2856 Langmuir 2008, 24, 2856-2868

Study of the Underlying Electrochemistry of Polycrystalline Gold

Electrodes in Aqueous Solution and Electrocatalysis by Large
Amplitude Fourier Transformed Alternating Current Voltammetry
Benchaporn Lertanantawong,† Anthony P. O’Mullane,‡ Werasak Surareungchai,†
Mithran Somasundrum,† L. Declan Burke,§ and Alan M. Bond*,‡
School of Bioresources and Technology, King Mongkut’s UniVersity of Technology, Thonburi, Thailand,
School of Chemistry, Monash UniVersity, Clayton, Victoria 3800, Australia, and Chemistry Department,
UniVersity College Cork, Cork, Ireland

ReceiVed August 8, 2007. In Final Form: NoVember 5, 2007

Polycrystalline gold electrodes of the kind that are routinely used in analysis and catalysis in aqueous media are
often regarded as exhibiting relatively simple double-layer charging/discharging and monolayer oxide formation/
removal in the positive potential region. Application of the large amplitude Fourier transformed alternating current
(FT-ac) voltammetric technique that allows the faradaic current contribution of fast electron-transfer processes to be
emphasized in the higher harmonic components has revealed the presence of well-defined faradaic (premonolayer
oxidation) processes at positive potentials in the double-layer region in acidic and basic media which are enhanced
by electrochemical activation. These underlying quasi-reversible interfacial electron-transfer processes may mediate
the course of electrocatalytic oxidation reactions of hydrazine, ethylene glycol, and glucose on gold electrodes in
aqueous media. The observed responses support key assumptions associated with the incipient hydrous oxide adatom
mediator (IHOAM) model of electrocatalysis.

Introduction surface. According to a recent account of the electrocatalytic

The concept of surface active sites was introduced into the
heterogeneous catalysis area by H. S. Taylor1 in 1925. In a recent
discussion of such sites, Ertl2 pointed out that atomic defects are
present on all solid surfaces, such as polycrystalline gold, and
even those of the well-defined, single crystal plane variety. The
atoms at such defect sites exhibit unusual coordination chemistry,
and have energetic and kinetic properties that differ from those
of terrace atoms on the same surface. According to Ertl, the
metal atoms present at these defect sites facilitate bond breaking
reactions. According to Somorjai,3 another related feature of
such atoms is that their protruding surfaces are unusually
electropositive, so that they tend to lose electrons to the bulk
phase. Thus, defect atoms exist as positive species which are
surrounded by a large local electric field which polarizes and
ruptures incoming molecules. The abnormal properties of surface
active site atoms are assumed to be a major contributor to the
unexpected catalytic properties of oxide-supported gold nano-
particles,4,5 which are currently the subject of widespread
investigation.
The properties of surface active sites are difficult to investigate
as (a) the states involved are unstable and may be of variable
character, (b) the coverages involved are usually quite low (in
some instances <1 % of a monolayer6), and (c) the chemistry
of the protruding atoms is significantly different from that of the
dominant well-embedded (terrace) atoms present on the same
* Correspondence to Alan Bond. E-mail: alan.bond@sci.monash.edu.au.
† King Mongkut’s University of Technology Thonburi.
‡ Monash University.
§ University College Cork.
(1) Taylor, H. S. Proc. R. Soc. London, Ser. A 1925, 108, 105.
(2) Ertl, G. AdVances in Catalysis, Impact of Surface Science on Catalysis;
Academic Press: London, 2000.
(3) Somorjai, G. A. Chem. ReV. 1996, 96, 1223.
(4) Haruta, M.; Yamada, N.; Kobayashi, T.; Iijima, S. J. Catal. 1989, 115, 301.
(5) Bond, G. C.; Thompson, D. T. Cat. ReV. Sci. Eng. 1999, 41, 319.
(6) Burke, L. D.; O’Sullivan, J. F. Electrochim. Acta 1992, 37, 585.
properties of gold,7 surface metal atoms may be subdivided into
two broad categories, the vast majority being in the low energy,
equilibrated metal surface (EMS), state, with a low percentage
constituting a high-energy metastable metal surface (MMS) state.
These two states are assumed to exhibit different oxidation
electrochemistries. The dominant form of surface atoms gives
rise to an EMS/monolayer or (R) oxide transition under conditions
of conventional dc cyclic voltammetry. The more reactive MMS
atoms undergo oxidation at less positive potentials within the
double-layer region (such behavior is known as premonolayer
oxidation), and the reaction is assumed to be a MMS/hydrous
or (β) oxide transition. However, (i) the coverage and hence the
dc cyclic voltammetric response derived from the MMS atoms
is quite low (it may be temporarily enhanced by severe thermal
or cathodic pretreatment), and (ii) the nature of the active state
seems to be variable and not easily controlled.7 The study of
polycrystalline gold electrodes in aqueous solution is important
from the viewpoint that many researchers in the analytical and
catalysis fields routinely work with electrodes that have been
pretreated chemically, electrochemically and thermally, thereby
generating ill-defined surfaces.
Despite its weak chemisorbing properties, gold can be an active
electrocatalyst, especially in basic media.8,9 Predominantly, these
electrocatalytic processes commence well within the double-
layer region under voltammetric conditions. The mechanism
proposed in the case of the group 11 metals largely ignores the
activated chemisorption approach and assumes that the important
factor in electrocatalysis is interfacial redox cycling of the active
state.9,10
Scheme 1 summarizes the basis of this incipient hydrous oxide
adatom mediator (IHOAM)8,9 electrocatalysis model in which
(7) Burke, L. D. Gold Bull. 2004, 37, 125.
(8) Burke, L. D.; Nugent, P. F. Gold Bull. 1997, 30, 43.
(9) Burke, L. D.; Nugent, P. F. Gold Bull. 1998, 31, 39.
(10) Burke, L. D.; Cunnane, V. J. J. Electroanal. Chem. 1986, 210, 69.

