Journal of Electroanalytical Chemistry 634 (2009) 90–97

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Journal of Electroanalytical Chemistry

journal homepage: www.elsevier.com/locate/jelechem

Square Wave Voltammetry and Voltcoulometry applied to electrocatalytic

reactions. Oxidation of ferrocyanide at a ferrocene modified gold electrode
J. González, C.M. Soto, A. Molina *
Departamento de Química Física, Universidad de Murcia, Espinardo 30100, Murcia, Spain

a r t i c l e i n f o a b s t r a c t

Article history: The electrochemical response of an electrocatalytic process taking place at a redox mediator modified
Received 27 May 2009 electrode has been analysed with Square Wave Voltammetry (SWV) and Square Wave Voltcoulometry
Received in revised form 15 July 2009 (SWVC) for which, a simple expression of the current and converted charge have been deduced for the
Accepted 23 July 2009
usual experimental situation of high catalytic rate constants. Both techniques give rise to peak-shaped
Available online 30 July 2009
responses whose peak parameters have been deduced in the case of reversible electrochemical step.
The influence of key parameters such as the square wave pulse amplitude, the rate constant of the chem-
Keywords:
ical step and the reversibility of the charge transfer has been studied. Moreover, the SWVC charge–poten-
Square Wave Voltammetry
Square Wave Voltcoulometry
tial curves allow an immediate determination of the catalytic rate constant, independently of the value of
Electrocatalysis the electrochemical rate constant. The theoretical predictions have been tested with the electrocatalytic
Monolayer oxidation of ferrocyanide mediated by a mixed 6-(ferrocenyl)hexanethiol-hexanethiol monolayer at a
Ferrocene disk gold electrode, and an excellent agreement between theory and experiments has been found.
Ó 2009 Elsevier B.V. All rights reserved.

1. Introduction the most important of which is their widely acknowledged inher-

Electrocatalysis with modified electrodes can be defined as the
use of electron mediators intentionally immobilised at the elec-
trode surface to reduce the activation overpotential and therefore
accelerate the reactions of molecules in solution that would other-
wise undergo a slow reaction at a naked electrode [1–3]. Among
the most used of modified electrodes are those based on the cova-
lent attachment of redox species forming an electroactive mono-
layer, such as those derived from alkanethiols with pendant
redox groups [4,5].
A theoretical modelling of the mechanism of mediation is
important in the comprehension of electrocatalytic processes.
The purpose of this model is to identify the key experimental fac-
tors which determine the response in order to obtain a deep insight
of the process. Since the electrochemical activation (through the
application of an electrical perturbation to the electrode) of the
immobilised mediator at the electrode surface is the first step of
the reaction, different electrochemical techniques have been used
in order to analyse the influence of both electrochemical and
chemical kinetics in the global response [6–11].
Among these techniques, those based on the application of a
sequence of potential pulses of discrete nature and, especially,
Square Wave Voltammetry, present several advantages, one of
* Corresponding author. Tel.: +34 868 887524; fax: +34 868 884148.
E-mail address: amolina@um.es (A. Molina).
ent ability to decouple faradaic currents from non-faradaic ones
[12–14]. Moreover, square wave multipotential perturbation al-
lows most of the non-desired effects to be minimized since the reg-
istered response is related with the difference of signals obtained
between successive half-cycles of potential [12–14].
In this paper we will analyse the behaviour of electrocatalytic
processes at monolayer modified electrodes when square wave
potentials sequence is applied, from which a peak shaped cur-
rent–potential response or Square Wave Voltammogram (SWV)
amplified by the catalytic rate constant is obtained, even when
the electrochemical step is reversible (in contrast to the behaviour
of nernstian charge transfer processes, which lead to practically
null current [10,14]).
In this paper we have also used Square Wave Voltcoulometry
(SWVC), a technique introduced by some of us in a previous paper
[14], which is based on the analysis of the difference of converted
charge signals obtained for two successive square wave half-cycles.
The SWVC charge–potential curve presents important advantages
as compared to the SWV one in the study of electrocatalytic reac-
tions, since SWVC allows the catalytic rate constant to be deter-
mined from the anodic limit charge, whose value is independent
of the square wave pulse amplitude and also of the reversibility
of the electrochemical step.
Moreover, important simplified expressions for the current–po-
tential and charge–potential responses have been deduced for the
usual experimental situation in which high values of the catalytic
rate constant are considered.

