Electrochimica Acta 54 (2009) 60466052

Contents lists available at ScienceDirect

Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

An electromechanical perspective on the metal/solution interfacial region

during the metallic zinc electrodeposition
David Gimenez-Romero , Francisco Vicente
Jernimo Agrisuelas, Jos Juan Garca-Jareno,
Departament de Qumica Fsica, Universitat de Valncia, C/ Dr Moliner, 50, 46100, Burjassot, Valncia, Spain

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

Article history: The difculty of studying the metal/solution interfacial region makes the use of non-conventional mea-
Received 7 October 2008 surement techniques indispensable. In this way, a careful in situ study by means of acoustic impedance
Received in revised form 9 March 2009 techniques coupled with nano-electrogravimetric techniques allowed this interface to be monitored dur-
Accepted 9 March 2009
ing the metallic zinc electrodeposition process. This paper proves the formation of a viscoelastic layer
Available online 28 March 2009
consisting of ultra-hydrated Zn(II)/Zn(I) salts as a key step in the metallic zinc electrodeposition mech-
anism in sulfate aqueous solutions. Surprisingly, this layer is located in the metal/solution interfacial
Keywords:
region and not on the reaction substrate. The chloride ions effect on the metallic zinc electrodeposition
Zinc electrodeposition
Zn(II)/Zn(I) salts
mechanism at these experimental conditions lies mainly in the stabilization of the zinc ions inside this
Nano-electrogravimetry layer.
Acoustic impedance 2009 Elsevier Ltd. All rights reserved.

1. Introduction
The analysis of the mechanism of electrode reactions is usu-
ally conducted with the implicit assumption that electrons must
be transferred one at a time. This often necessitates the assump-
tion of the existence of intermediates that are highly unstable, such
as monovalent ions of different metals formed in the course of elec-
trodeposition [1]. Considering that, it is recognized that adsorption
of intermediates plays a major role in electrode kinetics, which
could stabilize the intermediate and reduce the energy of activa-
tion for the consecutive mechanism, compared with that for the
two-electron transfer. In agreement with this, the kinetics of the
metallic zinc electrodeposition process can be explained by means
of the reduction of divalent zinc atoms through two consecutive
single-electron transfers [26].
At pH > 2.1, the metallic zinc deposits are coated by a passive
layer in aqueous solutions [7]. In the presence of chloride ions,
this layer is made up of simonkolleite, Zn5 Cl2 (OH)8 H2 O, and zincite,
ZnO, more or less hydrated [8]. ZnO is a IIVI n-type semiconduc-
tor with a direct band gap of 3.3 eV. Besides the wide band gap,
ZnO has several attractive properties, such as large exciton bind-
ing energy (60 meV at room temperature), high chemical stability,
good piezoelectric properties, non-toxicity and bio-compatibility,
which have drawn tremendous attention in recent years [9]. Owing
to stability in hydrogen plasma, ZnO thin lms can be employed
in fabrication of hydrogenated amorphous silicon solar cells [10].
Corresponding author.
E-mail address: David.Gimenez-Romero@uv.es (D. Gimenez-Romero).
ZnO thin lms also have potential for practical applications, notably
in short wavelength optical devices, especially in ultravioletblue
emission devices [11]. High-quality ZnO thin lms have been pre-
pared by several thin lm deposition techniques, including pulsed
laser deposition [12], chemical vapor deposition [13], molecular
beam epitaxy [14], sputtering [15], etc.
The metallic zinc electrodissolution process in sulfate aqueous
solution takes place by means of the formation of a viscoelastic
layer of Zn(I) and hydroxide ions in the metal/solution interfa-
cial region [1618]. The in situ use of gravimetric techniques such
as electrochemical techniques (EQCM) is a very powerful tool for
the study of the electrodeposition and electrodissolution processes
of metals. The analysis of the mass/electrical charge ratio allows
active species that take part in the reaction to be identied by
means of the calculation of the molar mass of the species exchanged
between the reaction substrate and the working solution [1821].
In addition, it is possible to follow in situ changes of the motional
resistance (acoustic impedance) for EQCM electrodes. This resis-
tance can be associated with changes of physical properties of
the metal deposited on the electrode surface and changes of the
viscoelastic properties of the interface in contact with the work-
ing electrode [2226]. During the last few years, the in situ use
of acoustic impedance techniques coupled with electrochemical
techniques has allowed the nature and properties of polarized inter-
facial regions to be monitored [21]. It is important to emphasize
that non-conventional measurement techniques are indispensable
for the study of the metal/solution interfacial region.
Accordingly, the main goal of this work is the study of the
metal/solution interfacial region during the metallic zinc elec-
trodeposition process in sulfate aqueous solution by acoustic and

0013-4686/$ see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2009.03.062
 J. Agrisuelas et al. / Electrochimica Acta 54 (2009) 60466052 6047

gravimetric techniques, with the purpose of detecting the possible

formation of a new Zn(I) layer during this process. Similar layers
made up of monovalent metal atoms were previously detected dur-
ing the electrodeposition processes of other metals [19,21].

