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Electrochimica Acta 54 (2009) 10271033

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Electrochimica Acta
j our nal homepage: www. el sevi er . com/ l ocat e/ el ect act a
Electrochemical behaviour of thin lms of Co/Al layered
double hydroxide prepared by electrodeposition
E. Scavetta
a,
, B. Ballarin
a
, M.Gazzano
b
, D. Tonelli
a,1
a
Department of Physical and Inorganic Chemistry, University of Bologna, Viale Risorgimento 4, INSTM, UdR Bologna, 40136 Bologna, Italy
b
Department of Chemistry, University of Bologna, Via Selmi 2, 40126 Bologna, Italy
a r t i c l e i n f o
Article history:
Received 28 April 2008
Received in revised form 7 July 2008
Accepted 19 July 2008
Available online 6 August 2008
Keywords:
Co/Al layered double hydroxide
Modied electrode
Thin lms
Electrodeposition
Electrochemical characterization
a b s t r a c t
Thin lms of controlled thickness of Co/Al layered double hydroxide with different Co and Al percent-
ages have been electrosynthesized by the cathodic reduction of a 0.03M Co and Al nitrate solution. The
electrochemical behaviour of the lms deposited on Pt or ITO electrodes has been deeply studied in 0.1M
NaOHsolution. Our ndings demonstrate that as soon as a potential is applied in the anodic direction, the
lms undergo an irreversible change of phase.
2008 Elsevier Ltd. All rights reserved.
1. Introduction
Layereddouble hydroxides (LDHs) have many applications, such
as precursors for coatings and catalysts [1,2], hosts for photoac-
tivation and photocatalysis [3,4], and anion exchangers [5], and
they are widely employed as electrode surface modiers, to be
used as amperometric or potentiometric sensors [68]. Recently,
Co-basedLDHs havebeenproposedas supercapacitors, energystor-
age devices that have higher energy densities than conventional
dielectric capacitors and longer cycle lifetimes than batteries, to be
used in telecommunication devices and electric hybrid vehicles [9].
One of the advantages of using Co/Al LDH as an electrode material
insteadof Co
3
O
4
is that thestructurecanbestabilizedbypartial iso-
morphous replacement of the cobalt active sites with Al, resulting
in an enhancement of the Co utilization ratio over Co
3
O
4
. More-
over, Co-containing layered double hydroxides have been used as
precursors to prepare Fisher-Trops catalysts [10,11] and are active
in the catalytic decomposition of N
2
O [12,13], selective conversion
of acetone to vinyl ketone [14], and steam reforming of methanol
[15].

Corresponding author. Tel.: +39 0512093256; fax: +39 0512093690.


E-mail address: scavetta@fci.unibo.it (E. Scavetta).
1
ISE member.
LDHs or hydrotalcite-like compounds (HTs) are lamellar materi-
als with the chemical formula [M
a
(II)
1x
M
b
(III)
x
(OH)
2
]
x+
(A
n
x/n
)
mH
2
O, shortly named M
a
/M
b
-A, where M
a
and M
b
are metals, A is
an anion and x ranges between 0.22 and 0.50, when M
a
is cobalt, in
order to have a pure HT phase [16,17]. LDHs containing a transition
metal like Ni or Co for example, have been proposed as materials
with improved charge transport in the range of applied potential,
especially in basic solution [1820].
Different methods have been proposed to modify electrode sur-
faces with LDH lms; the most common one consists of depositing
a xedamount of a colloidal solutionof the LDH, previously synthe-
sized in bulk by the coprecipitation method [21], onto the support.
A drawback of this method is the poor adhesion of the lm to the
support material. We have recently carried out a study to elec-
trosynthesize well-adhered thin lms of a Ni/Al LDHon Pt surfaces
[22,23]. The great advantage of the proposed method is the short
time needed to modify the electrode surface, whereas a drawback
is that the electrodeposited material has a poor crystallinity.
Here we describe the electrodeposition of Co/Al thin lms
with variable thickness and Co/Al ratios, which can be obtained
simply by changing the electrolytic bath composition and the elec-
trosynthesis length. The lms have been characterized by studying
their structure, composition and morphology by spectroscopic and
surface techniques. Furthermore, a detailed study on the electro-
chemical behaviour of the synthesized materials in 0.1M NaOH
solution has been carried out.
0013-4686/$ see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2008.07.078
1028 E. Scavetta et al. / Electrochimica Acta 54 (2009) 10271033
2. Experimental
2.1. Apparatus
All the electrochemical tests were carried out in a single
compartment, three-electrode cell. Electrode potentials were mea-
sured with respect to an aqueous saturated calomel electrode
(SCE). A Pt wire was used as the counter electrode. The CV
curves were recorded using a CHInstruments Mod. 660 C, con-
trolled by a personal computer via CHInstruments software. The
temperature was controlled using a HAAKE D8 thermostat. An
Autolab PGSTAT20 (Ecochemie, Utrecht, The Netherlands) poten-
tiostat/galvanostat interfaced with a personal computer was used
in spectro-electrochemical measurements. UVvis measurements
were obtained using a Hewlett-Packard 8453 diode array spec-
trophotometer with an in situ electrochemical cell (homemade).
X-ray diffraction (XRD) patterns were collected with Cu K
radiation (=1.5418) by means of an XPertPro PANalytical
diffractometer equipped with a fast XCelerator detector, perform-
ing steps of 0.06