10.1021/la702454k CCC: $40.75 © 2008 American Chemical Society

Published on Web 02/12/2008
Polycrystalline Au Electrodes in Aq Solution
Scheme 1
the M*/M(OH)n or MMS/β oxide transition is assumed to be
associated with a quasi-reversible electron-transfer process. This
process occurs at a potential Es, which represents a metastable,
or nonequilibrium, potential, for which both the oxidized and
reduced states of the couple are thermodynamically unstable.
The interfacial oxide can be a mediator for oxidation of a dissolved
reductant (Red) (when E > Es), whereas the mediator for reduction
can be M* (when E < Es). In the case of gold and other metal
surfaces, commonly the interfacial couple is thermodynamically
unstable and some element of activated chemisorption (or coor-
dination) of reactants with the active site species may be involved.
To date, the main evidence for premonolayer oxidation of
gold in aqueous media, and significant electrocatalysis, has been
based on data obtained by dc cyclic voltammetry. There are a
few reports of analysis of premonolayer oxidation behavior based
on spectroscopic, contact electrical resistance, and quartz crystal
microbalance data; and extensive work in this area, based on the
use of modern surface science techniques, has been carried out
in basic media by Doblhofer and co-workers11 for silver electrodes.
In the present study, a more sophisticated electrochemical
approach, large amplitude Fourier transformed alternating current
(FT-ac) voltammetry has been used to explore the behavior of
gold electrode surfaces in aqueous media. A significant advantage
in analyzing higher harmonic components that are readily
accessible from this technique is the ability to achieve almost
complete suppression of background capacitive current. This
feature of the higher harmonics has been exploited in the study
of solution-phase one-electron redox processes12,13 and surface-
confined systems of biological importance.14-16 Another ad-
vantage over dc and other ac techniques is kinetic discrimination.
For example, the resolution of overlapping reversible and
irreversible electron-transfer processes, such as [Ru(NH)6]3+/2+
reduction in the presence of oxygen17 and the separation of an
underlying electron-transfer process from a coupled catalytic
chemical reaction in the case of mediated glucose oxidation,18
has been achieved using higher harmonics that are readily
available with large amplitude FT-ac voltammetry. This approach
is now applied to detect the underlying interfacial redox chemistry
at a gold electrode occurring in the presence of an irreversible
electrocatalytic reaction of the kind that occurs during the course
of hydrazine oxidation.
(11) Savinova, E. R.; Zemlyanov, D.; Pettinger, B.; Scheybal, A.; Schlogl, R.;
Doblhofer, K. Electrochim. Acta 2000, 46, 175.
(12) Sher, A. A.; Bond, A. M.; Gavaghan, D. J.; Harriman, K.; Feldberg, S.
W.; Duffy, N. W.; Guo, S.-X.; Zhang, J. Anal. Chem. 2004, 76, 6214.
(13) Bond, A. M.; Duffy, N. W.; Guo, S.-X.; Zhang, J.; Elton, D. Anal. Chem.
2005, 77, 186A.
(14) Zhang, J.; Guo, S.-X.; Bond, A. M.; Honeychurch, M. J.; Oldham, K. B.
J. Phys. Chem. B 2005, 109, 8935.
(15) Guo, S.; Zhang, J.; Elton, D. M.; Bond, A. M. Anal. Chem. 2004, 76, 166.
(16) Fleming, B. D.; Barlow, N. L.; Zhang, J.; Bond, A. M.; Armstrong, F.
A. Anal. Chem. 2006, 78, 2948.
(17) Zhang, J.; Guo, S.-X.; Bond, A. M.; Marken, F. Anal. Chem. 2004, 76,
3619.
(18) Fleming, B. D.; Zhang, J.; Bond, A. M.; Bell, S. G.; Wong, L.-L. Anal.
Chem. 2005, 77, 3502.
Langmuir, Vol. 24, No. 6, 2008 2857
Experimental Section
Chemicals. Aqueous 0.5 M H2SO4 (APS Ajax Finechem) and
NaOH (AnalaR, BDH) solutions were made up with deionized water
(resistivity of 18.2 MΩ cm) purified by use of a Milli-Q reagent
deionizer (Millipore). Hydrazine (Sigma Aldrich), ethylene glycol
(Sigma), and glucose (BDH) were used as received.
Apparatus and Procedures. A description of the FT voltammetric
instrumentation used in this study is available elsewhere.13 Sine
waves of frequencies f ) 10 to 30 Hz and amplitudes of ∆E ) 80
to 150 mV were employed as the ac perturbation. dc voltammetric
experiments were carried out with this instrumentation by using a
zero amplitude perturbation. All voltammetric experiments were
undertaken at (20 ( 2)°C in an electrochemical cell that allowed
reproducible positioning of the working, reference, and auxiliary
electrodes and a nitrogen inlet tube. A 1.5 mm diameter gold electrode
(BAS) was used as the working electrode. This electrode was polished
with an aqueous 0.3 µm alumina slurry on a polishing cloth
(Microcloth, Buehler), sonicated in deionized water for 5 min, and
dried with tissue paper (Kimwipe) prior to use. The reference electrode
was Ag/AgCl (aqueous 3 M KCl) and the auxiliary electrode was
a coiled gold wire. Voltammetric experiments were commenced
after degassing the electrolyte solutions with nitrogen for at least 10
min prior to any measurement. When a cathodic polarization
procedure was used, the electrolyte solution was continuously
degassed with nitrogen.
Results and Discussion
Large Amplitude FT-ac Voltammetry at a Gold Elec-
trode in Acidic Solution. Initial studies used a sine wave of
frequency f ) 21.46 Hz and amplitude of ∆E ) 150 mV
superimposed onto the dc waveform (potential range 0 to 1.5 V
vs Ag/AgCl, scan rate (ν) ) 99.34 mV s-1). The separated dc
and ac components obtained after the FT-inverse FT sequence
are shown in Figure 1 for a polycrystalline gold electrode in 0.5
M H2SO4. The dc component (Figure 1a) is typical of a
conventional dc cyclic voltammogram reported for gold in
aqueous acid solution.19 Thus, the positive potential sweep
response (0 to 1.5 V) is featureless until the onset of the monolayer
oxide formation process at ca. 1.06 V. This reaction is sluggish,
it continues to the upper limit of the sweep and is represented
here in simple terms by eq 1. The subsequent negative potential
2Au + 3H2O ) Au2O3 + 6H+ + 6e- (1)
direction sweep (1.5 to 0 V) exhibits the expected hysteresis
effect in the reduction of the monolayer oxide film19 which is
followed by a featureless response until the end of the sweep at
0 V. The data in Figure 1 and all other figures have been plotted
in the current-potential format and separated into forward and
reverse scans to allow for greater clarity in presentation of the
ac harmonic data.