0022-0728/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jelechem.2009.07.014
 J. González et al. / Journal of Electroanalytical Chemistry 634 (2009) 90–97
The above theoretical expressions have been validated by ana-
lyzing the electrocatalytic oxidation of ferrocyanide mediated by
a mixed 6-(ferrocenyl)hexanethiol-hexanethiol monolayer in gold,
a system which shows a very fast electrochemical step for the fer-
roceno/ferrocinium conversion, followed by a simple electron
transfer between the iron complex in solution and that of the
monolayer. A reversible electrochemical step has been observed
from our results in Square Wave Voltammetry and Voltcoulometry,
and we have easily obtained the catalytic rate constant, and also
the formal potential and the surface coverage of the 6-
(ferrocenyl)hexanethiol.
2. Experimental
2.1. Reagents and chemicals
Ethanol (Merck), 6-(Ferrocenyl)hexanethiol (C6H22FeS), 1-Hexa-
nethiol (C6SH), NaClO4, potassium ferrocyanide (K4[Fe(CN)6]) (Sig-
ma–Aldrich) were reagent grade and used as received.
2.2. Electrochemistry
Square Wave Voltammetry (SWV) and Voltcoulometry (SWVC)
were performed by using a computer-driven potentiostat–galvano-
stat designed and constructed by Quiceltron.
A three-electrode cell was employed in the experiments with a
home-made disk gold electrode of diameter 0.01 cm as working
electrode. The counter electrode was a Pt foil, and the reference
electrode was a saturated calomel electrode (SCE). Solutions were
prepared with distilled deionized water (Milli-Q filtering system).
Nitrogen gas was passed through solutions for de-aeration for
20 min prior to measurements, with nitrogen atmosphere main-
tained over the solution during all the experiments. All the kinetic
and thermodynamic values obtained for the ferrocyanide system
correspond to series of five essays. The results are the mean of
the five experimental values. The errors correspond to the standard
deviation.
Background currents of the current–potential responses have
been calculated from a polynomical fitting of the baseline of the
experimental SWV curves at values sufficiently far from the peak
region, and subtracted from the ISW–E curves.
The coverages of the ferrocene moiety have been obtained from
the charge plateau of the charge–potential curves in Square Wave
Voltcoulometry, and also from the numerical integration of base-
line corrected cyclic voltammograms of freshly prepared monolay-
ers in an aqueous solution NaClO4 1.0 M. In all the cases, coincident
values have been obtained.
The roughness factor of the gold electrode, defined as the ratio
fr = Sr/Sg with Sr and Sg being the real surface and geometrical areas,
has been determined from the integration of the reduction peak re-
corded in a 1.0 M H2SO4 solution with a sweep rate v = 0.050 V s1,
by assuming a value of 400 lC cm2 for a monolayer of chemi-
sorbed oxygen at a polycrystalline gold electrode [15]. From these
measurements we have obtained fr = 5.91.
To avoid transport effects in the catalytic response, a magnetic
stirrer with a constant rotation rate was placed close to the elec-
trode surface, so a constant agitation was maintained during the
whole experiment. By proceeding in this way we have checked that
the values of the catalytic pseudo first order rate constant obtained
do not depend on the ferrocyanide concentration.
2.2.1. Preparation of the mixed ferrocene modified gold electrode
Monolayers of ferrocene were formed by the self-assembling
technique on gold substrates. The gold electrode was mechanically
polished on alumina slurry (0.05 lm, Buehler), washed and elec-
91
trochemically cleaned by cycling the potential first between 0 V
and 1.4 V (vs. SCE) in 2.0 M NaOH and, secondly, between 1.6 V
and 0.4 V (vs. SCE) in 1.0 M H2SO4 until a stable voltammogram
was obtained. It was then washed with ethanol and water, and
the electrode was immersed in mixed solution 2 mM 6-(Ferroce-
nyl)hexanethiol + 2 mM 1-Hexanethiol in a ratio 1:20 (V:V) respec-
tively, for 24 h at room temperature. Upon removal from the
deposition solution, the electrode was thoroughly rinsed with eth-
anol and water before use to remove the physically adsorbed
species.
3. Theory
3.1. General features of square wave current–potential and converted
charge–potential curves
Square Wave Voltammetry (SWV) and Square Wave Voltcoul-
ometry (SWVC) are two multipotential pulse techniques on which
a square wave sequence of potential pulses of height 2|ESW| with
the same duration, s, and superimposed to a staircase potential
of width 2s, is applied. |DEs| is the potential step in the staircase
and |ESW| is the square wave amplitude, in agreement with the
scheme given in Refs. [12,14,16,17]. The waveform can be applied
in single (direct scan only) or cyclic mode (direct and inverse
scans). In the latter, once the final potential has been reached,
the waveform is reversed, returning through the same sequence
of pulses to the initial potential. This potential sequence can be de-
scribed by the following equation:
)
 