(2) and counting 80s/step. The thin lm was


gently removed from the electrode with the help of a lancet and
placed on a zero background sample holder (The Gem Dugout,
State College, PA, USA).
To estimate the lmthickness, a portionwas etched witha 0.1M
HCl solution and then submitted to atomic force microscopy (AFM,
scanning Probe Microscope Vista 100, Burleigh Instruments) oper-
ating in contact mode with a force of 32nN.
The morphology and chemical composition of LDH lms were
investigatedby optical microscopy (Reichert-Jung MeF3Aequipped
withaJVC-TK-C1381colour videocamera) andbySEM/EDSanalysis,
using an EVO 50 Series Instrument (LEO ZEISS) equipped with an
INCAEnergy 350 EDS microanalysis system and INCASmartMap for
imaging the spatial variation of the elements in a sample (Oxford
Instruments Analytical). The accelerating voltage was 25kV, the
beam current 1.5nA and the spectra collection time 100s. The
Fourier transform infrared spectra (FT-IR) were recorded with a
Nicolet Nexus 470 spectrometer, congured with a Nicolet Con-
tinuum microscope and a MCT/B liquid-nitrogen-cooled detector.
Spectra were collected in ATR (attenuated total reectance) mode
through a Cassegrain objective (14), reaching a spatial resolution
of 100m
2
. Thespectrawererecorded(as sumof 256scans witha
resolution of 4cm
1
) in the spectral region of the mediuminfrared
(8004000cm
1
).
2.2. Chemicals
All chemicals (Fluka) were of reagent grade purity and used
as received. All solutions were prepared with doubly distilled
water from a glass distillation apparatus. The Co/Al-NO
3
LDH was
electrosynthesized from freshly prepared solutions of cobalt and
aluminium nitrates.
2.3. Preparation of modied electrodes
APt rodof 3 or 5mmdiameter, was insertedinside a Teontube.
The external surface was polished to a mirror-like surface with an
aqueous alumina(Logitech) slurryof threedifferent granulometries
(1, 0.3 and 0.05m) on a wet polishing cloth, rinsed with distilled
water and then sonically cleaned in a 1:1ethanol/water mixture,
for 10min, to remove any trace of alumina. After rinsing the bare
electrode withcarbondioxide-free water, it was dried at roomtem-
perature. For the spectro-electrochemical tests, indium tin oxide
(ITO)-coated rectangular glass slides (0.92.7cm) were employed.
Thelms of Co/Al-NO
3
LDHweredepositedontheelectrodesur-
face bycathodic reductionof a 0.03Msolutioncontaining Co(NO
3
)
2
and Al(NO
3
)
3
at different Co/Al molar ratios (2/1, 3/1, 4/1, 5/1) and
0.3M KNO
3
as supporting electrolyte.
The electrochemical reaction was carried out in a single com-
partment, three-electrode cell, by applying a potential of 0.9V vs.
SCE [22]. Different deposition times (10, 30, 60, 120s) were con-
sidered. After electrodeposition, the lms were rinsed gently with
doubly distilled water, dried in a dessicator over silica gel and then
promptly submitted to the characterization analysis.
3. Results and discussion
3.1. Electrodeposition from a solution with a Co/Al ratio of 3/1
As a rst step, the electrochemical depositions were performed
using a solution with a Co/Al ratio of 3/1, on the basis of previous
ndings for the Ni/Al LDH [22].
The deposited lms completely cover the Pt surface, and appear
quite homogeneous, with the presence of some particles of about
2m on their surface. The lms are very stable from a mechanical
point of viewfor all the investigated deposition times. Fig. 1 shows
the SEM microphotograph obtained for a 60s deposition time, but
all the deposits appear to be similar.