In the ac fundamental harmonic response (Figure 1b), a broad
peak not seen in the dc component is observed at 0.6 V on both
the forward and reverse scans. This potential region of 0.4 to 0.6
V, where fundamental harmonic current is found, corresponds
to that where premonolayer responses on gold have been reported
after appropriate electrochemical and thermal activation.20,21 The
monolayer oxide formation process (eq 1) also gives rise to a
broad fundamental harmonic ac component and a much sharper
response for the removal of the oxide, analogous to the dc data.
In the higher second, third, and fourth ac harmonic components
(Figure 1c,d,e), the broad feature at ca. 0.60 V gradually
(19) Conway, B. E. Prog. Surf. Sci. 1995, 49, 331.
(20) Burke, L. D.; O’Mullane, A. P. J. Solid State Electrochem. 2000, 4, 285.
(21) Burke, L. D.; Hurley, L. M.; Lodge, V. E.; Mooney, M. B. J. Solid State
Electrochem. 2001, 5, 250.
2858 Langmuir, Vol. 24, No. 6, 2008 Lertanantawong et al.

Figure 1. Large amplitude Fourier transformed ac cyclic voltammograms obtained for the dc (a) and fundamental to fourth harmonics (b-e)
for a gold electrode (black) and activated electrode (prepolarized at 0 V for 5 min) (red) in 0.5 M H2SO4. Conditions employed: f ) 21.46
Hz, ∆E ) 150 mV, and ν ) 99.34 mV s-1.

diminishes and is not detectable in the fourth harmonic. In contrast,
the monolayer oxide/removal process exhibits a significant
response even in the fourth harmonic. The current for the
monolayer oxide response for all harmonics begins to decay
when a potential of 1.10 V is reached, which is in the potential
region for compact monolayer oxide formation.19 However, the
higher harmonic data suggest that the initial stages of this process
may have a significant level of electrochemical reversibility which
is not evident from the dc data. The magnitudes of the currents
detected in the fundamental to fourth ac harmonics are larger
than that of the dc component. This is predicted for a process
that is electrochemically reversible and has been previously
demonstrated both experimentally and theoretically for solution
and surface-confined processes.15,17,22
The mechanism of oxide formation on gold and other
noble metals has been a topic of much discussion and it has
been postulated that the initial stages involve the formation of
an electroadsorbed layer of OH which undergoes a place
exchange reaction with the metal to form a quasi 3D lattice of
AuO.19,23 Upon increasing the anodic potential, a compact oxide
containing Au3+ species develops.24 This process is outlined in
eqs 2-5.
Au + H2O f Au - OHads + H+ + e- (2)
place exchange reaction
Au - OHads98OH- - Au+ (3)
(22) Gavaghan, D. J.; Bond, A. M. J. Electroanal. Chem. 2000, 480, 133.
(23) Woods, R. Electroanalytical Chemistry; Bard, A. J., Ed.; Marcel Dekker:
New York, 1977; Vol 9, p 27.
(24) Juodkazis, K.; Juodkazyte, J.; Jasulaitiene, V.; Lukinskas, A.; Sebeka, B.
Electrochem. Commun. 2000, 2, 503.
Polycrystalline Au Electrodes in Aq Solution
OH- - Au+ f O2- - Au2+ + H+ + e- (4)
2AuO + H2O f Au2O3 + 2H+ + 2e- (5)
The FT ac voltammetric data imply that the electron-transfer
processes are moderately fast. However, once the compact oxide
is formed, the gold electrode is essentially deactivated, which
results in a rapid decay in the ac harmonic components at potentials
above ca. 1.20 V.
Previous studies have shown that cathodic polarization of gold
electrodes in the hydrogen evolution region20 or thermal
pretreatment21 results in severe disruption of the outer layers of
the metal. These treatments therefore provide an unusually active
state of gold that can exhibit voltammetric responses in the double-
layer region. Figure 1 also contains dc and ac fundamental to
fourth harmonic voltammetric components obtained in 0.5 M
H2SO4 after the gold electrode had been subjected to cathodic
polarization at 0 V for 5 min. The dc data (Figure 1a) provide
evidence of a premonolayer process in the double-layer region
at ca. 0.22 V in the forward sweep. However, no significant
reduction component is detected on the reverse scan. (It should
be noted that the dc component recovered from the inverse FT
procedure gave data typical of conventional dc cyclic voltam-
mograms recorded without any sinusoidal perturbation.) The
fundamental harmonic component exhibits a new response at
0.22 V as well as the previous identified one at 0.60 V on the
forward sweep, but no new features are detected on the reverse
sweep. In comparison to the nonactivated gold electrode, the
entire response (including monolayer oxide formation/removal)
also shows an increase in current magnitude.
The new response detected at ca. 0.22 V on the activated gold
electrode is attributed20 to the oxidation of active adatoms of
gold (Au*) at the surface which have a low lattice coordination
number and are hence easily oxidized. The Au adatoms involved
in this premonolayer oxidation process are assumed to be in a
more active state than those responsible for the process at more
positive potential (0.60 V). As for the nonactivated gold electrode
case, the feature at 0.60 V decays quite rapidly in the higher ac
harmonic components, but the response at 0.22 V remains
significant even in the fourth harmonic, which suggests the rate
of electron transfer is reasonably fast. However, the lack of a
counter process in the reverse sweep indicates that the chemical
reversibility of this process is poor and that the product formed
in the electron-transfer step is unstable. The product of Au*
oxidation has been postulated as being a hydrous oxide species
that is anionic in nature7 and represented as [Au2(OH)9]3-ads.