Ep ¼ Einitial þ Intðpþ1
2
Þ  1 jDEs j þ ð1Þpþ1 jESW j; p ¼ 1; 2; . . . ; np=2
Ep ¼ Enppþ1 ; p ¼ ðnp=2Þ þ 1; . . . ; np
ð1Þ
The signal is measured at the end of each potential pulse and
the net response is the difference between the signal correspond-
ing to a pulse with odd index (forward) and the signal of the fol-
lowing pulse with even index (reverse). Typically, this signal is
the current, such that the usual ISW–E Square Wave Voltammetry
curve is defined as:
ISW ¼ I2p1  I2p ¼ If  Ir ; p ¼ 1; 2; . . . ; ðnp=2Þ ð2Þ
In a previous work we have also applied the square wave poten-
tial sequence to the analysis of the converted charge in an electro-
active monolayer [14]. Thus, in this case we obtain the QSW–E
curves of this process being,
Q SW ¼ Q 2p1  Q 2p ¼ Q f  Q r ; p ¼ 1; 2; . . . ; ðnp=2Þ ð3Þ
The subindexes f and r which appear in the expressions of the
square wave current and charge (Eqs. (2) and (3)), refer to the
pulses forward and reverse (equal to 2p1 and 2p, respectively).
Both QSW and ISW signals are plotted vs. the index potential, de-
fined as an intermediate potential value between each pair of con-
secutive pulses,
Eindex;p ¼ Ep þ ð1Þp jESW j ð4Þ
In this paper, we will apply SWV and SWVC techniques to the
study of a mediated electron transfer between a soluble species
and an electrode by means of an electroactive species immobilised
at the electrode surface forming a monolayer in agreement with
the following Scheme I with kox and kred being the heterogeneous
rate constants for the oxidation and reduction, respectively, of
0
the adsorbed mediator couple A/B, and kc the rate constant for
the chemical step. We will assume that the concentrations of spe-
cies C and D at the monolayer/solution interface are constant and
equal to their bulk values (cC and cD , respectively), so we can define
a pseudo first order rate constant,
92 J. González et al. / Journal of Electroanalytical Chemistry 634 (2009) 90–97

  
0
kc ¼ kc cC ð5Þ ISW egf egr
¼ kc gf  ð10Þ
Q MAX rev 1þe 1 þ egr
Moreover, we will suppose that there are no interactions be-
tween the adsorbates and also that no desorption is observed in with gf = gr + (2nF/(RT))|ESW|.
the time scale of the experiment. This response presents a peak whose potential and height are
The current corresponding to the above process has been previ- given by:
ously deduced in Ref. [11]. The transformed charged can be ob-
Rs Epeak 0
tained by carrying out the integral Q ¼ 0 Idt. By introducing SWV ¼ E ð11Þ
g 
these expressions into those corresponding to ISW and QSW (Eqs. Ipeak ¼ kc Q MAX tanh SW
ð12Þ
SWV
(2) and (3)), we obtain the analytical expressions of current and 2
converted charge and, therefore, we can fully characterise the with
behaviour of these two magnitudes.
nFjESW j
In the following we will consider a particular case of the process gSW ¼ ð13Þ
given in Scheme I, which is the most frequent in the literature (see
RT
[2,3,18–20]). This case corresponds to a fast catalytic reaction, i.e., Finally, the half-peak width takes the value
kc  1 s1, for any values of the electrochemical rate constants kred 0 qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi1
and kox. Introducing that restriction in Eqs. (2) and (3), the following v RT B 1 þ e 2gSW
þ 4egSW þ ð1 þ e2gSW þ 4egSW Þ2  4e2gSW C
limiting expressions for the current and charge can be obtained:
W re
1=2 ¼ ln @ qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiA
nF
1 þ e2gSW þ 4egSW  ð1 þ e2gSW þ 4egSW Þ2  4e2gSW
3.1.1. Current–potential curves ð14Þ
For fast catalyzed reactions the stationary (independent of
Note that the peak potential given by Eq. (11) does not depend
time) ISW–E response is given by (see Eqs. (2) and (3), and Eq.
on the characteristics of the square wave sequence, whereas the
(15) in Ref. [11]), rev
   peak current, Ipeak
SW , and the half-peak width, W 1=2 , depend on the
ISW kox;f kox;r square wave amplitude according to Eqs. (12) and (14). These
¼ kc  ð6Þ
Q MAX kT;f kT;r parameters present the following limiting values:
v
where W re
1=2 ¼ 90=n mV Ipeak nFjESW j
SW ¼ kc Q MAX 2RT for jnESW j < 10 mV
 v
kT;p ¼ kE;p þ kc W re
1=2 ¼ 2jESW j mV Ipeak
SW ¼ kc Q MAX for jnESW j > 120 mV
ð7Þ
kE;p ¼ kred;p þ kox;p ð15Þ
and QMAX = nFSCT, with S being the electrode area and CT the total From these expressions, it is evident that the square wave ISW–E
electroactive surface excess. curves corresponding to a catalytic mechanism like that given in
If we suppose a Butler–Volmer kinetics for the charge transfer Scheme I behave in a similar way to the QSW–E curves observed
step, the heterogeneous rate constants corresponding to this po- for a reversible charge transfer process (see Eqs. (10)–(14)) in
tential are [6,10]: [14] for the expressions of the peak parameters), with the current
) being amplified by the chemical rate constant kc.
kox;p ¼ egp kred;p
0 ð8Þ Note that, in agreement with the above Equations, for E ? 1
kred;p ¼ k eagp and E ? 1, the following limiting currents are obtained:
nF 
gp ¼ ðEp  E0 Þ ð9Þ ISW
RT ¼0 ð16Þ
Q MAX E!1
0 0
where p = f or r. k , a and E are the heterogeneous rate constant,
the charge transfer coefficient and formal potential of the surface
couple, respectively. 3.1.2. Charge–potential curves
For a reversible charge transfer, kox ? 1 and kred ? 1, and we In this case, the following QSW–E relation is obtained (see Eqs.
deduce from Eqs. (2), (6): (2) and (3), and Eq. (15) in Ref. [11]):
  
