Journal of Electroanalytical Chemistry 466 (1999) 234 – 241

Characterization of electrochemically deposited gold nanocrystals on

glassy carbon electrodes

Michael O. Finot a, George D. Braybrook b, Mark T. McDermott a,*

a
Department of Chemistry, Uni6ersity of Alberta, Edmonton, Alberta, T6G-2G2 Canada
b
Scanning Electron Microscopy Facility, Department of Earth and Atmospheric Sciences, Uni6ersity of Alberta, Edmonton,
Alberta, T6G-2G2 Canada

Received 15 December 1998; received in revised form 16 March 1999; accepted 23 March 1999

Abstract

The interfacial properties of gold nanocrystals deposited electrochemically onto glassy carbon substrates are characterized.
Electrochemical interrogations as well as microscopy have been utilized to examine systematically the influences of deposition
solution concentration and overpotential. The results of these studies indicate that the overall surface area of gold as well as
nanocrystal size, density, and surface texture, can be controlled by variation of deposition conditions. From this work, arrays of
gold particles which are suitable sites for future chemical modification can be produced on glassy carbon surfaces. These interfaces
will be utilized for the fabrication of analytical electrodes with segregated sites exhibiting selectivity and facile electron transfer.
© 1999 Elsevier Science S.A. All rights reserved.

Keywords: Gold nanocrystals; Glassy carbon; Upd lead; SEM; Surface area determination

1. Introduction chemisorption of alkanethiols (X(CH2)n SH) guided us

The electrochemical deposition of metal nanocrystals
onto carbon electrodes has been the subject of a large
number of investigations [1 – 16]. Interest is sparked, in
most cases, by the utility of this type of interface in
electrocatalysis and as model systems for electroplating.
The focus of many of these studies has been on the
early stages of electrochemical deposition in an effort to
elucidate the nucleation and growth mechanism of the
metal phase on the substrate. Our interest in the ratio-
nal design of chemically modified carbon electrodes has
prompted us to consider supported metal nanocrystals
as sites for future modification steps. The large body of
recent literature on the modification of gold (Au) elec-
trodes [17–19] and colloids [20 – 30] by the spontaneous
* Corresponding author. Tel.: +1-403-4923687; fax: + 1-403-
4928231.
E-mail address: mark.mcdermott@ualberta.ca (M.T. McDermott)
to explore the electrochemical deposition of Au parti-
cles. This initial report concentrates on characteriza-
tions of gold particles electrochemically deposited on
glassy carbon (GC) substrates.
Studies examining the electrochemical deposition of
Au onto various carbon substrates have recently
emerged [31–35]. These reports suggest that Au elec-
trodeposition from a variety of electrolytes occurs via a
nucleation and growth process on carbon and results in
3-dimensional Au deposits. Because of our desire to
adsorb specific functional groups spontaneously to sup-
ported gold nanocrystallites, the size, structure, and
distribution of these structures must be controlled. Ide-
ally, small, well-dispersed gold nanocrystallites are de-
sired as a foundation for chemical modification. Our
experiments are aimed at characterizing the overall Au
surface area deposited as well as the microcrystal struc-
ture, size and spatial density of the resulting particles.
The results of these experiments provide us with stan-
dard procedures for preparing Au nanocrystallites of

