ISSN 1023-1935, Russian Journal of Electrochemistry, 2006, Vol. 42, No. 9, pp. 995–1000.

© MAIK “Nauka /Interperiodica” (Russia), 2006.

Original Russian Text © T.Ya. Safonova, N.V. Smirnova, O.A. Petrii, 2006, published in Elektrokhimiya, 2006, Vol. 42, No. 9, pp. 1104–1109.

SHORT
COMMUNICATIONS

Adsorption of Polyethylene Glycol on Platinum Electrode

from Acidic Solutions
T. Ya. Safonova,a N. V. Smirnova,b and O. A. Petriia,z
a
Moscow State University, Vorob’evy Gory 1, Moscow, 119992 Russia
b Southern-Russia State Technical University, ul. Prosveshcheniya 132, Novocherkassk, 346400 Russia
Received March 13, 2006

Abstract—The effect of the molecular mass of polyethylene glycol (PEG) on its adsorption on platinized plat-
inum from aqueous solutions of 0.5 M H2SO4 and 1 M HCl is studied using the methods of open-circuit poten-
tial shifts and voltammetry. In sulfuric acid solutions, the PEG adsorption is accompanied by dehydrogenation
and hydrogenation processes, which probably involve the terminal groups of polymers. For PEG with the
molecular mass of 600–40000, the established stationary surface states turn out to be close to one another.
Anions Cl– inhibit the PEG adsorption and electrooxidation. The adsorption behavior of PEG samples studied
substantially differs from that of ethylene glycol under comparable conditions.
DOI: 10.1134/S1023193506090163

Key words: polyethylene glycol, platinum, adsorption

INTRODUCTION play the role of a polymolecular polydentate ligand in

Polyethylene glycol (PEG) additions are conven-
tionally used for regulating the processes of metal elec-
trocrystallization including those in practice ([1–17]
and references therein). In connection with this, the
authors of [2, 4–16] studied the PEG adsorption on dif-
ferent electrodes. Certain data on the PEG adsorption
on platinized platinum (Pt/Pt) electrodes were obtained
with the aim of gaining insight into the quasi-templat-
ing effect of PEG on the palladium electrocrystalliza-
tion [18, 19]. The studies of the adsorption of polymeric
molecules on electrodes are also of considerable inter-
est in their own right [20], making it possible to eluci-
date the role and character of the interaction of the
polymeric chain fragments with the electrode surface.
Particularly, it was concluded [21] that on a mercury
electrode PEG behaves as a cation-like surfactant and
shifts the potential of zero charge of mercury to less
negative values. In [22], PEG was used as a model of an
adsorbate, a single molecule of which, when adsorbed,
should displace a considerable number of water mole-
cules; hence, the description of its adsorption behavior
should invoke the use of more sophisticated isotherms
as compared with low-molecular adsorbates. Thus,
PEG may serve as an interesting model of a supramo-
lecular adsorbate. It was assumed that a PEG adlayer
can be considered as a model of a surface-immobilized
polymeric electrolyte permeable for low-molecular
components of the solution [15, 16]. The PEG ability to
z Corresponding author, email: petrii@elch.chem.msu.ru
the surface layer also attracts attention [16]. By the
example of PEG, it is possible, in principle, to develop
the approaches towards studying the effect of the chain
length of a molecule on its electrochemical and adsorp-
tion behavior. The attempts to gather information in this
direction were undertaken in [23]. Finally, PEGs are
interesting as substances that change the solution vis-
cosity at high concentrations and allow one to model
the effect of this factor on the electrode processes.
This work presents the results of studying the
adsorption of PEG with the molecular mass from 600 to
40000 in acidic solutions at a Pt/Pt electrode.
EXPERIMENTAL
We used an electrochemical three-electrode glass
cell with anodic and cathodic compartments separated
by a valve. The cell had a special vessel for introducing
the additions of deaerated solutions of polymers into
the supporting electrolyte solution. A reversible hydro-
gen electrode in the same solution served as the refer-
ence electrode; all potentials Er are related to this elec-
trode. The Pt/Pt electrode was prepared by the deposi-
tion on a platinum plate at a potential of 0.2 V
according to the procedure described earlier [24].
Cyclic voltamograms were recorded using a P-5827M
potentiostat and an N-308 potentiometer.
Different companies supplied PEGs with different
molecular masses, namely, 600 (Fluka AG); 1000,