2. Experimental

The electrochemical measurements were carried out in a typical

electrochemical three-electrode cell. Metallic zinc was deposited
on 25 mm2 diameter gold electrodes of a quartz crystal (Matel-
Fordahl). A platinum plate was used as the counter electrode and
the Ag|AgCl|KClsat electrode was used as the reference electrode -
this electrode has a potential of +0.1988 V relative to the standard
hydrogen electrode at 298 K-. Consequently, all potentials were
referred to the Ag|AgCl|KClsat electrode. Electrochemical measure-
ments were performed with an AUTOLAB potentiostat-galvanostat
(PGSTAT302). At the same time, gravimetric and acoustic measure-
ments were performed using an Electrochemical Quartz Crystal
Microbalance (RQCM, Maxtek Inc.).
The RQCM utilizes an internal phase lock oscillator referred to as
a voltage controlled oscillator to drive the quartz crystal. The crystal
current is monitored and the frequency of the oscillator is adjusted
until there is zero phase between the crystal voltage and current.
The magnitude of the current is directly proportional to the crystal
conductance. This current is monitored by the RQCM and displayed
as motional resistance [27].
Voltammetric experiments were carried out in ZnSO4 (Schar-
lau, reagent grade) 10 mM, Na2 SO4 (Scharlau, reagent grade) 1.32 M,
H3 BO3 (Scharlau, reagent grade) 0.32 M and NH4 Cl (Scharlau,
reagent grade) 0.26 M or (NH4 )2 SO4 (Sigma, ACS reagent) 0.13 M,
pH 4.80 and temperature 298.2 0.1 K [28]. Working solutions were
deaerated by bubbling Ar (Air Liquide) for 5 min.

3. Results and discussion

3.1. Nano-electrogravimetry-dc
The zinc electrodeposition and electrodissolution were followed
through the simultaneous measurement of current density and
mass changes on the electrode surface during a voltammetric scan
(Fig. 1). Several zones can be distinguished during this scan:
Fig. 1. Voltammetric scan between 0.20 V and 1.25 V. The working solution
was ZnSO4 10 mM, Na2 SO4 1.32 M, H3 BO3 0.32 M and NH4 Cl 0.26 M, pH 4.80, scan
rate 10 mV/s and temperature 298.2 0.1 K. (a) currentmass response, inset is the
potential as a function of time. (b) F(dm/dQ) function during the cathodic scan,
the potential range with the electric current equal to 0 A is not showed here since
the F(dm/dQ) function cannot be calculated at these potentials. The Ag|AgCl|KClsat
electrode was used as the reference electrode.

a) Between 90 s (1.10 V, cathodic scan) and 126 s (1.04 V, anodic
scan), the zinc is reduced and deposited on the gold electrode.
In the same potential range, the hydrogen evolution also occurs.
This zone is characterized by an important increase in mass on
the working electrode, around 8 g cm2 . The processes that
take place in this zone are:
Zn2+ + 2e Zn
and:
1 of the electrical charge balanced by the participation of this ion. In
H + + e H2
2
b) Between 126 s (1.04 V, anodic scan) and 209 s (0.20 V, anodic
scan), the deposited zinc is oxidized and the mass deposited on
the working electrode (reaction substrate) decreases.
Zn Zn2+ + 2e
As commented in Section 1, the mass/electrical charge ratio
allows the molar mass of the species exchanged between the reac-
tion substrate and the working solution during a faradaic process to
be calculated by means of the following expression that considers
Faradays laws of electrolysis [18]:
m  AWi
F =  mass changes due to uncharged species
Q ni i
(4a)
where F is the Faraday constant (96,500 C/mol), Q the electric
(1) charge passed and m the change of mass. AWi represents the
molar mass of the charged i species involved in the faradic process,
ni the electrical charge of i species and i represents a percentage
(2) some systems it is important to consider that uncharged species
such as the solvent can participate in the electrochemical process.
This participation can produce mass changes but their movement
does not cause a ux of electrical charge and therefore no faradic
current is associated to their movement. However, the participation
of these species can modify the obtained mass/charge ratio.
(3) The global mass/electrical charge ratio (F(m/Q) func-
tion) during the whole process of divalent zinc reduction
in sulfate aqueous solution with chloride ions is equal to
34 g mol1 . This value is similar to the theoretical value of
the F(m/Q) function corresponding to the metallic zinc elec-
trodeposition from a two-electron transfer, F(m/Q )theoretical =
6048 J. Agrisuelas et al. / Electrochimica Acta 54 (2009) 60466052

[molar mass (Zn)/electron number] = 65.4/ 2 = 32.7 g mol1 .