Q SW kox;f kox;r ð1 þ kc sÞ kc kox;f kox;r
¼    ð17Þ
Q MAX kT;f kT;r kT;r kT;f kT;r
This equation shows that a steady state (i.e., an independent of
time behaviour) cannot be obtained for the QSW–E curves.
E lectro d e M o n o layer So lu tio n
For a reversible charge transfer, kox ? 1 and kred ? 1, and we
deduce from Eqs. (3), (17):

Q SW egf egr ð1 þ kc sÞ
A D Q MAX rev
¼
1þe gf 
1 þ egr
ð18Þ

k c' The QSW–E response also presents a peak-shaped response but it

is distorted by the catalytic contribution (1 + kcs) which appears at
e− B C the backward term (see also Eq. (10) in [14]). We will discuss the
main features of this response below.
Note that, in agreement with the above Eqs., for E ? 1 and
⎯⎯→ B + e−
A ←⎯⎯
kox E ? 1, the following converted charge limits are obtained:
9
k red 
Q SW
Q MAX
¼0 >
=
k c′
B + C ⎯⎯ → A+ D  E!1
ð19Þ
Q SW
Q MAX
¼ kc s >
;
E!1
Scheme I.
 J. González et al. / Journal of Electroanalytical Chemistry 634 (2009) 90–97
These limits are independent of the reversibility degree of the
electrochemical step.
4. Results and discussion
4.1. Theoretical results
Figs. 1 and 2 show the theoretical (ISW/QMAX)  (E  E0) and
(QSW/QMAX)  (E  E0) curves, calculated from Eqs. (2), (3) and Eq.
(15) in [11], for different values of the catalytic rate constant kc
and a fixed square wave pulse amplitude ESW = 100 mV (Fig. 1),
and also for different values of the square wave pulse amplitude
and a fixed catalytic rate constant kc = 10 s1 (Fig. 2). In both cases
we have considered two values of the dimensionless heteroge-
neous rate constant (k0s) = 10 and 0.5, which refer to reversible
(Fig. 1a and b) and quasi-reversible (Fig. 1c and d) electrochemical
behaviour. In Fig. 1 we have included the case corresponding to a
simple charge transfer process (kc = 0), for comparison. Note that
this process gives rise to null current under nernstian conditions
(see Fig. 1a) [14].
From the ISW–E curves in Fig. 1a and c it can be seen that the
current increases with kc, whatever the reversibility degree of the
electrochemical step. Under reversible conditions (Figs. 1a and
2a), these curves present a peak shaped feature centred at the for-
mal potential of the immobilised electroactive species (dotted line,
see Eq. (11)). When the square wave pulse amplitude increases
(Fig. 2a), the peak becomes broader and it reaches a plateau whose
height becomes independent of ESW for ESW P 120 mV , in agree-
ment with Eqs. (12)–(15).
When the charge transfer step is quasi-reversible, the ISW–E
curve shows one or two peaks depending on the values of kc and
ESW. Typically, an increase of kc gives rise to a single peak located
at more positive potentials than E0 (see Fig. 1c). Concerning the
Fig. 1. Theoretical (ISW/QMAX)  (E  E0) (1a and 1c) and (QSW/QMAX)  (E  E0) (1b and 1d) curves calculated from Eqs. (2), (3) and Eq. (15) in [11] in Square Wave
Voltammetry and Voltcoulometry, respectively, for a catalytic mechanism. The values of kc and of the dimensionless heterogeneous rate constant (k0s) are on the curves.
DE ¼ 5 mV, ESW ¼ 100 mV, s ¼ 50 ms, Einitial = 400 mV, Efinal = 400 mV, T = 298 K, a ¼ 0:5 and n = 1.
93
influence of ESW, for low values of the square wave pulse ampli-
tude, a single peak appears, which becomes two asymmetric peaks
which are more separated the higher ESW (see Fig. 2c). In this case,
the usual quasi-reversible splitting of the ISW–E response is ob-
served at higher ESW values as kc increases. No simple expressions
for the peak parameters can be obtained in these conditions.
The QSW–E curves in Figs. 1 and 2 show a peak-shaped response
whose anodic limit is determined by the catalytic rate constant va-
lue (see Eqs. (17)–(19)). The catalytic term gives rise to a constant
value at anodic potentials, independently of the square wave pulse
amplitude ESW and the heterogeneous rate constant k0 (see Eq. (19)
and Fig. 2b and d). The peak height of the charge–potential curves
increases with ESW until a charge plateau equal to QMAX is obtained
for ESW P 120 mV in the reversible curves of Fig. 2b. For processes
with non-reversible charge transfer step a higher ESW is necessary
to reach a plateau independent of the square wave pulse
amplitude.
The peak potential expression of the QSW–E curves can be ob-
tained for reversible conditions by imposing dQSW/dE = 0 in Eq.
(18),
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi!
0RT kc s  ðegSW  egSW Þ 1 þ kc s
Epeak ¼E þ ln ð20Þ
nF egSW  ð1 þ kc sÞegSW