995
996 SAFONOVA et al.
Er, V
0.4
5'
6 The electrode potential preliminary stabilized at 0.4 or
0.3
4 circuit was broken and a portion of deaerated polymer
0.2
3 5
2 4'
1 Figure 1 shows the results of potential shift mea-
0.1
0 500 1000 1500 2000
t, s
Fig. 1. Open-circuit potential shifts of a Pt/Pt electrode
upon introduction of (1,1') ethylene glycol and (2–6, 4', 5')
PEG into 0.5 M H2SO4 and (5') 1 M HCl solutions at poten-
tials of (1–6, 5') 0.4, (4') 0.1, and (1') 0.05 V. Molecular
weight of PEG: (2) 600, (3) 1000, (4, 4') 4000, (5, 5') 15000,
and (6) 40000. Ethylene glycol concentration 0.5 M; poly-
ethylene glycol concentration 4.4 g/l.
1500, and 15000 (Shuchardt); as well as 4000, 20000,
and 40000 (Lobochem). The weight distribution of
samples did not exceed 1.1. Ethylene glycol of the
reagent grade was twice distilled under reduced pres-
sure. As a rule, the measurements were performed at
equal weight concentrations of PEG, because these
very concentrations were used earlier in our experi-
ments on the palladium electrocrystallization. Equal
weight concentrations correspond to the equal content
of –(CH2CH2–O)– groups in the studied solutions.
However, this means that the molar concentrations
decreased with the increase in the chain length. For
example, the concentration of 4.4 g/l, which was
largely used in this study, corresponds to the following
molar concentrations (mmol): 7.3 (600), 4.4 (1000), 1.1
(4000), 0.293 (15000), and 0.11 (40000). The systems
with equal molar concentrations in solutions will be
considered in further studies.
Solutions were prepared using water cleaned on a
Millipore unit. High-grade hydrochloric acid was sup-
plied by Merck. Extrapure sulfuric acid was twice dis-
tilled under a reduced pressure. Argon of ultra-high
purity grade was used for the removal of dissolved oxy-
gen from solutions. All measurements were carried out
at (20 ± 1)°ë.
RUSSIAN JOURNAL OF ELECTROCHEMISTRY
RESULTS AND DISCUSSION
To study the adsorption of PEG on a Pt/Pt electrode,
we measured the potential shifts upon bringing the PEG
additions in contact with the open-circuited electrode.
0.1 V in 0.5 M H2SO4 solutions. After the potential was
stabilized to a such degree that its shift did not exceed
0.1 mV/min upon switching off the polarization, the
solution was added to 0.5 M H2SO4.
surements. All the substances studied demonstrated the
1' same trend with respect to potential shifts, viz., for the
initial Er = 0.4 V, the potential shifted to lower values,
while for the initial Er = 0.1 V the potential shifted to
greater values. Thus, in the presence of PEG, the poten-
tial ultimately reached the value of ~0.175 V irrespec-
tive of the polymeric chain length.
According to the concepts developed earlier by the
example of organic substances of different classes [25],
a potential shift from 0.4 V to lower values points to the
electrooxidation of PEG molecules which probably
occurs via the dehydrogenation mechanism. A potential
shift from 0.1 V to higher values is the result of elec-
troreduction of PEG molecules, probably, by the hydro-
genation mechanism.
In principle, it is possible to assess the PEG adsorp-
tion rate from the initial rate of potential variation upon
the introduction of the adsorbate, namely, iads = ëdE/dt,
where iads is the adsorption rate and ë is the total capa-
citance of the electrode. These calculations should take
into account that the molar concentration of PEG
decreases with the increase in the chain length in the
solutions studied (see above). Assuming that, at the first
moment, the adsorption rate on a clean surface at 0.4 V
depends linearly on the PEG molar concentration, one
would expect the potential shift rate to decrease by a
factor of ~70 when going from PEG-600 to PEG-
40000. Actually, the experimental potential shift rate
decreased only by a factor of ~8. First of all, this result
shows that the adsorption is not limited by the adsor-
bate diffusion in solution, because the diffusion coeffi-
cient also decreases with the increase in the chain
length; hence, one should expect a still greater decrease
in the potential shift rate. The diffusion coefficients of
PEG were measured in [26]. The results of that study
can be approximated by the following relationship:
log D = 3.9022 – 0.55036 log M , where D is the diffu-
sion coefficient in cm2/s and M is the mass of PEG mol-
ecules. For the studied PEGs, the D values assessed using
this equation are as follows (cm2/s): 3.71 × 10–4 (600),
2.80 × 10–6 (1000), 2.24 × 10–6 (1500), 1.31 × 10–6 (4000),
0.63 × 10–6 (15000), and 0.37 × 10–6 (40000). Thus, for
Vol. 42 No. 9 2006
 ADSORPTION OF POLYETHYLENE GLYCOL ON PLATINUM ELECTRODE
a slow diffusion stage under a condition of linear diffu-
sion, in the solution studied, the potential shift rate
would have been expected to decrease by a factor of
~700 when going from PEG-600 to PEG-40000. Sec-
ond, the obtained relationship of the potential shift rates
for these PEGs allows one to conclude that the PEG
adsorption rate increases with the chain length. The rea-
sons for this phenomenon require additional studies.
It cannot be ruled out that the processes of dehydro-