The composition and thickness of the lms electrosynthesized
for different deposition times have been investigated by using
SEM/EDS and AFM, respectively, and the results are reported in
Table 1. The Pt mass percentage has been reported because it gives
information about the local thickness of the lm: the higher the Pt
percentage, the lower the thickness of the deposit. All the reported
data represent the averages of the results obtained by perform-
ing SEM/EDS or AFM analysis on three different zones of the same
electrode and repeating the measurements on ve different elec-
trodes modied in the same conditions. It can be noticed that Co
andAl mass percentages, especiallythosefor thelms depositedfor
shorter deposition times, are very low due to the small thickness.
The thickness of the lms ranges from about 110nm for the
thinnest one to 740nm for that obtained at the highest deposition
time. Fig. 2 shows an AFM image obtained for the lm electrosyn-
thesized for 30s. The lm thickness, obtained from the prole of
the AFM image, increases very quickly in the rst 10s, and then
continues in an almost linear fashion, until 120s (see Table 1). This
evidence canbe explained by hypothesizing that the rst deposited
layer slows down the LDH precipitation perhaps because the ef-
ciency of the electrochemical reaction is lower at a modied Pt
surface.
A key parameter for the existence of LDH structures is the
Me(II)/Me(III) ratio which, in the case of layered double hydrox-
Fig. 1. SEM image of the Co/Al layered double hydroxide electrosynthesized from a
solution with a Co/Al ratio of 3/1 for 60s deposition time.
E. Scavetta et al. / Electrochimica Acta 54 (2009) 10271033 1029
Table 1
Mean values (S.D.) of Co and Al mass percentages obtained fromEDS microanalysis and the corresponding calculated Co/Al molar ratios, for Pt electrodes modied with lms
obtained from a 0.03M solution of Co and Al nitrates (Co/Al molar ratio=3/1)
Deposition time (s) Co mass% Al mass% Pt mass% Co/Al ratio Thickness (nm)
10 0.98 (0.05) 0.22 (0.03) 82.1 (0.2) 2.03/1 110 (12)
30 1.08 (0.04) 0.25 (0.03) 79.1 (0.1) 1.98/1 180 (15)
60 1.55 (0.03) 0.37 (0.01) 75.3 (0.2) 1.92/1 356 (9)
120 2.55 (0.09) 0.50 (0.07) 68.6 (0.2) 2.30/1 740 (13)
Applied potential, 0.9V, for different deposition times. The lm thicknesses obtained from the prole of AFM measurements (such as the one shown in Fig. 2) are reported
in the last column.
ides containing Co, has to be between 1 and 3.54. All the lms,
even those electrosynthesized for very short times, display a ratio
close to 2. This evidence allows us to hypothesize that Co/Al LDH
electrodeposition occurs through a mechanism analogous to that
proposed for Ni/Al-NO
3
, i.e., the precipitation of the layered dou-
ble hydroxide takes place without the involvement of the M(III)
hydroxide [22].
As previously observed for the electrosynthesized Ni/Al-NO
3
LDH and Co/Al-NO
3
LDH, the Co/Al ratio is lower than the value at
which the two metals are present in the deposition solution. This
result can be explained by the very high stability of the LDHphases
with a Me(II)/Me(III) ratio of 2 [24].
The XRD pattern of the lm, obtained for a deposition time of
200s, is reported in Fig. 3. It is characterized by a low signal to
noise ratio, due to the low amount of the LDH material on the
electrode surface. All reections can be indexed as those typi-
cal of a hydrotalcite-like structure (JCPDS: 38-0487), which also
establishes the purity of the Co/Al LDH obtained from the elec-
trodeposition. In particular, the reections at 8.38, 4.18 and 2.66