Under conditions of low hydroxide ion concentration found in
0.5 M H2SO4, such a species may be quite unstable.
As seen in Figure 2, with use of a more cathodic polarization
potential of -0.4 V, the magnitude of the premonolayer response
is greatly enhanced in the potential region around 0.2 V. The
magnitude of the dc component (Figure 2a) is now comparable
to that observed for monolayer oxide formation, and the reverse
sweep contains evidence of a reduction component. Evidence of
more than one process is now found in this potential region. The
fundamental to fourth ac harmonic components also demonstrate
that the premonolayer oxidation response around 0.2 V dominates
the forward sweep in comparison to the monolayer oxide
formation process. On the reverse sweep, there is a clear response
observed in the same potential region around 0.2 V which is
lower in magnitude than that seen in the forward sweep, as
expected if the product is unstable in a solution of low pH. Under
these more severe activation conditions, the outer layers of the
gold lattice are disrupted via hydrogen embrittlement to a
Langmuir, Vol. 24, No. 6, 2008 2859
significantly greater extent than when cathodic polarization is
applied at 0 V. In this process, the entry of hydrogen into the
metal generates strain in the lattice which results in the expulsion
of gold atoms from bulk metal to the surface.25 The insertion of
energy into the system (assumed to be related to the cathodic
polarization potential) is retained to some degree by metal atoms
which have converted from a low to a high energy state with a
low lattice coordination number. The resulting Au* or MMS
state readily undergoes oxidation as seen by the large current at
potential around 0.2 V. The electron-transfer step is most likely
quasi reversible according to the magnitude of the current in the
higher harmonic components. The magnitude of the current in
the reverse sweep indicates that the stability of the hydrous oxide
species is enhanced when a higher surface coverage of the initial
MMS state is achieved by using a cathodic polarization potential
of -0.4 V.
In Figure 3, the influence of the standard electron-transfer rate
constant for a simple Asurf + e- a Bsurf surface-confined one-
electron transfer process (the Au* to hydrous oxide transition is
assumed to be surface-confined) is shown via simulation using
the Butler-Volmer formulation with electron-transfer rate
constants of k ) 1 × 1010, 10, and 1 s-1 with a charge-transfer
coefficient of 0.5. Other parameters included in the simulation,
and which closely match experimental conditions, were as
follows: surface coverage ) 8 × 10-11 mol cm-2 (calculated
from the charge passed for the response at 0.22 V), sweep rate
) 100 mV s-1, f ) 21.46 Hz, ∆E ) 150 mV, uncompensated
resistance ) 80 Ω, E0 ) 0.20 V, and the potential limits were
-0.20 to 0.60 V. Simulations that mimic the potential dependent
double-layer capacitance are not yet available and hence the
background current contributions are not included in the model.
When the process is fully reversible, well-defined ac harmonic
components are achieved (Figure 3a), whereas when much slower
kinetics are involved (Figure 3b, c), the symmetry of the response
is lost, particularly in the second to fourth harmonics. Full details
of the simulation can be found in ref 15. Quantitative agreement
between simulated and experimental data is not expected, given
that the Au*/Au hydrous oxide transition is a far more complex
than that simulated, since the experimental case involves an
unstable product and a surface coverage of Au* species that is
extremely difficult to estimate because the activity of the surface
is likely to be dependent on factors such as electrode history,
potential cycling rate, and potential limits. Furthermore, the gold
species have been speculated as having a level of mobility on
the surface, which according to Kolb26 provides imaging problems
during STM experiments. Recently, it was demonstrated that the
atomic structure of gold is not static in the presence of weakly
absorbing molecules even at temperatures as low as 80 K.27
Therefore, simulations are only used qualitatively to illustrate
that the Au*/Au hydrous oxide transition is likely to have a
significant degree of electrochemical reversibility.
Cathodic polarization in the hydrogen evolution region is not
the only means of activating a gold surface. Even mild abrasion
of the electrode surface with emery paper results in the generation
of active gold as illustrated by the FT-ac harmonic responses in
Figure S1. In the dc component, a rise in anodic current is detected
from 0.76 V until the onset of monolayer oxide formation (at
1.06 V). Significant responses in the forward sweep for each of
the ac harmonics are also seen at ca. 0.95 V. Analogous behavior
was recently reported in dc cyclic voltammograms in the double-
(25) Cobden, P. D.; Nieuwenhuys, B. E.; Gorodetskii, V. V.; Parmon, V. N.
Platinum Met. ReV. 1998, 42, 141.
(26) Kolb, D. M.; Schneeweiss, M. A. Electrochem. Soc. Interf. 1999, 8, 26.
(27) Baber, A. E.; Jensen, S. C.; Iski, E. V.; Sykes, E. C. H. J. Am. Chem. Soc.
2006, 128, 15384.
2860 Langmuir, Vol. 24, No. 6, 2008
Figure 2. Large amplitude Fourier transformed ac cyclic voltammograms obtained for the dc (a) and fundamental to fourth harmonics (b-e)
for an activated gold electrode (prepolarized at -0.40 V for 20 min) in 0.5 M H2SO4. Conditions employed: f ) 21.46 Hz, ∆E ) 150 mV,
and ν ) 102.95 mV s-1.
layer region after use of either conventional polishing procedures
or chemical treatment in piranha solution.28
The second and higher harmonic components of a large
amplitude FT-ac experiment are extremely effective in dis-
criminating against background capacitive current and hence in
emphasizing faradaic currents of processes involving fast electron-
transfer kinetics, as shown in studies of surface-confined redox
active biological moieties such as azurin.15 In the present example,
the background capacitive current dominates the dc response,
but its influence is essentially absent in the fourth harmonic.
Consequently, the existence of significant fourth harmonic
currents, in a potential region often regarded as purely capacitive,
supports the view that the origin of these responses is faradaic,
and that electron-transfer kinetics are fast.
(28) Rafaela Fernanda Carvalhal, R. S. F., Lauro Tatsuo Kubota,, Electroanalysis
2005, 17, 1251.
Lertanantawong et al.