genation and hydrogenation are accompanied by the
destruction of PEG molecules. The ultimately estab-
lished potential is determined by the hydrogen
adsorbed on the electrode, the surface coverage of
hydrogen being regulated by the rates of the mentioned
processes of oxidation and reduction of PEG mole-
cules.
In hydrochloric acid solutions, the potential shifts
much more slowly upon the introduction of PEG
(Fig. 1, curve 5') as compared with sulfuric acid solu-
tions, i.e. the adsorption of chloride anions hinders the
adsorption and dehydrogenation of PEG.
When ethylene glycol is introduced at 0.4 V, the
potential reaches lower values as compared with PEG
[27]. This points to a higher rate of dehydrogenation of
ethylene glycol molecules as compared with PEG. At
the same time, the potential shift from its initial value
in the hydrogen region upon the addition of ethylene
glycol occurs at a lower rate as compared with PEG,
even for the higher ethylene glycol concentrations, i.e.
the hydrogenation of ethylene glycol is a slower pro-
cess than that of PEG. It is this ratio of dehydrogenation
and hydrogenation rates that leads to the establishment
of lower steady-state potentials in ethylene glycol solu-
tions as compared with PEG solutions.
Cyclic voltamograms were measured in PEG solu-
tions after the potential shifts were recorded and the
steady-state values of Er were established. In some
experiments, the voltamograms were recorded after the
potential reached its steady-state value and then was
changed stepwise to 0.05 V. Voltamograms were also
measured after stabilizing the electrode in PEG solu-
tions at Er = 0.05 V or other hydrogen-region potentials
(0.15, 0.2 V). The stabilization time was chosen such as
to reach a steady-state surface state. Figure 2 shows the
resulting voltamograms.
The analysis of Fig. 2 makes it possible to conclude
that, on a qualitative level, PEGs with different chain
lengths behave similarly but display certain quantita-
tive differences (these differences can be partly
explained by the changes in the electrode surface state
due to aging). For example, all the curves demonstrate
the PEG oxidation peaks at the potentials of the double-
layer region and the beginning of the oxygen adsorp-
RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 42
997
tion region and also the currents of PEG oxidation in
the oxygen region. Irrespective of the PEG chain
length, the cathodic branches of curves change little in
the oxygen reduction region, only a slight decrease in
the oxygen amount can be observed. Obviously, this
result points to desorption of the PEG oxidation prod-
ucts in the oxygen potential region and to the absence
of PEG adsorption on the surface occupied by oxygen.
For PEG with low molecular weights, the cathodic
curves demonstrate a decrease in the amount of
strongly bound hydrogen; this effect decreases with the
increase in the chain length. The cathodic curves of vol-
tamograms are virtually independent of the conditions
under which the anodic curves were measured. At the
same time, the anodic curves in the potential range of
0.05–1.2 V strongly depend on the preliminary opera-
tions before their measurement. As a rule, after the elec-
trode was in contact with PEG at 0.05 V, a high peak in
the hydrogen region and the oxidation currents in the
double layer region appear in the anodic branch. This
can be explained by the appearance of the products of
PEG reduction at 0.05 V and their subsequent oxidation
as the potential shifts in the anodic direction. After the
electrode was kept at 0.2 V, the further voltammogram
demonstrates a decrease in the adsorption of both
weakly and strongly bound hydrogen. In cyclic volta-
mograms measured in the range of 0.05–1.4 V, a certain
stationary state, intermediate between those observed
in the former two cases, is reached.
As follows from Fig. 3, when hydrochloric acid
serves as the supporting electrolyte, no effect of PEG
on the hydrogen adsorption is observed, and the PEG
oxidation currents appear only at the potentials above
~0.9 V. These experiments confirm the above conclu-
sion that chloride ions inhibit the PEG adsorption and
electrooxidation.
With the aim of studying the behavior of PEG
chemisorption products, both the electrode and the cell
were washed with the supporting electrolyte solution
after the experiments involving PEG. However, these
attempts failed, because it proved impossible to com-
pletely remove PEG from the system even by repeated
washings. This is apparently explained by the high sur-
face activity of PEG and its adsorption on the cell walls.
Hence, the experiments were carried out in solutions
with the lower initial concentration of PEG. According
to Fig. 4, in this case, the voltammogram demonstrates
a slight decrease in the amount of adsorbed hydrogen
and the appearance of an oxidation peak, which is
largely located in the double layer potential region and
typical of the oxidation of one-carbon species. Accord-
ing to Fig. 4, the chemisorption of ethylene glycol, in
contrast to the adsorption of PEG studied, is accompa-
nied by the intense removal of adsorbed oxygen and the
No. 9 2006
998 SAFONOVA et al.