For that, it is possible to say that almost all reduction reactions
at these experimental conditions are mainly attributable to a
two-electron transfer for each deposited zinc atom. The small dif-
ference between the theoretical and experimental value (around
1.3 g mol1 ) may be caused by a small zinc passivation process,
which is conrmed by means of the small increase of the mass
located on the reaction substrate during the whole voltammetric
scan (see Fig. 1a). In agreement with this, Morad et al. proved that
a passive layer coats the zinc sheets in aqueous solutions at pH >
2.1 [7].
The electrodic mechanisms are better studied by a punctual
analysis of the mass/electrical charge ratio. To calculate this ratio,
the rst step is to obtain the dm/dt vs t curve from the experimental
m vs t curve. The dm/dt function is divided into the current density
and multiplied by the Faraday constant. Thus, it can be written that
[18]:

dM dM (g)/dt dM(g)/dt Fig. 2. Voltammetric scan between 0.20 V and 1.25 V. The working solution was
F = F (C mol1 ) = F (C mol1 ) ZnSO4 10 mM, Na2 SO4 1.32 M, H3 BO3 0.32 M and NH4 Cl 0.26 M, pH 4.80, scan rate
dQ dQ (C)/dt i (A)
80 mV/s and temperature 298.2 0.1 K. F(dm/dQ) function during the cathodic scan,
dm (g cm2 )/dt the potential range with the electric current equal to 0 A is not showed here since
= F (C mol1 ) (4b) the F(dm/dQ) function cannot be calculated at these potentials. The Ag|AgCl|KClsat
j (A cm2 ) electrode was used as the reference electrode.