0022-0728/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S 0 0 2 2 - 0 7 2 8 ( 9 9 ) 0 0 1 5 4 - 0
 M.O. Finot et al. / Journal of Electroanalytical Chemistry 466 (1999) 234–241
known size and number density supported on GC for
the purpose of further chemical modification.
2. Experimental
2.1. Reagents
Potassium tetrachloroaurate (III), (KAuCl4, 98%
Aldrich), lead oxide, (PbO, Certified, Fisher), sodium
fluoride (NaF, Analytical Grade, BDH), potassium fer-
ricyanide (K3Fe(CN)6, Certified, Caledon), potassium
chloride (KCl, Anachemia), sulfuric acid, (H2SO4,
Fisher), perchloric acid, (HClO4, Caledon) were all used
as received. All solutions were prepared using Nano-
pure (18 MV cm) water and purged with prepurified
argon prior to use.
2.2. Electrode preparation
The GC electrodes (Tokai GC-20, Electrosynthesis
Company, NY) were prepared by polishing on Micro-
polish polishing cloth (Buehler) in alumina/water slur-
ries. Two grades of polishing alumina were employed,
1.0 mm alpha alumina, and 0.3 mm alpha alumina
(Buehler). Upon polishing, the electrodes were rinsed,
sonicated for 10 min, rinsed, sonicated further for 10
min, rinsed, and stored in a beaker of water. This
procedure was repeated after polishing with each size of
alumina. Nanopure water was used throughout the
polishing process and the electrodes were used immedi-
ately after being polished.
2.3. Electrochemistry
All electrochemical experiments were performed in
an inverted three-electrode cell. The cell was connected
to a Pine Model AFCBP1 bipotentiostat with platinum
auxiliary and Ag AgCl KCl(sat.) reference electrodes.
The auxiliary electrode was separated from the bulk
solution using a glass frit. All potentials in the text are
referred to the Ag AgCl reference electrode unless
stated otherwise. The GC electrodes were mounted in
the cell between a viton o-ring and a metal plate and
held in place by the use of a metal clip. The geometrical
electrode area is defined by the circumference of the
o-ring and forms the bottom of the cell. Chronoamper-
ometry in Fe(CN)6− 3/ − 4 yielded a working electrode
area of 0.31 cm2.
The capacitance of polycrystalline gold electrodes
was measured in 0.1 M NaF. Differential capacitance
was determined using a 63 Hz, 20 mV peak-to-peak
triangular wave centered at − 0.6 V. The peak to peak
current of the output waveform is proportional to the
capacitance [36].
235
2.4. SEM imaging
Scanning electron microscopy analysis of the gold
deposits was carried out using a JEOL model 6301FXV
scanning electron microscope at an acceleration voltage
of 15–20 kV and a working distance of 4–5 mm. Image
analysis was performed visually (i.e. manually counting
particles) and with commercial software (Image Tool,
version 2.00, University of Texas Health Science Center
in San Antonio) for particle counting and diameter
measurement.
3. Results and discussion
Our efforts here are focused on controlling the size,
density and structure of Au nanocrystals electrode-
posited on GC in order to perform future steps to
modify these structures chemically. Toward this end, we
have studied particles formed from a potential step as a
function of the initial bulk AuCl4− concentration and as
a function of overpotential (h) at constant concentra-
tion. Because of our desire to produce arrays of
nanometer sized, well-dispersed Au particles, the depo-
sition concentrations used here (10 − 4 to 10 − 5 M) are
significantly lower than those employed in previous
studies [31–35]. Our characterizations are aimed at
elucidating the surface area and crystal structure of the
electrodeposited Au as well as the size and density of
the nanocrystals. Because both the GC substrate and
the Au nanocrystals are active electrode materials,
methodologies which could distinguish the two materi-
als were employed.
3.1. Au nanocrystal deposition
Au nanocrystals were deposited on GC from 0.5 M
H2SO4 solutions of KAuCl4 by employing a 5 s poten-
tial step from 1.1 V to some final potential. An
overview of the electrochemical behavior of this system
is provided in Fig. 1. Fig. 1(A) is a current–potential
curve for a cyclic voltammetric experiment at a polished
GC electrode in 2 × 10 − 4 M KAuCl4 in 0.5 M H2SO4.
This wave exhibits an initial cathodic current at 0.8
V and a sharp peak at 0.5 V corresponding to the
reduction of solution bound Au(III) to Au(0). We
attribute the initial wave at 0.8 V to the reduction of
adsorbed AuCl4− . Voltammetric evidence for the ad-
sorption of Au complexes to carbon electrodes similar
to Fig. 1(A) has been observed previously [31,34]. An
anodic current ‘crossover’, signifying metal nucleation
and growth, is not observed at the scan rate employed
in Fig. 1(A) [3,4]. Voltammetry which more closely
resembles reported current–potential curves for nucle-
ation and growth is observed at scan rates slower than
