldrich 98 %),
lithium perchlorate (Aldrich, 98 %) and perchloric acid
(Fisher Scientific, 70 %). These were used as received
without further purification. All dilute solutions were pre-
pared using ultrahigh quality water with a resistivity not
less than 18 MW cm (Elga, High Wycombe, Bucks, UK).
The experimental set-up is shown in Figure 1. A standard
three-electrode configuration is used, with a Pt mesh
(Johnson Matthey plc, London, UK) counter electrode
and an SCE reference (Radiometer, Copenhagen, Den-
mark) that is connected to the main cell via a KCl/gelat-
ine salt bridge. Experiments with a separated counter
electrode showed no change from those reported in the
in the text as would be expected given the tiny amounts
of charge passed. A 125 mm Pt working electrode was
fabricated by sealing Pt wire (Johnson Matthey plc,
London, UK) into a soda glass capillary using a literature
procedure.[17] A 20 kHz ultrasonic horn transducer system
(Sonics and Materials, VCX400) with a stepped 3 mm mi-
crotip (titanium alloy, Jencons, Leyton Buzzard, UK) is
employed. The ultrasonic power was determined calorimetrically
according to the procedure of Margulis et al.[18] and the “9 %
power” used was found to correspond to 215 W cm
2. The tip of
the horn is positioned at a distance of 10 mm perpendicular to the
working electrode surface using an x–y–z micropositioning device.
A cooling coil is utilised to prevent the cell overheating. The signal
to the potentiostat is provided by a TTi TG1304 programmable
function generator (Thurlby Thandar Instruments Ltd, Huntingdon,
Cambs, UK) and the output is processed and displayed by a Tektro-
nix TDS 3032 oscilloscope.
Acknowledgements
The authors wish to thank Prof. C. Amatore for making available
the designs for the fast scan potentiostat developed his group.
A.D.C. thanks the EPSRC for funding and Windsor Scientific for
CASE support.
Keywords: charge transfer · chronoamperometry ·
electrochemistry · sonoelectrochemistry
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ChemPhysChem 2006, 7, 807 – 811 > 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemphyschem.org 811