where both species are in the working solution,

Considering Faradays laws of electrolysis, it is possible to say
F(dm/dQ)theoretical = 0 g mol1 . As commented above, all mono-
that this function has the same physical meaning as the F(dm/dQ)
valent zinc ions are reduced to metallic zinc and therefore, it is
function, but interpreted punctually at each polarization potential.
possible to say that the monovalent zinc ions may remain into the
Next, Fig. 1b shows the mass/electrical charge ratio at each
metal/solution interfacial region and they do not spread to the
potential (F(dm/dQ) function) during the metallic zinc electrodepo-
interior of the working solution. If they spread to the interior of
sition mechanism at these experimental conditions. As this gure
the working solution, then not all monovalent zinc ions could be
shows, this reaction may take place via different reaction steps
completely reduced electrochemically.
given that the F(dm/dQ) ratio is not constant during the cathodic
Fig. 3 shows the same nano-electrogravimetric study during the
whole scan. As commented above, the metallic zinc electrodeposi-
metallic zinc electrodeposition process in sulfate aqueous solu-
tion occurs via two consecutive single-electron transfers.
tion without chloride ions. The shape and values of the F(dm/dQ)
By using the changes of the F(dm/dQ) function, nano-
function do not change much with (Fig. 1b) or without (Fig. 3b) chlo-
electrogravimetrydc mode (cyclic voltammetry) allows the
ride ions into the working solution. Accordingly, the species that
different electronic transfer steps that take place during a faradaic
are exchanged between the substrate and the solution during the
process to be differentiated. Thus, this function divides the kinet-
metallic zinc electrodeposition are not inuenced to a large extent
ics of metallic zinc electrodeposition in sulfate aqueous solution
by these anions. Nonetheless, the divalent zinc reduction is really
with chloride ions into ve zones, Fig. 1b. Zone 1 is characterized
favored by chloride ions since it begins at more anodic potentials
by a constant value of the F(dm/dQ) function about 25 g mol1
in the presence of these ions. Considering that, chloride ions may
and it is delimited between 0.95 V and 1.05 V. The reactions that
only stabilize zinc species located in the working solution.
occur at these potentials take place at the beginning of the cathodic
Monovalent zinc ions are also stabilized by hydroxyl ions since
scan and hence, they may be mainly related to the rst single-
the F(dm/dQ) function in the zone 1 changes when the pH is
electron transfer considered in the global mechanism of metallic
increased, Figs. 1 and 4. Compared to the chloride ions concen-
zinc electrodeposition. However, the value of the F(dm/dQ) function
tration, the F(dm/dQ) function depends for the most part on the
at these potentials is different than the theoretical value corre-
hydroxyl ions concentration given that the values of the F(dm/dQ)
sponding to the single-electron formation of monovalent zinc ion;
function changes more when the pH is increased than when
that is, 65.4 g mol1 for a heterogeneous process or 0 g mol1 for a
the chloride ions concentration is changed. Therefore, the reac-
homogeneous process. Therefore, the two single-electron transfers
tion intermediate detected during the zinc electrodeposition may
established in the kinetics of metallic zinc electrodeposition may
be stabilized in the metal/solution interfacial region by hydroxyl
be overlapped at these potentials.
anions and slightly, by chloride ions.
To separate these reaction steps, the evolution of the F(dm/dQ)
On the other hand, the zone 2 of the voltammetric scan is
function was determined at different scan rates, see Fig. 2. The
characterized by a sudden decrease of the F(dm/dQ) function up to
F(dm/dQ) function in this potential range so tends to zero as the
42.5 g mol1 in the potential range between 1.05 V and 1.10 V,
scan rate is increased. As a result, the value of the F(dm/dQ) function
Fig. 1b. This decrease is more signicant when Zn(I) ions are more
that corresponds to the rst single-electron transfer considered in
stable into the working solution; that is, when the values of the
the global mechanism of metallic zinc electrodeposition in sulfate
F(dm/dQ) function in the zone 1 tend to zero (Figs. 1b, 2 and 4). If
aqueous solution with chloride ions may be equal to 0 g mol1 . It  
1e
involves neither deposition nor adsorption of species on the reac- the Zn(II)solution Zn(I)solution F(dm/dQ ) = 0/ 1 = 0 g mol1
tion substrate; m = 0 g and subsequently, F(dm/dQ) = 0 g mol1 . reaction took place at zone 1, then the Zn(I)solution
Thus, the rst reaction step of this reaction kinetics may correspond 1e  
Zn(0)substrate F(dm/dQ ) = 65.4/ 1 = 65.4 g mol1 reac-
to: tion should be also observed at more cathodic potentials. Hence,
the zone 2 would correspond to the elimination of Zn(I) species
Zn2+ + 1e Zn+ (5) previously accumulated in zone 1. The rate of this last process
 J. Agrisuelas et al. / Electrochimica Acta 54 (2009) 60466052
Fig. 3. Voltammetric scan between 0.20 V and 1.40 V. The working solution was
ZnSO4 10 mM, Na2 SO4 1.32 M, H3 BO3 0.32 M and (NH4 )2 SO4 0.13 M, pH 4.80, scan
rate 10 mV/s and temperature 298.2 0.1 K. (a) currentmass response. (b) F(dm/dQ)
function during the cathodic scan, the potential range with the electric current equal
to 0 A is not showed here since the F(dm/dQ) function cannot be calculated at these
potentials. The Ag|AgCl|KClsat electrode was used as the reference electrode.
Fig. 4. F(dm/dQ) function during the cathodic scan between 0.20 V and 1.25 V,
the potential range with the electric current equal to 0 A is not showed here since
the F(dm/dQ) function cannot be calculated at these potentials. The working solution
was ZnSO4 10 mM, Na2 SO4 1.32 M, H3 BO3 0.32 M and NH4 Cl 0.26 M, pH 6.15, scan
rate 10 mV/s and temperature 298.2 0.1 K. The Ag|AgCl|KClsat electrode was used
as the reference electrode.
6049
increases at these potentials due to the fact that there is an excess of
Zn(I) ions in the metal/solution interfacial region. Thus, the value of
the F(dm/dQ) function comes back quickly to values corresponding
to the zone 1 when this accumulation is partially eliminated, as
can be observed in Fig. 1b. At more cathodic potentials, the rate
of this second reaction step increases due to the decrease of the
polarization potential.
The zone 3 of Fig. 1b is characterized by a constant value of
the F(dm/dQ) function about 33 g mol1 . Divalent zinc ions are
reduced directly to metallic zinc at these potentials, Zn(II)solution
2e  
Zn(0)substrate F(dm/dQ ) = 65.4/ 2 = 32.7 g mol1 . Con-
sequently, the zinc reduction kinetics can be considered as a
two-electron transfer at more cathodic potentials given that the
rate of the second single-electron transfer is higher that the rate of
the rst transfer at these potentials.
In view of that, the cathodic voltammetric peak of Fig. 1 is delim-
ited by the Zn(I) accumulation process at anodic potentials (zone
1) and by the metallic zinc electrodeposition process via a two-
electron transfer at cathodic potentials (zone 3). Consequently, the
electron transfer associated with this voltammetric peak may cor-
respond to the elimination of the excess concentration of Zn(I) ions
in the metal/solution interfacial region. Fig. 3b shows how this
peak is not observed when there are not accumulation of Zn(I) ions
into the interfacial region (when the value of zone 2 is not around
65.4 g mol1 ).
Finally, the zone 4 of the cathodic scan is characterized by
a decrease of the F(dm/dQ) function up to 40 g mol1 between
1.18 V and 1.22 V. This decrease cannot be due to the second
single-electron transfer of the metallic zinc electrodeposition pro-
cess because this deposit occurs via a two-electron transfer at these
potentials, as commented above. The decrease of the F(dm/dQ)
function in zone 4 may be caused by the formation of the passive
layer observed by means of Fig. 1a. The hydrogen discharge that
occurs at these potentials increases the pH of the metal/solution
interfacial region and it so favors the zinc hydroxide precipitation
[29,30]. This discharge also causes the increase of the F(dm/dQ)
function in the zone 5 from 40 g mol1 to 35 g mol1 since the
proton reduction is the most important contribution to the mea-
sured current at these potentials. The hydrogen discharge does not
mean a net mass change on the electrode surface and therefore,
the absolute value of F(dm/dQ) function decreases because m
remains invariable whereas Q increases. However, and as com-
mented above, this reaction is coupled with a precipitation reaction
at more anodic potentials and for that reason, the value of the
F(dm/dQ) function is more negative at these potentials because the
mass of the working electrode increases due to the zinc hydroxide
precipitation.
In this section, the kinetics of metallic zinc electrodeposition in
sulfate aqueous solution has been separated in two single-electron
transfer steps through the F(dm/dQ) function. The rst process
involves the formation of monovalent zinc ions into the interfacial
region, which are stabilized by hydroxyl and in a minority, chlo-
ride anions, and later, these ions are reduced to metallic zinc on the
reaction substrate. Both reactions are consecutive since the value of
the F(m/mQ) function during the global process of metallic zinc
electrodeposition corresponds mainly to a two-electron transfer for
each deposited zinc atom.
3.2. Acoustic impedance
The acoustic behavior of a quartz resonator loaded with a thin
layer can be described in terms of a ButterworthVan Dyke (BVD)
equivalent circuit model [2224]. The elements of this model are
related to the physical properties of the crystal, the coating and
the solution. The relation between the mechanical properties and
6050 J. Agrisuelas et al. / Electrochimica Acta 54 (2009) 60466052