This Eq. indicates that the peak potential is located at more neg-
ative values than E0 and it moves towards the formal potential as
ESW increases. When high values of the square wave pulse ampli-
tude are used, the QSW–E curves show a broad plateau which is
centred at a potential E = E0  RT/(2nF) ln (1 + kcs), in agreement
with the above equation.
Another interesting characteristic of the QSW–E curve is the
cross potential for which the converted charge is null. For revers-
ible conditions, it is given by (see Eq. (18) for QSW = 0),
94 J. González et al. / Journal of Electroanalytical Chemistry 634 (2009) 90–97
Fig. 2. Theoretical (ISW/QMAX)  (E  E0) (2a and 2c) and (QSW/QMAX)  (E  E0) curves (2b and 2d) calculated from Eqs. (2), (3) and Eq. (15) in [11] in Square Wave
Voltammetry and Voltcoulometry, respectively, for a catalytic mechanism. kc = 10 s1. The values of ESW and of the dimensionless heterogeneous rate constant (k0s) are on the
curves. Other conditions as in Fig. 1.
 g 
RT e SW  egSW ð1 þ kc sÞ
EQ SW ¼0 ¼ E0 þ ln
nF kc s
That expression simplifies for high values of the square wave
pulse amplitude,
RT
EQ SW ¼0 ffi E0  lnðkc sÞ þ ESW
nF
such that this potential moves linearly towards positive values with
ESW (see Fig. 2b).
For quasi-reversible conditions (Figs. 1d and 2d), the shape of
the QSW–E curves is similar to the reversible ones, although the
peak heights are smaller than those obtained for the reversible
case.
Fig. 3 shows the influence of the reversibility degree of the elec-
trochemical step on the theoretical ISW–E and QSW–E curves of the
process given in Scheme I. These curves have been calculated from
Eqs. (2), (3) an (15) of [11] for different values of the dimensionless
heterogeneous rate constant (k0s), with ESW ¼ 50 mV, s ¼ 10 ms
and kc ¼ 20 s1 .
From Fig. 3a, the complex influence of (k0s) in the ISW–E curves
can be seen. These responses present a single broad peak for
0
reversible conditions ðk s ¼ 10Þ, that changes into two higher
peaks as k0s decreases, and finally becomes one peak again, which
decreases and moves towards more positive potentials for totally
0
irreversible charge transfers ðk s ¼ 0:01Þ. The disparity of peak fea-
tures observed in this figure is the result of the great sensitivity of
the current to the electrochemical and catalytic rate constants of
the process.
In the case of the QSW–E curves of Fig. 3b, the variation of k0s
causes two clear effects: firstly, the decrease of the peak height
with k0s, in the same way to that observed for a simple charge
transfer step (see [14]), and secondly, the anodic charge appears
at more positive potentials the lesser k0 is. Note that the QSW–E
curves (Fig. 3b) present an important advantage over the ISW–E
ones (Fig. 3a), since they present an anodic limit charge which is
ð21Þ
independent of the electrochemical rate constant and which only
depends on the catalytic rate constant, in agreement with Eq.
(19)). Therefore, kc can be immediately obtained from this limit.
ð22Þ 4.2. Experimental results
We have verified the applicability of the equations given in this
paper by analysing the experimental Square Wave Voltammo-
grams and Square Wave Voltcoulogramms of a ferrocene-contain-
ing monolayer on a gold electrode in presence of potassium
ferrocyanide.
Ferrocene self assembled monolayers have been widely used in
electrochemical studies since they give rise to ideal or nearly ideal
voltammetric behaviour when the ferrocene moiety is diluted with
an electroinactive alkanethiol [4,5,18,20]. Moreover, these mono-
layers present very good stability, a low degree of defects and
interactions, very good blocking ability for the electrode surface
and a high chemical versatility [5].
We have formed a 6-(ferrocenyl)hexanethiol-hexanethiol
(FcC6SH–C6SH, 1:20) mixed monolayer by following the procedure
described in the Section 4.2, and the redox reaction of the ferrocene
moiety as electrochemical mediator has been investigated in the
presence of potassium ferrocyanide as reducing agent. Thus, the
ferrocenium formed at anodic potentials is reduced to ferrocene
by the ferrocyanide in solution and the whole process becomes a
surface catalytic reaction, in agreement with Scheme II.
This process implies a first electrochemical step with a very fast
conversion of the ferroceno/ferrocinium couple, due to the short
length of the alkyl chain, and also a second chemical step with a
simple electron transfer between the iron complex in solution
and that of the monolayer. Moreover, the thiols block the gold sur-