Large Amplitude FT-ac Voltammetry at a Gold Electrode
in the Presence of Hydrazine in Acidic Solution. Hydrazine
oxidation at a gold electrode in acidic solution was chosen as
an example of a chemically irreversible29 electrocatalytic process.
The proposed mechanism is given in eq 6. Previous studies using
NH2 - NH3+ f N2 + 5H+ + 4e- (6)
the FT-ac technique have shown that the higher harmonic
components almost completely discriminates between reversible
and nonreversible components, e.g., [Ru(NH)6]3+/2+ reversible
reduction in the presence of oxygen17 and the ferrocene mediated
oxidation of glucose.18 In these examples, the dc current is
dominated by the oxygen reduction reaction and the catalytic
(29) Gomez, R.; Orts, J. M.; Rodes, A.; Feliu, J. M.; Aldaz, A. J. Electroanal.
Chem. 1993, 358, 287.
Polycrystalline Au Electrodes in Aq Solution
Figure 3. Simulated large amplitude Fourier transformed ac cyclic voltammograms obtained for the fundamental to fourth harmonics for
a surface-confined reversible electron-transfer process at different values of k ) (a) 1 × 1010, (b) 10, and (c) 1 s-1. Other parameters included:
surface coverage of 8 × 10-11 mol cm-2, ν ) 100 mV s-1, ∆E ) 150 mV, f ) 21.46 Hz, uncompensated resistance ) 80 Ω, E0 ) 0.20
V. See reference 15 for further details.
oxidation of glucose respectively, which obscured the underlying
reversible electron transfer chemistry. Illustrated in Figure 4 are
the dc and ac fundamental to fourth harmonic components
obtained at a gold electrode in 0.5 M H2SO4 containing 10 mM
hydrazine. The dc component exhibits a broad oxidation response
on both the forward and reverse sweep, with the current
commencing and terminating at a potential of ca. 0.52 V. The
reverse sweep does not show any reduction component below
the latter value, as expected for an irreversible catalytic oxidation
process.
From the dc data, it cannot be ascertained if there is any
underlying interfacial redox cycling of the active state. However,
the presence of significant currents in both the forward and reverse
sweeps in the fundamental to fourth harmonic components implies
that this is the case. The onset potential of ca. 0.52 V for hydrazine
oxidation coincides with the potential region for Au*/Au hydrous
oxide transition observed for an unactivated and moderately
activated gold electrode (Figure 1) in acid only. There is also a
large enhancement in the ac harmonic response over the potential
range of 0.6 to 0.8 V in the presence of hydrazine compared to
gold in acid alone, presumably because the oxidized state, rather
than remaining as the hydrous oxide, is rapidly reduced back to
the active metal state by hydrazine, thereby inducing a repetitive
redox cycle like that illustrated in Scheme 1.
Recent numerical simulations30 for a mechanism where a
surface-confined one-electron-transfer process is reversible and
the coupled catalytic reaction involves a dissolved substrate is
pseudo first order show that enhancement in the magnitude of
the ac harmonic components is predicted when the bimolecular
rate constant is very fast. A somewhat analogous scenario prevails
(30) Zhang, J.; Bond, A. M. J. Electroanal. Chem. 2007, 600, 23.
Langmuir, Vol. 24, No. 6, 2008 2861
in the present case, since it is assumed that the surface-confined
Au*/Au hydrous oxide electron-transfer process is coupled to
the catalytic reaction involving dissolved hydrazine. The change
in shape of the harmonic components also suggests that the
mechanism of the underlying redox process is possibly affected
by the presence of hydrazine. Thus, the response on unactivated
gold in this potential region is broad, whereas in the presence
of hydrazine, the ac responses become better defined in the higher
harmonics.
It should be noted that in the dc and fundamental to fourth ac
harmonic components that currents are detected around 0.2 V.
This is due to the gold electrode remaining in an active state as
a result of previous electrochemical activation experiments. It
is often difficult to completely remove the active state response
for a gold electrode in aqueous solution, which again highlights
the importance of such phenomena when using this material in
electrochemical experiments.
Large Amplitude FT-ac Voltammetry at a Gold Elec-
trode in Basic Solution. Illustrated in Figure 5 are the dc and
fundamental to fifth ac harmonic components for both the positive
and negative potential scan directions (ν ) 51.48 mV s-1, f )
21.46 Hz, ∆E ) 150 mV, potential range ) -1.2 to 0.7 V) for
a polycrystalline gold electrode in 0.5 M NaOH. The dc data
(Figure 5a) show, as in the case for gold in acid solution, that
the positive sweep is featureless until the onset of monolayer
oxide formation at 0.06 V. On the subsequent negative potential
direction sweep, the monolayer oxide is removed and is followed
by a featureless response until the end of the sweep at -1.20 V.
However, in each of the fundamental to fifth harmonic responses,
there is a well-defined premonolayer oxidation response seen in
the forward sweep at -0.15 V which does not decay significantly
with respect to current magnitude in the higher harmonics. Equally
2862 Langmuir, Vol. 24, No. 6, 2008
Figure 4. Large amplitude Fourier transformed ac cyclic voltammograms obtained for the dc (a) and fundamental to fourth harmonics (b-e)
for a gold electrode in 0.5 M H2SO4 containing 10 mM hydrazine. Conditions employed: f ) 21.46 Hz, ∆E ) 150 mV, and ν ) 104.31
mV s-1.
well-defined responses are observed on the reverse sweep. In
comparison with unactivated gold electrode in acidic solution,
the ac harmonics are larger in magnitude, are present on the
reverse sweep, and are better defined. In particular, the shape of
the fourth and fifth harmonics exhibit features close to those
predicted for a fully reversible surface-confined electron-transfer
process (Figure 3).
The monolayer oxide formation/reduction processes also
exhibit significantly larger harmonic responses than detected in
acidic solution. This is consistent with a reversible electron-
transfer process occurring during the early stages of oxide
formation. The mechanism for gold oxide formation in base is
assumed31 to occur via the scheme outlined in eqs 7-8.
Au + 3OH- f Au(OH)3 + 3e- (7)
post electrochemical step
2Au(OH)3 98 Au2O3 + 3H2O (8)
(31) Burke, L. D.; Cunnane, V. J.; Lee, B. H. J. Electrochem. Soc. 1992, 139,
399.