correspond to diffraction by basal planes (003), (006) and (012),
respectively, and are compatible with an LDH-containing nitrate.
The XRD pattern is related to a poor crystalline phase, probably
due to the fast kinetics of the LDH precipitation which hinders an
ordered stacking of the brucite layers.
Fig. 4 reports the FT-IR spectrum of the same lm which shows
a broad band at high frequency (33753415cm
1
) due to the OH
Fig. 3. XRD pattern of the Co/Al layered double hydroxide electrosynthesized from
a solution with a Co/Al ratio of 3/1 for 200s deposition time.
stretching of water molecules and hydroxyl groups of the brucitic
layers, a narrower absorption band at 1630cm
1
due to H
2
O vibra-
tion of the water molecule, and two bands at 1360 and 1390cm
1
,
due to the interlayer carbonate and nitrate anions, respectively.
Fig. 2. Three-dimensional AFMimage, collected by working in contact mode, of the HT lm(Eapp =0.9V, t =30s) obtained froma 0.03Msolution of Co and Al nitrates (Co/Al
molar ratio, 3/1), after etching with 0.1M HCl.
1030 E. Scavetta et al. / Electrochimica Acta 54 (2009) 10271033
Fig. 4. FT-IR spectrum of the Co/Al layered double hydroxide electrosynthesized
from a solution with a Co/Al ratio of 3/1 for 200s deposition time. The inset shows
a magnication of the region between 1200 and 1550cm
1
.
The typical band of carbonate conrms that this species is present
in the interlayer space, probably deriving from the adsorption of
atmospheric carbon dioxide, despite the very short lengths of the
deposition and the use of N
2
atmosphere.
It was not possible to record signicant peaks in the skeletal
region (600420cm
1
), because of the very low signal/noise ratio,
due to the small amount of material.
3.1.1. Electrochemical behaviour
As a rst step, we investigated the electrochemical behaviour
of the lms deposited for 60s in 0.1M NaOH solution. The open
circuit potential (ocp) was measured for the freshly prepared lm,
after a stabilization period of 10min, and resulted in 0.0545V. A
potential triangular waveform(in the potential range of 00.700V)
was applied to the electrode starting with the segment in the pos-
itive direction. In the rst cycle an irreversible oxidation peak was
observed (see Fig. 5). The ocp value was measured again at the end
of the rst cycle and the recorded value was 0.0700V. Starting from
the second cycle, two couples of peaks could be observed, the rst
one with E
1/2
=0.15Vand the second with E
1/2
=0.35V. The electro-
chemical signals were stable and practically did not change after
Fig. 5. Cyclic voltammogramms recorded in 0.1M NaOH at a Pt electrode modied
with the lmelectrosynthesized (Eapp =0.9V; t =60s) froma 0.03Msolution of Co
and Al nitrates (Co/Al molar ratio=3/1); potential scan rate =0.05V/s.
Table 2
Mean values (S.D.) of Co and Al mass percentages obtained from EDS microanalysis
and the corresponding calculated Co/Al molar ratios, for a Pt electrode modied
with the lm obtained from a 0.03M solution of Co and Al nitrates (Co/Al molar
ratio=3/1) at E=0.9V, and t =60s, for the fresh lm and after 100 voltammetric
cycles in 0.1M NaOH
Fresh lm After 100 cycles
Al mass % 0.37 (0.01) 0.41 (0.06)
Co mass % 1.55 (0.03) 1.52 (0.04)
Co/Al molar ratio 1.92/1 1.90/1
several hundreds of cycles, indicating the good stability of the lm
modifying the electrode.
The current signals observed from the second cycle forward are
similar tothoseobtainedbyWanget al. for achemicallysynthesized
Co/Al LDH submitted to thermal treatment [9].
The peak couples (I, I