I, mÄ
I, mÄ 4
6
10 (‡) (b)
6 3
5
3
2
5
4
0 1
1
0
–3

–5
–6

–10
0 0.5 1.0 1.5 0 0.5 1.0 1.5
6 5
10 (c) (d)
3
5 2
3 4
4
5 3
1
0
1
0
–3

–5 –6

–10 –9
0 0.5 1.0 1.5 0 0.5 1.0 1.5
Er, V Er, V

Fig. 2. Voltammograms of a Pt/Pt electrode measured in 0.5 M H2SO4 (1) in the absence and (2–6) in the presence of 4.4 g/l PEG
with molecular weights of (a) 600, (b) 1000, (c) 4000, and (d) 40000. Curves 1 and 2 are cyclic voltamograms in the potential range
from 0.05 to 1.4 V. Curves 3 were obtained upon introduction of PEG at the open-circuit potential of 0.4 V immediately after the
potential reached its steady-state value and was shifted to 0.05 V. Curves 4–6 were measured after the electrode was kept in a PEG
solution at (4) 0.05, (5) 0.2, and (6) 0.15 V for 10–50 min and the potential was shifted to 0.05 V. Potential scan rate 10 mV/s.

appearance of a considerable amount of one-carbon
species characterized by a pronounced electrooxidation
peak at ~0.8 V.
The obtained results show that platinum behaves
differently in the presence of PEG and in the presence
of ethylene glycol; in any case, as regards certain
details, this transition would probably be more distinct
for PEGs with molecular weights below 600.
It seems interesting to compare the results obtained
on Pt/Pt electrodes with those on the adsorption of PEG
on smooth platinum, which were obtained by the volta-
mmetry and quartz single-crystal microbalance
(QSCM) methods [14]. In the latter study, it was found
that the adsorption of PEG is hindered in solutions that
contain chloride anions and this effect increases with
the chloride concentration in solution. Based on the
QSCM results, the limiting surface coverage for PEG
was found to be ~0.21, although the recorded anodic
voltamograms demonstrated only a minor reduction of
the hydrogen adsorption. Thus, a comparison of the
electrochemical and QSCM results indirectly confirms
that certain faradaic processes, which are unambigu-
ously observed on Pt/Pt in the hydrogen potential
region, could also occur on smooth platinum. At the
same time, our measurements (Fig. 2) suggest that,

RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 42 No. 9 2006

 ADSORPTION OF POLYETHYLENE GLYCOL ON PLATINUM ELECTRODE
I, mÄ
8 1.8
4 1.2
2
1
0 0.6
–4
–8
0 0.4 0.8 1.2
Er, V
Fig. 3. Cyclic voltamograms of a Pt/Pt electrode measured
in 1 M HCl containing (1) 0 and (2) 4.4 g/l PEG-15000.
Potential scan rate 10 mV/s.
under certain conditions on Pt/Pt electrodes, it is possi-
ble to reach higher coverages (up to 0.5–0.6), as follows
from the decrease in the hydrogen adsorption. Because
PEG molecules are large (e.g. for PEG-4000 in its
spherical form, the diameter is ~1.8 nm), this result can
be attributed to the blocking of pores by the adsorbate.
In [14], as well as in our study, the currents of PEG oxi-
dation were observed at the potentials of both double-
layer and oxygen regions.
The results obtained to date are insufficient to
describe in detail the PEG adsorption on platinum. It
seems most probable that, as on copper electrodes [9],
the PEG molecules are adsorbed in the form of more or
less collapsed spheres. In such a case, the electrochem-
ical transformations mainly involve the terminal groups
of polymeric chains. This assumption allows us to
explain, for instance, the relatively small effect of PEG
on the adsorption of hydrogen and oxygen, because a
sphere has only a small number of points of contact
with the electrode surface. Note that similar effects are
typical of the adsorption of polytungstates, which also
form spherical particles that fail to block the pores in
platinized platinum.
ACKNOWLEDGMENTS
This work was supported by the Russian Foundation
for Basic Research, project no. 05-03-32592a, and the
Foundation for the support of leading scientific schools
of the Russian Federation, grant no. NSh-2089.2003.3.
RUSSIAN JOURNAL OF ELECTROCHEMISTRY Vol. 42
999
I, mÄ
2
3
1
0
0 0.5 1.0 1.5
Er, V
Fig. 4. Voltamograms of a Pt/Pt electrode measured in (1)
pure 0.5 M H2SO4 and after the accumulation of adsorbate
at open circuit from solutions of (2) 0.5 M ethylene glycol
and (3) 0.44 g/l PEG-40000 and washing the electrode with
the supporting electrolyte. The initial potential upon the
introduction of additives was 0.4 V. Potential scan rate
10 mV/s.
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