5 mV s − 1. Furthermore, no anodic current is observed
236 M.O. Finot et al. / Journal of Electroanalytical Chemistry 466 (1999) 234–241
on the reverse sweep indicating the irreversibility of the
reduction of AuCl4− . In 0.5 M H2SO4, we do not
observe electrochemical dissolution of deposited Au
within the potential limits employed in our characteri-
zations (1.5 to − 0.4 V). All overpotentials stated here
are relative to the standard potential for AuCl4− reduc-
tion to Au(0) which is 0.8 V versus Ag AgCl KCl(sat.).
Note that from Fig. 1(A), Au deposition on GC occurs
at an overpotential of 300 mV.
The first 50 ms of a representative current response
to a potential step from 1.1 to 0.0 V in 2 × 10 − 4 M
KAuCl4 (0.5 M H2SO4) is shown in Fig. 1(B). The
initial sharp current spike is due to the charging of the
double-layer. The curve then exhibits a hump shaped
response following the charging current spike. The posi-
tion and size of this hump varies with overpotential and
thus is likely the tail of a current peak commonly
observed for the electrochemical nucleation and 3-di-
mensional (3-D) growth of metal crystallites [34]. After
the hump, a current decay is observed which is linear
with t − 1/2 indicating a planar diffusion regime. This
situation develops due to overlap of growing hemi-
spherical diffusion layers which initially provide mass
transport for nanocrystal growth [3]. From plots of I
vs. t − 1/2, diffusion coefficients ranging between 1 and
3 × 10 − 5 cm2 s − 1 are determined for the AuCl4− com-
plex which agree with reported diffusion coefficients for
metal complexes [37]. The position of the hump in Fig.
1(B) within the first 10 ms argues that the growth of the
Fig. 1. (A) Cyclic voltammetry of 2.0 × 10 − 4 M AuCl4− in 0.5 M
H2SO4 at a polished GC electrode, n =100 mV s − 1. (B) Current
response to a potential step of 1.1 to 0.0 V for a polished GC
electrode in 2.0 × 10 − 4 M AuCl4− in 0.5 M H2SO4.
Au nuclei is relatively rapid. Because the rising portion
of the peak is experimentally inaccessible under our
conditions, an analysis of the nucleation mechanism
(i.e. instantaneous vs. progressive) is not possible from
current transients [3].
3.2. Au oxide reduction
The extent to which we can chemically modify the
electrode surface will ultimately depend on the surface
area of exposed Au. Insights into this parameter are
provided by the electrochemical reduction of Au sur-
face oxides [38–44]. Following the deposition of the Au
nanocrystals, the surface was oxidized by a potential
step from 0.0 to 1.4 V in 0.5 M H2SO4 for 5 s.
Although both the GC surface and Au particles are
likely to be oxidized at this potential, the oxide film on
the Au can be selectively reduced by a potential sweep
[38–44]. In separate experiments, these conditions were
assessed on polycrystalline gold electrodes and shown
to achieve  1 monolayer of chemisorbed divalent
oxygen on the Au surface [41–44]. For example, a
charge of 930 mC cm − 2 was measured for the reduction
of the oxide layer formed on a 0.10 cm2 polycrystalline
Au electrode. The same electrode exhibited a double
layer charge of 42 mF cm − 2 at − 0.6 V in 0.1 M NaF.
Assuming a capacitance of 22 mF cm − 2 for a metallic
Au electrode with a roughness factor of 1, we estimate
the roughness factor of this electrode to be 1.9.
Thus, a roughness corrected value of 489 mC cm − 2 is
obtained which agrees well with the theoretical value of
482 mC cm − 2 for the reduction of a monolayer of
divalent oxygen from a gold surface [41,42].
Fig. 2 contains the linear sweep voltammograms for
Au oxide reduction on Au nanocrystals as a function of
AuCl4− concentration for h= − 800 mV (Fig. 2(A))
and as a function of deposition overpotential in 1.0×
10 − 4 M AuCl4− (Fig. 2(B)). The sharp wave appearing
at  0.935 V in all the voltammograms is consistent
with the reduction of an oxide film on Au. The observa-
tion of this wave confirms the deposition of metallic Au
onto GC under the conditions employed. The area
under the oxide reduction waves for repeated oxidation
cycles varies by no more than 5% implying that rough-
ening of the Au nanocrystals is negligible [41].
An assessment of the amount of Au deposited by
electrolyses means was made based upon the Au oxide
reduction currents observed at GC electrodes exposed
to AuCl4− in 0.5 M H2SO4 at open circuit. Electroless
deposition of Au was found to constitute no more than
5% of the amount of Au deposited electrochemically. In
addition, poising the GC electrode at 1.1 V prior to and
during its initial exposure to AuCl4− has no effect on
the amount of Au electrochemically deposited. Thus,
the currents observed for the reduction of Au oxides
reflects the surface area of electrochemically deposited
Au.
 M.O. Finot et al. / Journal of Electroanalytical Chemistry 466 (1999) 234–241 237