face in such a way that the FeðCNÞ46 oxidation will take place due
solely to the ferrocene mediation at the monolayer with a very
 J. González et al. / Journal of Electroanalytical Chemistry 634 (2009) 90–97
Fig. 3. Theoretical (ISW/QMAX)  (E  E0) (a) and (QSW/QMAX)  (E  E0) (b) curves
calculated from Eqs. (2) and (3) and Eq. (15) in [11] in Square Wave Voltammetry
and Voltcoulometry, respectively, for a catalytic mechanism. kc ¼ 20 s1 ,
ESW ¼ 100 mV and s ¼ 10 ms. The values of the dimensionless heterogeneous rate
constant (k0s) are on the curves. Other conditions as in Fig. 1.
high efficiency (i.e., the catalytic way is observed at potentials
500 mV lower than those corresponding to a gold electrode with
a C6SH monolayer).
We have initially evaluated the electrochemical behaviour of
the FcC6SH–C6SH mixed monolayer in an aqueous NaClO4 1.0 M
medium with Square Wave Voltammetry, cyclic voltammetry
and multipulse chronoamperometry. Fast electrochemical charge
transfer processes which can be considered as reversible have been
observed, such that Eqs. (10) and (18) for the ISW–E and QSW–E
curves will be applied to characterise the catalytic responses of this
system.
Figs. 4 and 5 show the experimental (ISW/QMAX)  (E  E0) and
(QSW/QMAX)  (E  E0) curves of the FcC6SH–C6SH mixed monolayer
at a disk gold electrode of 100 lm diameter in a solution 1.0 M Na-
ClO4, obtained for different values of potassium ferrocyanide con-
centration (i.e., different values of the catalytic rate constant kc),
and a fixed square wave pulse amplitude ESW ¼ 70 mV (Fig. 4),
and also for different values of the square wave pulse amplitude
Scheme II.
95
Fig. 4. (solid lines) Experimental (ISW/QMAX)  (E  E0) (a) and (QSW/QMAX)  (E  E0)
(b) curves obtained in SWV and SWVC for a mixed FcC6SH–C6SH monolayer in 1.0 M
NaClO4 solution with different ferrocyanide concentrations. Electrode radius
r 0 ¼ 50 lm. Es = 5 mV. ESW = 70 mV. The values of FeðCNÞ4 6 concentration (in mM)
appear on the curves. (symbols) Theoretical (ISW/QMAX)  (E  E0) (a) and (QSW/
0
QMAX)  (E  E ) (b) curves calculated from Eqs. (10) and (18) by using the following
0
parameters: E0 = 0.100 V, ESW = 70 mV, kc = 2.5  104 M1 s1, n = 1, QMAX = 1.95 nC
and T = 298 K.
and a fixed ferrocyanide concentration 10 mM (Fig. 5). The pulse
time length used in all the experiments was 3 ms. In Figs. 4 and
5 we have also included theoretical curves calculated from Eqs.
(10) and (18) for comparison (symbols). The experimental values
of QMAX, kc and E0 have been obtained as discussed below. More-
over, double layer contribution to the QSW–E curves has been cor-
rected by following the procedure described in the Appendix A.
The ISW–E curves in Fig. 4a show a well defined peak whose
height increases with the FeðCNÞ4 6 concentration. No splitting of
the response or potential shift has been observed under these
conditions.
Concerning the influence of the square wave potential ampli-
tude shown in Fig. 5a, the current also increases with ESW until a
clear current plateau is observed for ESW P 110 mV. All this evi-
dence clearly points to the presence of a catalytic process in line
with Scheme II, and also to the reversible character of the charge
transfer step (see Figs. 1a and 2a). Therefore, a simple determina-
tion of the formal potential of the redox attached couple can be
carried out by simply measuring the peak potentials of the ISW–E
curves in line with Eq. (11). By doing this, we have found
E0 = (100 ± 5) mV vs. SCE. The high standard deviation observed
in the experimental formal potential value could be related to
96 J. González et al. / Journal of Electroanalytical Chemistry 634 (2009) 90–97
Fig. 5. (solid lines) Experimental (ISW/QMAX)  (E  E0) (a) and (QSW/QMAX)  (E  E0)
(b) curves obtained in SWV and SWVC for a mixed FcC6SH–C6SH monolayer in 1 M
NaClO4 solution with 10 mM in potassium ferrocyanide. Electrode radius
r0 ¼ 50 lm. Es = 5 mV. The values of ESW (in mV) appear on the curves. (symbols)
Theoretical (ISW/QMAX)  (E  E0) (a) and (QSW/QMAX)  (E  E0) (b) curves calculated
from Eqs. (10) and (18) by using the following parameters: E0 = 0.100 V,
kc ¼ 250 s1 , n = 1, QMAX = 1950 pC and T = 298 K.
some heterogeneity of the redox centers of the monolayer, as has
been previously pointed out in [18].
In Fig. 4b it can be observed how the increase of the ferrocya-
nide concentration has no significant effects to the peak height of
the QSW–E curves (a fact which again supports the reversible char-