the motional resistance of the BVD equivalent circuit model can be

described by means of the following equation [22]:
3

2 2 film
2 2 G
dfilm
2 quartz dquartz dquartz
Rm = + film

8K 2 c66 22 A 2 A
4e26  )2 (G
(Gfilm )2
film

2
dquartz

solution solution
+ 2 A
(6)
4e26 2

where d is the layer thickness,  the mass density, the angular fre-
quency,  the viscosity and G the complex shear modulus. K2 is the
electromechanical coupling factor for lossless quartz (7.74 103
[24]), quartz the effective viscosity of quartz (3.5 104 kg m1 s1
[24]), c66 the piezoelectrically stiffened elastic constant for loss-
less quartz (2.947 1010 N m2 [24]),  22 the quartz permittivity
(3.982 1011 A2 s4 kg1 m3 [24]), e26 the piezoelectric stress con-
stant for quartz (95.3 103 A s m2 [24]) and A the active electrode
area. Fig. 5. Currentmotional resistance response during the voltammetric scan
 between 0.20 V and 1.25 V. The working solution was ZnSO4 10 mM, Na2 SO4
The complex shear modulus of the lm is equal to Gfilm +

 
1.32 M, H3 BO3 0.32 M and NH4 Cl 0.26 M, pH 4.80, scan rate 10 mV/s and temperature
jGfilm (j = 1). It is important to emphasize that Gfilm << Gfilm 298.2 0.1 K. The Ag|AgCl|KClsat electrode was used as the reference electrode.
for a viscoelastic layer and however, Gfilm 
>> Gfilm for a rigid lm.
Therefore, an increase of the density and thickness of the lm
implies the increase of the motional resistance in viscoelastic lms
as well as the decrease of the motional resistance in rigid lms.
The motional resistance is the addition of four different terms:
the resistances related to the properties of the quartz crystal, the
working solution, the electrolyte and the lm (the addition of the
different resistances associated with the different layers that com-
pose the reaction system). Thus, the Eq. (6) is transformed into:

3 
2 2
2 quartz dquartz dquartz 2 Zn
2
dZn
Rm = 
8K 2 c66 22 A 2 A
4e26 GZn

2
dquartz 2
3
2 film 2 G
dfilm 2
dquartz

solution solution
+ film
+
2 A  )2 (G
4e26 (Gfilm film
)2 2 A
4e26 2

(7)

where the Zn designates the physical properties of the metallic Fig. 6. Currentmotional resistance response during the voltammetric scan
zinc and lm designates the physical properties of the layer located between 0.20 V and 1.25 V. The working solution was ZnSO4 10 mM, Na2 SO4
around the metallic zinc. 1.32 M, H3 BO3 0.32 M and (NH4 )2 SO4 0.13 M, pH 4.80, scan rate 10 mV/s and temper-
The viscoelastic materials have higher values of the acoustic ature 298.2 0.1 K. The Ag|AgCl|KClsat electrode was used as the reference electrode.

impedance than the rigid materials. Consequently, if there is a

viscoelastic material near to the microbalance substrate, then the
Conversely, the motional resistance increases during the zinc elec-
measured motional resistance corresponds for the most part to the
trodeposition from 100 s (1.20 V). The motional resistance should
contribution of the viscoelastic material. Thus, this resistance can
decrease if only the metallic zinc deposition growth took place.
be simplied as follows:
Hence, the motional resistance increase indicates the formation
3