Lertanantawong et al.
However, oxide formation is also possible via
2Au + 6OH- f Au2O3 + 3H2O + 6e- (9)
These well-defined ac harmonic responses for gold electrodes
in basic media at ca. -0.15 V can be expected if the product of
the Au*/Au hydrous oxide transition is a species such as
[Au2(OH)9]3-ads, which is stable under conditions of high
hydroxide ion concentration.
Cathodic polarization at -1.2 V was employed to activate the
surface of the polycrystalline gold electrode. In this case, the dc
data do not show any evidence of an active gold response (Figure
5) but the higher ac harmonic components exhibit current
enhancement at potentials around -0.15 V, consistent with an
increase in Au* coverage of the surface. The enhancement is
particularly pronounced in the fourth and fifth ac harmonics
where the responses now mimic behavior close to that expected
for a fully reversible surface-confined electron-transfer process
(compare Figure 5e with Figure 3a). Under conditions achieved
with cathodic polarization, the monolayer oxide formation/
removal processes are only slightly perturbed compared to
Polycrystalline Au Electrodes in Aq Solution Langmuir, Vol. 24, No. 6, 2008 2863

Figure 5. Large amplitude Fourier transformed ac cyclic voltammograms obtained for the dc (a) and fundamental to fifth harmonics (b-f)
for a gold electrode (black) and activated electrode prepolarized at -1.20 V for 5 min (red) and 20 min (blue) in 0.5 M NaOH. Conditions
employed: f ) 21.46 Hz, ∆E ) 150 mV, and ν ) 51.48 mV s-1.

unactivated gold, in both the dc and ac harmonics (Figure 5).
The FT-ac technique highlights underlying processes not
observable in dc assessments, which show only a capacitive
double-layer charging region. Given the ability of the FT-ac
technique to discriminate against capacitive current in the fourth
and fifth harmonics, it can assumed that the process observed
at -0.15 V is faradaic in nature.
Increasing the cathodic polarization time from 5 to 20 min has
an extreme effect on the voltammetry of a gold electrode in basic
media (Figure 5, blue line). Under these conditions, the dc
response shows a large increase in current just prior to the
switching potential of 0.7 V at the positive end of the sweep.
This has been observed previously and attributed to the catalytic
evolution of oxygen.31 The subsequent negative potential sweep
contains the usual response due to monolayer oxide removal as
well as a new and larger peak due to the reduction of a Au
hydrous oxide species formed during the oxygen evolution
process.32 The fundamental to fifth ac harmonic responses now
exhibit much larger currents at -0.15 V than found when using
the milder activation conditions used in the previous experiment
(Figure 5). Indeed, in the fourth and fifth harmonic ac components
the response in this potential region is dominated by the Au*/Au
hydrous oxide transition and little evidence for the monolayer
oxide formation/removal process is observable. It can also be
seen that there are minor process present at ca. -0.45 and -0.91
V attributed to the oxidation of more active Au adatoms whose
coverage is much lower than those that are oxidized at more
(32) Burke, L. D.; Moran, J. M.; Nugent, P. F. J. Solid State Electrochem.
2003, 7, 529.
2864 Langmuir, Vol. 24, No. 6, 2008
Figure 6. Large amplitude Fourier transformed ac cyclic voltammograms obtained for the dc (a) and fundamental to fifth harmonics
(b-f) for a gold electrode in 0.5 M NaOH containing 10 mM hydrazine. Conditions employed: f ) 21.46 Hz, ∆E ) 150 mV, and ν )
52.15 mV s-1.
positive potential (-0.15 V). Related premonolayer responses
also have been observed recently by dc cyclic voltammetry at
ca. -0.55 and -0.25 V (vs SCE) in basic solution after a gold
electrode had been cathodically polarized at -1.6 V for 5 min.33
Large Amplitude FT-ac Voltammetry at a Gold Elec-
trode in Basic Solution in the Presence of Hydrazine. Fig-
ure 6 contains the dc and ac fundamental to fifth harmonic
components for both the positive and negative potential scan
directions for a polycrystalline gold electrode in 0.5 M NaOH
containing 10 mM hydrazine (ν ) 52.15 mV s-1, f ) 21.46 Hz,
∆E ) 150 mV). The absence of a dc reduction response, as seen
in acidic solution, indicates that hydrazine oxidation is an overall
chemically irreversible process that occurs according to eq 10.
N2H4 + 4OH- f N2 + 4H2O + 4e- (10)
The forward positive potential direction sweep contains a well-
defined catalytic peak for hydrazine oxidation at a potential at
Lertanantawong et al.
-0.5 V. The reverse sweep contains a large plateau region from
0.20 to -0.50 V but no evidence of reduction. The fundamental
to fifth harmonic responses show evidence of two processes
occurring at ca. -0.45 and -0.18 V. The magnitude of the latter
response is comparable to that achieved when a gold electrode
in base alone was severely activated (Figure 5), whereas the
response at the more negative potential is greatly enhanced.
As is the case in acidic media, the magnitude of the catalytic
response in basic media is significantly greater than that seen for
unactivated gold in base as the oxidized hydrous oxide state is
rapidly reduced back to the active adatom state, facilitating a
reversible redox cycle. The presence of hydrazine also enhances
the process at -0.45 V which was only slightly detectable even
after severe activation. The ac harmonic response at -0.18 V
is assumed to be electrochemically quasi reversible on the basis
(33) Abu-Rabi, A.; Jasin, D.; Mentus, S. J. Electroanal. Chem. 2007, 600,
364.
Polycrystalline Au Electrodes in Aq Solution
Figure 7. Large amplitude Fourier transformed ac cyclic voltammograms obtained for the dc (a) and fundamental to fifth harmonics (b-f)
for a gold electrode in 0.5 M NaOH containing 10 mM ethylene glycol. Conditions employed: f ) 21.46 Hz, ∆E ) 150 mV, and ν ) 52.15
mV s-1.
of comparison to the simulation provided in Figure 3. This study
illustrates the effectiveness of the FT-ac technique in probing
underlying interfacial electron-transfer chemistry in the presence
of a large irreversible catalytic process where almost total
discrimination of the two processes is achieved in the higher
harmonics.