Table 1
Surface area determination of electrochemically deposited gold
nanocrystals on GC via oxide reduction analysis

105[KAuCl4]/M Qobs/mC Au area/cm2 b % Geometric

area

20.0 15.0 91.6 a 0.031 90.003 10.0 9 1.1

10.0 11.8 9 1.0 0.024 9 0.002 8.1 9 0.7
5.0 8.9 9 1.1 0.018 90.002 6.0 90.7
1.0 2.9 9 0.8 0.006 90.002 2.0 90.5
Overpotential/
mV
−400 7.4 9 0.2 c 0.015 90.0004 4.8 9 0.1
−600 9.7 90.7 0.020 9 0.001 6.5 9 0.3
−800 11.8 91.0 0.0249 0.002 8.1 +0.7
−1000 16.6 90.6 0.034 9 0.001 10.9 90.3

a
Statistics based on six measurements for each concentration.
b
A value of 489 mC cm−2 was used as the charge required to
reduce a monolayer of divalent oxygen on a polycrystalline Au
surface.
c
Statistics based on three measurements for each overpotential.
Fig. 2. Linear sweep voltammograms for the reduction of gold
surface oxides from electrochemically deposited gold nanocrystallites.
(A) Deposition solution concentration series for h = −800 mV: (a) modified GC substrate [56]. The stripping of upd Pb
2.0× 10 − 4 M; (b) 1.0× 10 − 4 M; (c) 5 0 ×10 − 5 M; (d) 1 0 ×10 − 5 has been used by several authors to characterize the
M, AuCl4− . (B) Overpotential series for [KAuCl4] = 1.0×10 − 4 M; surface of Au substrates [45,53,55] and was employed
(a) − 1000 mV; (b) − 800 mV; (c) − 600 mV; (d) −400 mV. here to assess the microcrystal structure of the elec-
trodeposited Au nanocrystals.
The trend in Fig. 2(A) reveals higher peak currents Lead was deposited onto the GC supported Au
for oxide reduction as the bulk AuCl4− concentration particles by stepping the potential from open circuit to
increases. This result is not unexpected and implies that − 0.4 V for 5 s. Fig. 3 contains Pb stripping voltam-
the surface area of deposited gold tracks solution con- mograms from Au nanocrystals electrodeposited under
centration for a given deposition potential and time. A our varied concentration (Fig. 3(A)) and overpotential
similar trend is observed as a function of overpotential
(Fig. 2(B)) where greater overpotentials achieve higher
Au surface areas. Using the observed charge (Qobs)
obtained by integrating the area under each of the
waves in Fig. 2 and the charge expected for complete
monolayer coverage as described above, quantitative
surface areas can be determined for each deposition
condition. Table 1 contains the quantitative results
from the analysis of the data in Fig. 2. As illustrated in
Table 1, areas corresponding to 2 – 11% of the geometri-
cal area of the GC electrode can be made available for
future modification by varying either the bulk AuCl4−
concentration or the overpotential.