) and(II, II

) correspond, respectively, tothe


reactions (1) and (2) which are written referring, for simplicity, to
Co(OH)
2
since in this material Co is octahedrally coordinated with
OH as it occurs in LDH [25,26]:
Co(OH)
2
+OH

CoOOH + H
2
O + e

(1)
CoOOH + OH

CoO
2
+H
2
O + e

(2)
The lm was again analyzed with SEM/EDS and XRD after 100
voltammetric cycles in 0.1M NaOH. Table 2 shows the results from
EDS analysis, from which we can observe that the oxidation of the
lmdoes not induceanysignicant modicationinits composition.
As far as the XRD analysis, the pattern recorded for the oxidized
lm resulted super imposable to that of the fresh lm (reported in
Fig. 3).
Theelectrochemical experiment was repeatedusinganITOglass
electrode modied in the same way as platinum to monitor the
lm colour changes. The results are reported in Fig. 6. The freshly
prepared lmappeared weakly pink (
max
=525nm) in agreement
with the expected colour of the Co/Al layered double hydroxide
phase [27]. After the rst cycle, the lm irreversibly changed its
colour becoming pale yellow, suggesting a partial oxidationof some
Co(II) sites [28].
The successive cycles were accompanied by a reversible change
incolour of the lmfrompale yellow(most reducedform) to brown
(most oxidized form) which displayed an absorbance maximum at
about =435nm and a shoulder between 600 and 700nm. Fig. 6B
evidences the reversible electrochromismof the LDHlmreporting
the T% measured at =425nm as a function of time and potential;
the T% values range from 82% at E=0.0V to 60% at E=0.7V.
These observations can be explained by hypothesizing that dur-
ing the rst scan a change of phase occurs in the lm. The Co(III)
moles, produced in the rst segment of the rst scan, were calcu-
latedby integrationof the anodic current andresultedin1.510
8
,
which represents about 20% of the total Co moles in the lm. We
can therefore hypothesize that an irreversible oxidation of some
Co(II) sites, perhaps the inner sites, takes place. This hypothesis is
compatible both with the change of the ocp value and of the lm
colour, which has become pale yellow to indicate the presence of
Co(III) sites in the LDH structure.
We could hypothesize that the oxidation of Co(II) gave rise to
a new hydrotalcite-like structure, Co(II)/Co(III)/Al(III), which was
stabilized by the concomitant intercalation of OH