Large Amplitude FT-ac Voltammetry at a Gold Elec-
trode in Basic Solution in the Presence of Ethylene Glycol.
Illustrated in Figure 7 are the dc and ac harmonic components
(ν ) 52.15 mV s-1, f ) 21.46 Hz, ∆E ) 150 mV) for a
polycrystalline gold electrode in 0.5 M NaOH, but now containing
10 mM ethylene glycol. The dc response (Figure 7a) reveals that
oxidation of ethylene glycol commences at ca. -0.20 V until it
reaches a peak at 0.18 V where monolayer oxide commences.
At more positive potentials, the gold surface is deactivated, and
the electrocatalytic reaction shuts off completely. On the reverse
Langmuir, Vol. 24, No. 6, 2008 2865
sweep a small cathodic peak is observed at 0.20 V which is due
to the removal of the oxide layer after which there is a large
increase in anodic current due to the recommencement of ethylene
glycol oxidation. The absence of a dc reduction response for the
remainder of the reverse sweep indicates an irreversible reaction
which can be represented by eq 11. The fundamental to fifth
(CH2OH)2 + 10OH- f (CO2)22- + 8H2O + 8e- (11)
harmonic responses provide evidence of two processes at ca.
-0.15 and 0.20 V on both sweep directions. The process at the
latter is again assumed to be due to a reasonably fast electron-
transfer process associated with the initial stages of monolayer
oxide formation. The process at -0.15 V, as seen in the hydrazine
case, is assigned to the repetitive cycling of the Au*/Au hydrous
oxide transition induced by the presence of ethylene glycol, noting
2866 Langmuir, Vol. 24, No. 6, 2008
Figure 8. Large amplitude Fourier transformed ac cyclic voltammograms obtained for the dc (a) and fundamental to fifth harmonics
(b-f) for a gold electrode in 0.5 M NaOH containing 10 mM glucose. Conditions employed: f ) 21.46 Hz, ∆E ) 150 mV, and ν )
51.48 mV s-1.
that an unactivated gold electrode in base gave a much smaller
response at this potential (Figure 5). From the magnitude and
shape of the harmonics it can be concluded that this underlying
interfacial redox process is close to reversible as is the case with
a highly activated gold electrode in basic solution (Figure 5).
However, the current magnitude of this response is less than that
observed in the hydrazine case (Figure 6) even though equal
concentrations were used. This is possibly due to the fact that
ethylene glycol reacts less rapidly with the Au hydrous oxide
state than hydrazine which is a very efficient reductant.34
Large Amplitude FT-ac Voltammetry at a Gold Elec-
trode in Basic Solution in the Presence of Glucose. In the
case of large amplitude FT-ac voltammetry at a polycrystalline
gold electrode in 0.5 M NaOH containing 10 mM glucose, the
dc current (Figure 8a) shows that glucose oxidation commences
at -0.70 V. At -0.30 V a further increase is detected until 0.18
Lertanantawong et al.
V where monolayer oxide formation deactivates the gold surface
and the electrocatalytic reaction ceases. On the reverse sweep,
a small cathodic peak at 0.20 V associated with the removal of
the oxide layer, is followed by a large anodic current region due
to recommencement of oxidation of glucose with a broad minor
shoulder centered at ca. -0.60 V also present. The ac harmonics
(Figure 8b,c,d,e) all exhibit three distinct processes on both the
forward and reverse sweeps centered at ca. -0.45, -0.15, and
0.20 V. The latter response, as noted previously, is associated
with monolayer oxide formation/removal processes. The two
processes at -0.45 and -0.15 V indicate the possibility of two
different mediating species being involved in the oxidation of
glucose. Such behavior has been postulated35 on the basis of dc
cyclic voltammetry.
(34) Djokic, S. S. J. Electrochem. Soc. 1997, 144, 2358.
Polycrystalline Au Electrodes in Aq Solution
As in the ethylene glycol case, the current magnitude of the
premonolayer responses is lower than observed in the hydrazine
case (but greater than for unactivated gold) presumably because
glucose does not interact as rapidly with the oxidized state of
Au*. However, the shape and magnitude of the ac components
indicates that there are underlying quasi-reversible interfacial
redox processes that take place during the electrocatalytic
oxidation of glucose.
Comparison of the Behavior of Gold Electrodes in Aqueous
Acidic and Basic Media. FT-ac voltammetric studies reveal
that the extent of premonolayer oxidation is low at an unacti-
vated gold electrode in aqueous solution. A small broad fun-
damental harmonic minor response was found in acid solution
at 0.60 V (Figure 1b). However, in basic media a significant Au*
oxidation response was detected at -0.20 V in all five ac
harmonics examined. The electron-transfer component of the
response in base is assumed to be rapid on the basis of compari-
son with simulated FT-ac voltammetry for a fully reversible
surface-confined electron-transfer process. The dc response in
either 0.5 M H2SO4 or 0.5 M NaOH showed no evidence of any
faradaic process in the so-called gold electrode double-layer
region. This highlights the sensitivity of the FT-ac technique to
faradaic processes that involve fast electron-transfer kinetics.
The possibility of a capacitive effect being the sole origin of
processes found by ac voltammetry also can be ruled out as this
technique is extremely effective in achieving very high faradaic
to capacitive current ratios, particularly in the fourth and fifth
harmonics.
Interestingly, a substantial current response also is found in
the fundamental and higher ac harmonics in the potential region
involving monolayer oxide formation and its removal in both
acidic and basic solutions. It has been postulated that the initial
stages of monolayer oxide formation at a gold electrode involves
a fast electron-transfer process, outlined in eqs 4 and 7, before
conversion to the compact anhydrous Au2O3 oxide layer. The
shapes of the fourth and fifth ac harmonics indicate that the
electron-transfer step associated with monolayer oxide formation
in base is more reversible than in acid, as also is the case for the
premonolayer oxidation responses found at 0.60 V in acid and
-0.45 V in base. The latter is related to the enhanced stability
of hydrous oxide species when a high concentration of hydroxide
ion are present in solution.