3.3. Stripping of underpotentially deposited lead

A monolayer of lead (Pb) adatoms will form on Au

surfaces at potentials slightly more positive than for
bulk deposition of Pb [45 – 55]. This underpotentially
deposited (upd) Pb monolayer can be subsequently
stripped oxidatively from the Au. Similar to the case of
the oxide reduction experiments, our control experi-
ments indicate that Pb deposits underpotentially solely
on the Au nanocrystals. Contrary to a recent report, we
do not observe Pb stripping currents from the un-
Fig. 3. Linear sweep voltammograms for the stripping of upd lead
from electrochemically deposited gold nanocrystallites. (A) Deposi-
tion solution concentration series for h = − 800 mV: (a) 1.0× 10 − 5
M; (b) 5.0 × 10 − 5 M; (c) 1.0 ×10 − 4 M; (d) 2.0 × 10 − 4 M, AuCl4− .
(B) Deposition overpotential series for [KAuCl4]= 1.0 ×10 − 4 M; (a)
− 400 mV; (b) − 600 mV; (c) − 800 mV; (d) −1000 mV.
238 M.O. Finot et al. / Journal of Electroanalytical Chemistry 466 (1999) 234–241
(Fig. 3(B)) conditions. The sloping background current
in all the voltammograms of Fig. 3 is due mainly to the
GC substrate. Two oxidative stripping waves are ob-
served; a sharp wave at −0.2 V which is diagnostic of
Pb stripping from the Au(111) crystal plane and a
broader wave at 0.025 V corresponding to stripping
from the Au(110)/Au(100) crystal planes [46 – 52,54].
Closer examination of the Au(111) wave for some of
the voltammograms (i.e. Fig. 3(A), curves c and d; Fig.
3(B), curves a, b, c) reveals the presence of a shoulder
at slightly more positive potentials (− 0.17 V). This
feature has been attributed to Pb stripping from
Au(111) terraces of extended lengths, greater than 11
Au atoms [51,52,54,55]. Close observation of all the
voltammograms in Fig. 3 suggests that the Au
nanocrystals deposited on GC under the present condi-
tions are polycrystalline with a combination of (111);
(110) and (100) sites. Additionally, in some cases, parti-
cles are composed of Au(111) terraces of extended
length.
Two trends are apparent in Fig. 3(A) as the bulk
concentration of AuCl4− increases (a – d). First, the
observed current for each Pb stripping wave tracks
deposition solution concentration. This observation
mirrors the oxide reduction in Fig. 2(A) and confirms
the increase in overall Au surface area resulting from
depositions from higher concentration solutions. There
is good agreement between the surface area of the Au
nanocrystals derived from oxide stripping and that
derived from lead upd. However, the Au surface area
determination by Pb stripping is unreliable due to the
uncertainty associated with the integration and summa-
tion of several waves and the variation in the values of
charge associated with the desorption of a monolayer
of adsorbed lead atoms reported in the literature (225–
362 mC cm − 2) [45,47,49,54]. Secondly, the microstruc-
ture of the deposited nanocrystals evolves with bulk
concentration as gauged by the shoulder on the
Au(111) peak at − 0.17 V. This wave becomes more
pronounced on nanocrystals deposited from 1.0× 10 − 4
and 2.0 ×10 − 4 M solutions indicating the formation of
larger Au(111) terraces. From rough integration of the
waves, the percentage of the Au(111) crystal face area
for the 2.0×10 − 4 M solution (28%) is similar to that
of polycrystalline Au [45].
The dependence of overpotential on the microstruc-
ture of electrodeposited Au nanocrystals is deduced
from Fig. 3(B). Lead stripping currents increase as the
deposition overpotential increases (a – d) reflecting the
increase in Au surface area shown in Table 1. However,
the stripping signature for particles deposited at low
overpotential (e.g. curve a in Fig. 3(B)) includes a
significant shoulder on the Au(111) wave arguing that,
although a relatively small amount of Au is deposited
at low overpotential (Table 1), the resulting particles
exhibit a significant (111) texture which is comprised of
larger terraces. For higher overpotentials, although the
total stripping current increases, the wave at − 0.17 V
becomes less prominent, indicating smaller (111) planes.
These observations taken together suggest that at low
overpotentials, a small number of Au particles nucleate
and grow to significant sizes during deposition. In this
case, the applied overpotential provides enough driving
force to activate only certain nucleation sites and three
dimensional Au particle growth is favored. Higher
overpotentials access more nucleation sites and a larger
density of smaller particles results. This model is con-
firmed in the SEM analysis in the next section.
3.4. SEM analysis
Oxide reduction and lead stripping indicate that the
amount of Au deposited onto GC tracks both the bulk
AuCl4− concentration and the deposition overpotential.
Although these analyses yield a quantitative perspec-
tive, they do not provide insights into the manner in
which the change in the gold surface area is manifested
in terms of the interfacial architecture. That is, oxide
reduction and lead stripping results cannot resolve
whether the variation in surface area is due to changes
in particle size, particle density, or a combination of
these two scenarios. Stripping of upd Pb provides some
insights, particularly for variations in overpotential. To
build upon these insights a visual representation of the
Au nanocrystals was obtained with SEM. Fig. 4 con-
tains representative images depicting the effect of bulk
AuCl4− concentration (parts A and B) and overpoten-
tial (parts C and D).
The Au nanocrystals in the SEM images of Fig. 4
appear as circular bright spots surrounded by a tex-
tured background of darker GC substrate. As shown in
Fig. 4(A), deposition at low concentration (1.0×10 − 5
M) yields a low number of small nanocrystals. Fig. 4(B)
illustrates that at higher concentrations (2.0× 10 − 4 M),
a high density of relatively monodisperse particles is
deposited. Quantitative results from SEM image analy-
sis for nanocrystal number density, which reflects the
number of nucleation sites on the GC electrode, and
nanocrystal diameter, which represents particle growth,
are listed in Table 2.
The results in Table 2 show that both the number
density and diameter of Au nanocrystals electrode-
posited on GC electrodes increase with bulk AuCl4−
concentration. These trends are responsible for the
increase in electrodeposited Au surface area indicated
by Au oxide reduction (Fig. 2 and Table 1). If the Au
nanocrystals are modeled as hemispheres, a value for
the Au surface area can be estimated using the diame-
ters and number densities in Table 2. Comparison of
surface area values calculated from SEM data with
those determined by oxide reduction yields a range of
correlation from 10% agreement to a difference by a
 M.O. Finot et al. / Journal of Electroanalytical Chemistry 466 (1999) 234–241 239