acter of the charge transfer step), whereas the anodic limit is
strongly affected, in agreement with Eqs. (5) and (19).
Fig. 5b shows the influence of the square wave pulse amplitude
on the experimental QSW–E curves. It can be seen that whereas the
peak height increases with ESW until charge plateau for
ESW > 110 mV is obtained, the anodic limit region remains unaf-
fected, in line with Fig. 2b and Eq. (19). Both the charge plateau
and the anodic limit values are independent of the electrochemical
reversibility, in line with Eqs. (17)–(19). From the measurement of
the charge plateau for ESW = 130 mV we have obtained QMAX =
(2.0 ± 0.1) nC, which, taking into account the roughness factor of
fr = 5.91, leads to a surface coverage CFc = (2.6 ± 0.1)  1010
mol cm2, a value in line with those previously reported in [18,21].
Moreover, the ratio between the charges of the plateau and the
anodic limit should be equal to kcs in agreement with Eq. (19).
From the curves in Fig. 5 for ESW P 110 mV we have obtained
kcs = 0.75 which, for the time pulse s = 3 ms leads to kc = 250 s1.
If we take into account the FeðCNÞ4 6 concentration used in these
0
curves we obtain kc =2.5  104 M1 s1 (see Eq. (5)).
The value of the chemical rate constant can be also obtained in
two other ways.
– Once QMAX is known, kc can be determined from the current pla-
teau (Fig. 5a), whose value is QMAXkc, in agreement with Eq. (15).
We have used the value QMAX = 2.0 nC in Fig. 5a, thus obtaining
kc = 250 s1.
– kc can be determined by plotting the cross potential of the QSW–E
curves vs. ESW, obtaining an excellent linearity (see insert Figure
in Fig. 5b) in agreement with Eq. (22). By taking into account the
E0 previously measured from the ISW–E curves, a value of
kc = 265 s1 is finally obtained.
In these Figures we have included the theoretical ISW–E and
QSW–E curves for comparison (symbols), calculated by using Eqs.
(10) and (18) with kc = 250 s1, QMAX = 1.95 nC and E0 = 0.100 V.
The agreement between theoretical and experimental results con-
firms the accuracy of the experimental parameters deduced.
5. Conclusions
In this paper we have obtained general expressions for the
square wave current–potential (ISW–E) and charge–potential
(QSW–E) curves of an electrocatalytic process applicable for any
reversibility of the electrochemical step. Important simplified
expressions have also been deduced for high enough values of
the catalytic rate constant, which is the most usual experimental
situation.
The peak potential of the ISW–E curves coincides with formal po-
tential ðEpeak 0
SWV ¼ E Þ of the immobilised redox couple in the case of
reversible charge transfer.
One of the main advantages of the SWVC is that the cata-
lytic rate constant can be determined from the anodic limit
value of the QSW–E curve, independently of the square wave
pulse amplitude and also of the reversibility of the electrochem-
ical step.
The theoretical predictions for SWV and SWVC have been veri-
fied by studying the electrocatalytic oxidation of ferrocyanide
mediated by a mixed 6-(ferrocenyl)hexanethiol-hexanethiol
0
monolayer in gold electrode, with kc = 2.5  104 M1 s1 being
the rate constant for the chemical step.
Acknowledgments
The authors greatly appreciate the financial support provided
by the Dirección General de Investigación Científica y Técnica (Pro-
ject Number CTQ2006-12552/BQU), and the Fundación SENECA
(Project Number 08813/PI/08). C.M. Soto thanks the Ministerio de
Educación y Ciencia for the grant received.
Appendix A. Non-faradaic contribution to the converted charge
of an electrocatalytic response in Square Wave Voltcoulometry
(SWVC)
The experimental SWVC converted charge corresponding to the
reaction mechanism given in Scheme I can be considered as the
sum of a pure faradaic contribution, QSW,f, and a non-faradaic
one, QSW,nf:
Q SW ¼ Q SW;f þ Q SW;nf ðA:1Þ
The expression of the faradaic component is given by Eq. (3)
and, under reversible conditions for the charge transfer step, by
Eq. (18). The non-faradaic terms in Eq. (A.1) can be obtained by
following the procedure discussed in [14] and, the reversible elec-
trochemical step is given by:
 J. González et al. / Journal of Electroanalytical Chemistry 634 (2009) 90–97
Fig. 6. Experimental QSW  (E  E0), QSW,f  (E  E0) and theoretical QSW,nf  (E  E0)
(calculated from Eq. (A.2)) curves obtained in SWVC for a mixed FcC6SH–C6SH
monolayer in 1 M NaClO4 solution with FeðCNÞ4 10 mM. Other conditions as in
6
Fig. 4.
 