2 G of a viscoelastic layer during the metallic zinc electrodeposition
2
dquartz 2 film
2
dfilm   . Fig. 6 shows
Rm = film
+ constant (8) process, as Eq. (8) establishes since Gfilm << Gfilm
2 A  )2 (G
4e26 (Gfilm film
)2 how this viscoelastic layer is also observed during the metallic
zinc electrodeposition in sulfate aqueous solution without chloride
In view of that, Fig. 5 shows the change of the motional resistance ions. Accordingly, the acoustic techniques by means of the motional
measured during the metallic zinc electrodeposition in sulfate resistance allow the growth of a viscoelastic layer during the metal-
aqueous solution with chloride ions. This gure shows how the lic zinc electrodeposition process in a sulfate solution to be in situ
zone 1 of the voltammetric scan is characterized by a constant monitored.
value of the motional resistance, indicating that faradaic processes The viscoelastic layer detected here during the metallic zinc
that occur at these potentials are not on the reaction substrate. This electrodeposition may consist of divalent zinc atoms since it begins
conrms that the monovalent zinc detected at these potentials by its growth from the zone 3 of Fig. 1, when these ions are accumu-
means of the F(dm/dQ) function (see above) may be located in the lated around the reaction substrate in order to be reduced by a
metal/solution interfacial region. two-electron transfer. The metallic zinc cannot generate this vis-
Fig. 5 shows also how the motional resistance decreases dur- coelastic layer, given that the metallic zinc is a rigid material. As
ing the cathodic voltammetric peak, zone 2 of Fig. 1a. Thus, and the divalent zinc ions are initially in the working solution and this
as the zinc is a rigid material, this result is in concordance with layer does not exist initially, the monovalent zinc ions may also con-
the deposit of a metal at these potentials, as commented above. stitute the detected viscoelastic layer. As commented above, these
 J. Agrisuelas et al. / Electrochimica Acta 54 (2009) 60466052
Fig. 7. Schematic representation of mechanism proposed for the metallic zinc elec-
trodeposition process.
ions are located in the metal/solution interfacial region. Corroborat-
ing this, the literature establishes the presence of Zn(II)O/Zn(I)OH
during metallic zinc electrodeposition [31,32]. Indeed, the metal-
lic zinc electrodissolution process in sulfate aqueous solution takes
place by means of the formation of a viscoelastic layer of Zn(I) and
hydroxide ions into the metal/solution interfacial region [1618]
-the formation of this layer is also observed in Fig. 5 through the
increase and subsequent decrease of the motional resistance during
the metallic zinc electrodissolution processes.
As commented above, this interfacial layer is detected in sul-
fate solutions with chloride ions and also in chloride-free solutions.
Therefore, it is possible to say that this layer is composed of Zn(I)
and Zn(II) ions and hydroxyl ions (the species present in sulfate solu-
tions both with and without chloride ions), being only stabilized by
chloride ions. Thus, the viscoelastic layer formed during the metallic
zinc electrodeposition can be dened as a type of Zn(II)/Zn(I) mixed
hydroxide. The formation of zinc hydroxides has been observed
above during the kinetics of metallic zinc electrodeposition [7]. It is
important to emphasize that this layer may have an ultra-hydrated
character given that the zinc hydroxides are rigid materials whereas
the acoustic impedance detects the formation of a viscoelastic layer
whereas nano-electrogravimetric measurements observe neither
deposition nor adsorption of species different from metallic zinc.
Simonkolleite is the zinc hydroxide that blocks the electroac-
tive zinc area and thus, its corrosion becomes more difcult [8].
This material is accumulated both in anodic (electrodissolution)
and cathodic (electrodeposition) sites [8] and it is mainly com-
posed of zinc hydroxide where the chloride ions exist in a minority
[33]. Similarly, the viscoelastic layer detected above is mainly com-
posed of hydroxyl ions whereas chloride ions only stabilized it. For
that, a simonkolleite-like material could be formed during the zinc
faradaic processes at these experimental conditions. Nonetheless,
the simonkolleite is only formed by divalent zinc ions whereas the
detected layer is composed of Zn(II) and Zn(I) ions.
The simonkolleite has a similar structure and composition to the
hydroxides double salts [34]. Thus, the viscoelastic layer detected
during the zinc faradaic processes could be a layer of Zn(II)-Zn(I)
hydroxides salts. The ultra-hydrated character of this intermedi-
ate layer conrms the formation of these zinc salts. Accordingly,
the simonkolleite accumulation in electrodeposition sites would be
easy explained from the non-stability of monovalent zinc in the air
given that Zn(I) ions that constituted this intermediate layer would
be oxidized quickly to Zn(II) ions when a polarization potential is
not applied.
It is important to highlight that this layer is detected by the
motional resistance but however, the F(dm/dQ) function indicates
only the electrodeposition of metallic zinc atoms on the reac-