Fig. 4. SEM images of electrochemically deposited gold nanocrystallites on glassy carbon. Deposition solution concentration series; (A) 1.0 × 10 − 5
M and (B) 2.0 ×10 − 4 M, AuCl4− (h= − 800 mV). Deposition overpotential series; (C) − 400 mV, and (D) − 1000 mV, ([KAuCl4]= 1.0× 10 − 4
M).

factor of 2. However, the use of a hemisphere as a
model for the shape of the nanocrystals may not be a
valid assumption. In addition, we note that our SEM
images probably do not reveal Au nanocrystals of very
small diametersB 5 nm.
Parts C and D of Fig. 4 illustrate the effect of
overpotential on Au nanocrystal distribution and size.
At low overpotentials, Fig. 4(C), a number of large
(50 – 80 nm) particles are observed coexisting with
smaller nanocrystals. Higher overpotentials (Fig. 4(D))
yield an array of evenly distributed, relatively
monodisperse particles. Table 2 lists quantitatively the
values for Au nanocrystal number density and diameter
as a function of overpotential. The increase in number
density with overpotential implies that the number of
active sites on GC for Au nanocrystal nucleation in-
creases with overpotential, consistent with a recent
report [34]. For lower overpotentials, the growth of a
small number of initial nuclei is favored over the estab-
lishment of new nucleation sites as indicated by the
large size of the particles apparent in Fig. 4(C). This
mechanism is also consistent with the Pb stripping
results which indicate a relatively low Au surface area
comprised of larger Au(111) terraces. Taken together,
the data in Table 2 imply that the size, density, and
structure of Au nanocrystals on GC electrodes can be
systematically controlled via variations in deposition
solution concentration and overpotential. This control
will be exploited in our future work aimed at modifying
these nanocrystals.
The magnitude of the number density values ob-
served here (109 –1010 cm − 2) are larger than those
reported for Au nucleation on polished GC from con-
centrated LiCl solutions [34] and agree well with the
number density of other metals electrodeposited on GC
[57]. However, a direct comparison with particle num-
ber densities from previous reports is clouded because
of inconsistencies in electrode handling and preparation
240 M.O. Finot et al. / Journal of Electroanalytical Chemistry 466 (1999) 234–241

Table 2 (NSERC) and the Department of Chemistry, Univer-

Results from SEM image analysis for electrochemically deposited
sity of Alberta. We thank Don Resultay, Department
gold nanocrystals on GC
of Earth and Atmospheric Sciences, for use of the thin
105[KAuCl4]/M a Particle density/mm−2 Diameter/nm sections preparation laboratory.

1.0 15 9 3 c 109 3 d
5.0 68 9 7 13 9 3
10.0 8997 189 4
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