anions from
the solution in the interlayer spacing. This nding is analogous to
that obtainedafter thermal treatment of Co-basedLDHs, chemically
synthesized, for which the authors observed an easy oxidation of
Co(II) [27,28]. Moreover it is well known that LDH structures con-
taining Co both as divalent and trivalent cations can be synthesized
in bulk [29,30].
E. Scavetta et al. / Electrochimica Acta 54 (2009) 10271033 1031
Fig. 6. (A) UVvis spectroelectrochemistry in0.1MNaOHfor anITOelectrode modied withthe lm, electrosynthesized as described in Fig. 5, recorded before the application
of the potential (black curve), after 1 cycle (green curve) and during the second cycle (pink and red curves) at the potentials shown in the legend. (B) Plot of %T (=425nm)
as a function of time and applied potential. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of the article.)
The hypothesis of the Co(II)/Co(III)/Al(III) LDH formation is
supported also by the UVvis spectrum and, particularly, by the
shoulder observed between 600 and 700nm. This feature can
be ascribed to the dd transitions in the low spin octahedrally
coordinated Co(III) species and becomes stronger as the oxidation
proceeds, in agreement with the observed darkening of the lm.
In order to assess if reactions (1) and (2) are consecutive pro-
cesses that involve Co(II) centres, or if only Co(III) sites produced
in the rst oxidative step are involved in reaction (2), we have
conducted CV experiments at different scan ranges. From the CV
curves, reported in Fig. 7, we can observe that the two peak systems
are independent of each other, an observation which conrms the
second hypothesis.
The effect of the scan rate was studied by performing tests in
the range from 0.001 to 0.2V/s. The height of the anodic peak of
both redox couples is linearly dependent on the scan rate until a
value of 0.05V/s, indicating a thin layer-like behaviour. At higher
scan rates the behaviour of the electrode becomes diffusive. Fig. 8
shows a plot of I
pa
(I) as a function of the scan rate and square root
of the scan rate; similar behaviour was found also for I
pa
(II).
Fig. 7. Cyclic voltammogramms recorded in 0.1M NaOH at a Pt electrode modied
with the lm electrosynthesized (Eapp =0.9; t =60s) from a 0.03M solution of Co
and Al nitrates (Co/Al molar ratio=3/1); potential scan rate =0.01V/s.
Films electrosynthesized for different deposition times (10, 30,
60, 120s) were prepared to study the effect of the lm thickness
on the electrochemical behaviour of the material. It was not pos-
sible to perform electrochemical tests on lms deposited for times
longer than 120s, since in such a case the lms were mechani-
cally unstable and began to ake off. All of the modied electrodes
behave like that obtained for a deposition time of 60s: in the
rst cycle an irreversible anodic peak is observed, then the sig-
nal remains unchanged. From the integration of the peak in the
rst segment we can calculate the number of moles of Co(III) pro-
duced, which increases as the thickness of the lmincreases, being
7.410
9
for the lmelectrosynthesized for 10s and 1.910
8
for
the thicker one. Fig. 9 shows the cyclic voltammograms (second
and third cycle) recorded for electrodes modied with lms syn-
thesized for different deposition times. We can observe an increase
of both the capacitive and faradic current, the former being linked
to the thickness increase and the latter being related to the increase
of electroactive Co centers.
Fig. 8. Plot of Ipa (I) vs. scan rate (black points) and the square root of scan rate (red
points). (For interpretation of the references to color in this gure legend, the reader
is referred to the web version of the article.)
1032 E. Scavetta et al. / Electrochimica Acta 54 (2009) 10271033
Fig. 9. Cyclic voltammogramms recorded in 0.1M NaOH at a Pt electrode modied
with the lm electrosynthesized (Eapp =0.9V) for different deposition times listed
in the legend, from a 0.03M solution of Co and Al nitrates (Co/Al molar ratio=3/1);
potential scan rate =0.01V/s.
3.2. Effect of Co/Al ratio
The effect of the Co/Al ratio was studied by preparing lms elec-
trodeposited for 60s fromdeposition solutions with variable Co/Al
ratios (2/1, 3/1, 4/1 and 5/1).
Each lm was analyzed with SEM/EDS and then submitted to
electrochemical characterization in 0.1M NaOH solution.
Table 3 reports the characteristic parameters of lm composi-
tion and thickness obtained for the different modied electrodes.
In the same table is also reported, for each lm, the number
of Co(III) moles produced during the rst oxidative segment
(see Fig. 10) which was calculated by integrating the anodic
current.
As a rst observation we can note that the thickness of the lms
are quite similar, while the lmcomposition is strongly affected by
the Co/Al ratio in the deposition solution, increasing as the ratio
increases. In all cases, the Co/Al ratio in the lm is lower than the