tion substrate (a rigid material). Therefore, the layer of Zn(II)-Zn(I)
hydroxides salts is formed in the metal/solution interface and not on
the reaction substrate. Thus, the motional resistance only detects
6051
the viscoelasticity change of the interfacial layer located around
this substrate; this phenomenon is known in the literature as
depletion layer effects [35,36]. As a result, the metallic zinc elec-
trodeposition mechanism in sulfate solution would occur via the
formation of a viscoelastic layer of Zn(II)-Zn(I) hydroxides salts in
the metal/solution interfacial region, as Fig. 7 schematizes. In spite
of the fact that the experimental conditions in zinc oxide synthe-
sis processes could be different than our conditions, these results
could be of the interest to this important industrial process as well
as the electrochemical techniques that are used to monitor the
metal/solution interfacial region. Furthermore, the characterization
of this viscoelastic layer could allow the physical characteristics of
metallic zinc and zinc oxide layers deposited by electrochemical
techniques to be controlled, with the technological importance that
entails.
4. Conclusions
In situ acoustic techniques allow the metal/solution interfacial
region to be monitored during the metallic zinc electrodeposi-
tion process. Thus, a viscoelastic layer of ultra-hydrated Zn(II)-Zn(I)
hydroxides salts located in the metal/solution interfacial region
was found to be determinant in the kinetics of this electrodepo-
sition process in sulfate aqueous solution. Chloride ions stabilize
only Zn(II)/Zn(I) ions inside this hydroxide layer. Considering these
results, it is possible to say that the rate-limiting reaction step in
multi-electron transfers can be identied with respect to the polar-
ization potential by means of acoustic and nano- electrogravimetric
techniques.
Acknowledgements
This work was supported by FEDER-CICyT project CTQ2007-
64005/BQU. D. Gimenez-Romero acknowledges his position to the
Generalitat Valenciana.
References
[1] E. Gileadi, J. Electroanal. Chem. 532 (2002) 181.
[2] M. Sluyters-Rehbach, J.S.M.C. Brenkel, J.H. Sluyters, J. Electroanal. Chem. 19
(1968) 85.
[3] N.S. Hush, J. Blckledge, J. Electroanal. Chem. 5 (1965) 490.
[4] M.A. Nunez-Flores, A. Ruano, F. Vicente, Anal. Quim. 84 (1988) 289.
[5] F. Ganne, C. Cachet, G. Maurin, R. Wiart, E. Chauveau, J. Petitjean, J. Appl. Elec-
trochem. 30 (2000) 665.
[6] D. Gimenez-Romero, J.J. Garca-Jareno, F. Vicente, J. Electroanal. Chem. 572
(2004) 235.
[7] M.S. Morad, J. Appl. Electrochem. 29 (1999) 619.
[8] Q. Qu, L. Li, W. Bai, C. Yan, C. Cao, Corros. Sci. 47 (2005) 2832.
[9] S.J. Pearton, D.P. Norton, K. Ip, Y.W. Heo, T. Steiner, Prog. Mater. Sci. 50 (2005)
293.
[10] J. Lofer, R. Groenen, J.L. Linden, M.C.M. van de Sanden, R.E.I. Schropp, Thin Solid
Films 392 (2001) 315.
[11] M.H. Huang, S. Mao, H. Feick, H. Yan, Y. Wu, H. Kind, E. Webber, R. Russo, P. Yang,
Science 292 (2001) 1897.
[12] K. Ramamoorthy, C. Sanjeeviraja, M. Jayachandran, K. Sankaranarayanan, P.
Misra, L. Kukreja, Curr. Appl. Phys. 6 (2006) 103.
[13] M. Purica, E. Budianu, E. Rusu, M. Danila, R. Gavrila, Thin Solid Films 403404
(2002) 485.
[14] X. Yang, J. Zhang, Z. Bi, Y. He, Q. Xu, W. Hongbo, W. Zhang, X. Hou, J. Cryst. Growth
284 (2005) 123.
[15] M.K. Puchert, P.Y. Timbrell, R.N. Lamb, J. Vac. Sci. Technol. A 14 (1996) 2220.
D. Gimenez-Romero, M. Keddam, F. Vicente, J. Phys. Chem. B
[16] J.J. Garca-Jareno,
109 (2005) 4593.
D. Gimenez-Romero, M. Keddam, F. Vicente, J. Phys. Chem. B
[17] J.J. Garca-Jareno,
109 (2005) 4584.
[18] D. Gimnez-Romero, J.J. Garca-Jareno, F. Vicente, J. Electroanal. Chem. 558
(2003) 25.
D. Gimenez-Romero, F. Vicente, J. Electrochem. Soc.
[19] J. Gregori, J.J. Garca-Jareno,
153 (2006) B206.
[20] D. Gimenez-Romero, J.J. Garca-Jareno, F. Vicente, Electrochem. Commun. 6
(2004) 903.
[21] D. Gimenez-Romero, J.J. Garca-Jareno, J. Agrisuelas, C. Gabrielli, H. Perrot, F.
Vicente, J. Phys. Chem. C 112 (2008) 4275.
6052 J. Agrisuelas et al. / Electrochimica Acta 54 (2009) 60466052
[22] B. Parzen, Design of Crystal and Other Harmonic Oscillators, Wiley, New York,
1983.
[23] D. Gimenez-Romero, J. Agrisuelas, J.J. Garca-Jareno, J. Gregori, C. Gabrielli, H.
Perrot, F. Vicente, J. Am. Chem. Soc. 129 (2007) 7121.
[24] V.E. Granstaff, S.J. Martin, J. Appl. Phys. 75 (1994) 1319.
[25] K. Biset, C. Gabrielli, H. Perrot, J. Therasse, Biosens. Bioelectron. 13 (1998) 259.
[26] H. Muramatsu, E. Tamiya, I. Karube, Anal. Chem. 60 (1988) 2142.
[27] Maxtek Inc., Operation and service manual of RQCM, 2nd ed.
[28] T. Ohtsuka, A. Komori, Electrochim. Acta 43 (1998) 3269.
[29] S.C. Chung, J.R. Cheng, S.D. Chiou, H.C. Shih, Corros. Sci. 42 (2000) 1249.
[30] B. Canava, D. Lincot, J. Appl. Electrochem. 30 (2000) 711.
[31] K. Raessi, A. Saatchi, M.A. Golozar, J.A. Szpunar, J. Appl. Electrochem. 34 (2004)
1249.
[32] C. Cachet, R. Wiart, J. Electrochem. Soc. 141 (1994) 131.
[33] I. Odnevall, C. Leygraf, Corros. Sci. 34 (1993) 1213.
[34] H. Tanaka, A. Fujioka, A. Futoyu, K. Candor, T. Ishikawa, J. Solid State Chem. 180
(2007) 2061.
[35] W.W. Lee, H.S. White, M.D. Ward, Anal. Chem. 65 (1993) 3232.
[36] Q. Xie, J. Wang, A. Zhou, Y. Zhang, H. Liu, Z. Xu, Y. Yuan, M. Deng, S. Yao, Anal.
Chem. 71 (1999) 4649.