eg2p
Q SW;nf ¼ 2jESW j cmA þ d ðA:2Þ
1 þ eg2p
where d = cmB  cmA, and cmA and cmB are the non-faradaic capaci-
tance of the totally reduced or totally oxidized electroactive mono-
layer, respectively.
Eq. (A.2) indicates that the QSW,nf response gives rise to a baseline
which for E  E0 and E  E0 takes the constant values 2|ESW|cmA
and 2|ESW|cmB, respectively.
Thus, by combining Eqs. (A.1), (A.2), and (18) we deduced that
at cathodic potentials the converted charge is only non-faradaic
(i.e., Q SW;EE0 ¼ 2jESW jcmA ), whereas at anodic potentials, once the
faradaic conversion has finished, the charge takes the value
Q SW;EE0 ¼ Q MAX kc s þ 2jESW jcmB . Therefore the cmA value can be
obtained directly as the cathodic limit charge divided by 2|ESW|,
and cmB can be obtained from the slope of a plot of Q SW;EE0 vs.
2|ESW|. Once these non-faradaic capacitances and the value of the
formal potential are obtained, we can calculate the non-faradaic
97
contribution from Eq. (A.2) and we can correct the experimental
charge by subtracting it from the measured response, thus obtain-
ing the pure faradaic charge.
This procedure has been carried out in Fig. 6, in which we have
plotted the QSW–E response obtained for a mixed FcC6SH–C6SH
monolayer in a solution 1 M NaClO4 with 10 mM potassium
ferrocyanide. Under these conditions we have obtained the
following non-faradaic capacitances: cmA ¼ 8:21 lF=cm2 and
cmB ¼ 34:4 lF=cm2 . The corrected pure faradaic QSW–E curve has
been obtained by calculating the non-faradaic component (Eqs.
(A.1) and (A.2)) by using E0 ¼ 0:100 V), and subtracting it from
the experimental response.
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