value in the bulk solution and compatible with the ratio character-
istic for a hydrotalcite-like structure containing cobalt.
It is very interesting to note that the moles of Co(II) oxidized
during the rst voltammetric scan, are practically the same inde-
pendently of the Co/Al ratio.
XRD analysis has been performed on the lms electrosynthe-
sized for 200s in order to ascertain if all of the lms have a
hydrotalcite-like structure. The patterns, reported in Fig. 11, show
common features, with broad diffraction maxima located at the
angles typical of a hydrotalcite-like phase.
Fig. 12 shows the CV curves obtained in 0.1MNaOHsolution for
the lms electrodeposited for 60s fromsolutions containing differ-
ent Co/Al ratios. An increase of peak couple I can be observed as the
Co/Al ratio increases, while peak couple II is almost unchanged.
The increase of the rst peak couple can be easily explained
with the increase of Co(II) centres and the consequent decrease
Fig. 10. First segment of the cyclic voltammogramms recorded in 0.1MNaOHat a Pt
electrode modied with the lm electrosynthesized (Eapp =0.9V; t =60s), from a
0.03Msolutionof Co andAl nitrates (Co/Al molar ratio=2/1; 3/1; 4/1; 5/1); potential
scan rate =0.05V/s.
Fig. 11. XRD patterns of the Co/Al layered double hydroxide electrosynthesized for
t =200s from solutions with Co/Al molar ratio=2/1 (A); 3/1 (B); 4/1 (C); 5/1 (D).
of Al(III) in the lm; both effects contribute to make the electron
hopping process responsible of the conduction of the material eas-
ier.
A very important feature of the voltammetric curves is the fact
that, as the Co/Al ratio increases, the intensity of the second peak
couple is almost unchanged, in agreement with the hypothesis that
only the Co(III) sites produced in the rst step, whose number is
constant, are involved in the redox process associated to the second
peak couple of the voltammogramms (reaction (2)).
Table 3
Mean values (S.D.) of Co and Al mass percentages obtained from EDS microanalysis and the corresponding calculated Co/Al molar ratios for Pt electrodes modied with the
lms obtained from a 0.03M solution of Co and Al nitrates (Co/Al molar ratio=2/1; 3/1; 4/1 and 5/1)
Co/Al ratio in the deposition solution Co mass % Al mass % Co/Al ratio Number of Co(III) moles Thickness (nm)
2/1 1.36 (0.06) 0.68 (0.02) 0.99 1.510
8
367 (11)
3/1 1.55 (0.03) 0.37 (0.01) 1.92/1 1.510
8
356 (9)
4/1 1.70 (0.10) 0.30 (0.04) 2.60/1 1.610
8
360 (14)
5/1 1.98 (0.04) 0.26 (0.01) 3.48/1 1.610
8
378 (10)
Applied potential, 0.9V, for 60s. In the last column are reported the lm thicknesses obtained from AFM measurements.
E. Scavetta et al. / Electrochimica Acta 54 (2009) 10271033 1033
Fig. 12. Cyclic voltammogramms (second cycle) recorded in 0.1M NaOH at a Pt
electrode modied with the lm electrosynthesized (Eapp =0.9V; t =60s), from a
0.03Msolutionof Co andAl nitrates (Co/Al molar ratio=2/1; 3/1; 4/1; 5/1); potential
scan rate =0.01V/s.
4. Conclusions
We have successfully prepared Co/Al thin lms by electrode-
position: this synthetic approach allows for control of the lm
composition and thickness, just by changing the bath composition
and the electrosynthesis length.
Thelms havebeenpreparedbyreductioninpotentiostatic con-
ditions of a 0.03M solution of cobalt and aluminium nitrates. The
deposits appear very uniform and homogeneous with thicknesses
ranging from about 110 to 740nm. The Co/Al ratio in the resulting
lms is in agreement with that of a hydrotalcite-like structure and
always results lower than the two metal values in the electrodepo-
sition solution. XRD has clearly identied a brucitic structure and
FT-IR spectra have shown the presence of both NO
3

and CO
3
2
as
the interlayer anions.
The electrochemical characterization of the materials has been
carried out in 0.1M NaOH solution studying the effect of both the
electrosynthesis length, at a xed Co/Al ratio, and of the Co/Al ratio
and at a xed deposition time, on the electrochemical behaviour
of the material. Our ndings demonstrate that as soon as a poten-
tial is applied in the anodic direction, in basic solution, a change
of phase occurs in the lm. From the UVvis spectra and cyclic
voltammetric responses, we have hypothesized that the newphase
is Co(II)/Co(III)/Al(III) LDH. Fromthe secondvoltammetric cycle for-
wards, all of the lms display, tworeversible couples of peaks which
are higher as the deposition time increases and whose signal is
stable for several hundreds of cycles. The two processes involve,
respectively, the redox couple Co(II)/Co(III) and Co(III)/Co(IV) and
are accompanied by a reversible change of colour from pale yellow
to brown. Our results allow us to hypothesize that the main con-
tribution to reaction (2) comes from the Co(III) centers irreversibly
produced in the rst oxidative scan.
Acknowledgments
Thanks to MIUR and to the University of Bologna for nancial
support and to Dr. Sandra Stipa for her help in SEMmeasurements.
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