Cathodic polarization of gold in the hydrogen evolution region
results in three premonolayer oxidation processes at different
potentials which were identified from FT-ac voltammetry in both
acid (0.22, 0.60, and 0.95 V) and base (-0.91, -0.45, and -0.15
V) whose magnitude depend on the applied potential and duration
(compare Figures 1 and 2). A dc oxidative response (0.22 V)
from an activated gold electrode in acid was detected but no
reductive counterpart was in evidence in dc cyclic voltammo-
grams. After a related form of activation pretreatment in base,
a significant enhancement in the oxidative response at -0.15 V
in the ac fundamental to fifth harmonics was observed, along
with a significant reductive counterpart. However, the dc data
showed no evidence of a premonolayer oxidation response. It is
clear that cathodic pretreatment (Figure 2) generates significant
FT-ac responses within the double-layer region in both the forward
and reverse sweeps. The assumption here is that the active site
is invariably present (at a very low coverage) at the metal surface
as demonstrated for nonactivated electrodes (Figure 1, black
line). Its coverage and hence response as detected by the FT-ac
technique is temporarily enhanced by appropriate electrochemical
pretreatment.
(35) Burke, L. D.; Ryan, T. G. Electrochim. Acta 1992, 37, 1363.
Langmuir, Vol. 24, No. 6, 2008 2867
The existence and the amount of coverage of active sites has
been the most widely accepted explanation for the variability
observed in the performance of gold catalysts36 even though the
identification of such active gold sites at room temperature
using surface science techniques such as LEED, STM, and
AFM is extremely difficult.37 Practical surfaces such as poly-
crystalline gold used in catalytic systems and often in analytical
applications are far from ideal and are not totally defect free. The
clearest analogy to the present work is the use of surface enhanced
raman spectroscopy (SERS) to explore the behavior of gold
(plus silver and copper) electrode surfaces. To observe a SERS
response for these electrodes in aqueous media, it is necessary
to roughen the surface by oxidation-reduction cycling (ORC)
pretreatment.38 The present FT-ac voltammetry approach in
combination with other surface techniques offer unique insights
into the electrochemistry of polycrystalline gold which is quite
complex.
As highlighted in a recent review of the electrochemical
behavior of gold in aqueous media, virtually all electrocatalytic
reactions on this surface occur within the so-called double-layer
region at potentials values where Au* to Au hydrous oxide
transitions have been postulated to occur, in the absence of
reagent.7 Therefore, gold in aqueous media may behave
analogously to a chemically modified electrode. In the latter
case, a relatively inert electrode material such as carbon or indium
tin oxide is modified (to enhance its electrocatalytic activity) by
attaching, for example, a layer of redox active material. For a
gold electrode, bulk gold or EMS atoms function as the inert
support while the Au* or MMS atoms act as the redox mediators.
A mediated electrocatalytic process is then established as outlined
in Scheme 1 which is the basis of the IHOAM model. In most
previous studies, only the dc catalytic current was available to
provide evidence for such a scheme. The FT-ac technique offers
the advantage of being able to identify mediated electrocatalytic
schemes by probing underlying reversible electron-transfer
processes. The higher harmonics effectively discriminate between
electron transfer and coupled chemical processes.
A substantial enhancement of the magnitude of the premono-
layer responses for gold electrodes in acidic and basic media was
detected in the presence of hydrazine, ethylene glycol, and glucose
compared to an unactivated electrode from the fundamental to
fourth harmonics. Analogous behavior was predicted recently
by theoretical studies of large amplitude alternating current
voltammetry for a reversible surface-confined electron-transfer
process coupled to a pseudo first-order electrocatalytic process
where significant enhancement of the magnitude of the ac
harmonics was seen when the bimolecular reaction rate con-
stant for the catalytic reaction was very fast. However, the
enhancement in the magnitude of the ac responses seen for the
ethylene glycol and glucose case in basic media was not as
significant as seen for the hydrazine case suggesting that the
regeneration of the Au* state is not as effective. The results from
this study using FT-ac voltammetry support the IHOAM model
of electrocatalysis and offer further insights into the nature of
active sites.
Conclusions
The large amplitude FT-ac technique readily reveals the
presence of significant Faradaic processes at potentials within
the so-called double-layer region of gold electrodes in acidic and
(36) Menegazzo, F.; Manzoli, M.; Chiorino, A.; Boccuzzi, F.; Tabakova, T.;
Signoretto, M.; Pinna, F.; Pernicone, N. J. Catal. 2006, 237, 431.
(37) Burke, L. D.; Hurley, L. M. Electrochim. Acta 1999, 44, 3451.
(38) Desilvestro, J.; Weaver, M. J. J. Electroanal. Chem. 1986, 209, 377.
2868 Langmuir, Vol. 24, No. 6, 2008
basic media, where the current has often been assumed to be
purely capacitive in nature. The origin of these faradaic processes
has been related to an active state model in which protruding or
low coordination adatoms (Au*) on the gold surface are present
at low coverages and are oxidized in the double-layer region to
form Au hydrous oxide species. During the course of overall
irreversible electrocatalytic reactions, the FT-ac technique has
revealed that there exists one or in some cases two underlying
interfacial electron-transfer process that are fast and extremely
effective in mediating the reactions. Although only qualitative,
the FT-ac results emphasize that the electrochemical behavior
of polycrystalline gold electrodes in aqueous solution is complex
in the double-layer region where most electrocatalytic processes
occur.
Lertanantawong et al.
Acknowledgment. Funding from the Australian Research
Council in support of this project is gratefully acknowledged.
B.L. acknowledges the National Center for Genetic Engineering
and Biotechnology and King Mongkut’s University of Technol-
ogy Thonburi for providing funding to participate in this work
in Australia.
Supporting Information Available: Figure S1 shows large
amplitude Fourier transformed ac cyclic voltammograms obtained
for an activated (mildly abraded) gold electrode in 0.5 M H2SO4.
This material is available free of charge via the Internet at
http://pubs.acs.org.
LA702454K