Electrochimica Acta 47 (2002) 3663
/3674

www.elsevier.com/locate/electacta

Electrocatalysis of methanol oxidation

T. Iwasita
Instituto de Quı́mica de São Carlos, Universidade de São Paulo, Cx.P. 780, 13560-970 São Carlos, SP, Brazil

Received 10 January 2002; received in revised form 10 February 2002

Abstract

Most relevant aspects of methanol electrooxidation on Pt electrodes, including voltametric as well as spectroscopic data on the
system are presented and discussed. Parallel reaction pathways have been demonstrated, producing CO2 and HCOOH or HCHO as
soluble products, to an extent that depends on several parameters of the systems like methanol concentration, electrode roughness,
and time of electrolysis. Several issues like the intermediates of the reaction and the yields of oxidation products remain yet unclear.
A status of-the-art on these and other aspects of methanol oxidation is presented, which may be useful for future investigations. This
is the aim of the present contribution and referenced papers were accordingly selected. # 2002 Published by Elsevier Science Ltd.

Keywords: Methanol; Fuel cell; Electrocatalysis; Electrooxidation; FTIR

1. The methanol system

From the different small organic molecules (HCOOH,

H2CO, CH3OH), methanol is the one being most
intensively investigated at present. Methanol oxidation
reaction has been the subject of a large number of
studies in the past [1,2]. Early works [3
/6] already
showed up a complex reaction mechanism, the electro-
catalysis of methanol oxidation being the most difficult
task in the realization of a direct acid methanol fuel cell
(DMFC). Since methanol oxidation reaction has been
reviewed several times, e.g. [7
/10], in the present paper
we intend just to present the most relevant aspects of the
electroacatalysis of methanol oxidation, thus giving a
status of-the-art on the system.
The thermodynamic potential for methanol oxidation
to CO2, lies very close to the equilibrium potential of
hydrogen:
CH3 OHH2 O 0 CO2 6 H 6e E  0:02 V
However, compared with hydrogen oxidation, this
reaction is by several orders of magnitude slower. As
early suggested by Breiter [5], the total oxidation process
consists of a pattern of parallel reactions which can, in
principle, be formulated as follows:
0013-4686/02/$ - see front matter # 2002 Published by Elsevier Science Ltd.
PII: S 0 0 1 3 - 4 6 8 6 ( 0 2 ) 0 0 3 3 6 - 5
Both of these pathways require a catalyst, which
should be able to (a) dissociate the C /H bond and (b)
facilitate the reaction of the resulting residue with some
O-containing species to form CO2 (or HCOOH). On a
pure Pt electrode, which is known to be the best catalyst
for breaking the C /H bond, complete oxidation takes
place via two processes occurring in separate potential
regions:

/ The first process, involving adsorption of methanol
molecules, requires several neighboring places at the
surface. Since methanol is not able to displace
adsorbed H atoms, adsorption can only begin at
potentials where enough Pt sites become free from H,
i.e. near 0.2 V versus RHE for a polycrystalline Pt
electrode.

/ The second process requires dissociation of water,
which is the oxygen donor of the reaction. On pure Pt
electrode, a strong interaction of water with the
catalyst surface is only possible at potentials above
0.4
/0.45 V versus RHE.
Thus, on a pure Pt catalyst methanol oxidation to
CO2 cannot begin below, say 0.45 V. However, the
adsorbate layer does not exhibit a good reactivity below
3664 T. Iwasita / Electrochimica Acta 47 (2002) 3663
/3674
approximately 0.7 V, i.e. a high rate of oxidation at pure
Pt occurs at potentials without technological interest.
2. Methanol adsorption
It was suggested that methanol adsorption takes place
in several steps, forming different species due to
dissociation of the molecule:
CH3 OH 0 C H2 OHHe 0 C HOHHe Establishing the nature of the adsorbed species
x xx
0 C OHHe 0 C OHe  
xxx x cules is a difficult task. The issue was approached in a
where x stands for a Pt site [6]. It was suggested that
formaldehyde and formic acid could be formed from the
intermediates CH2OH and CHOH, respectively [6].
If a cyclic voltammogram is started after contacting a
polycrystalline Pt electrode with a methanol containing
solution at a potential of 0.05 V or less, methanol
adsorption can be observed as soon as hydrogen cover-
age decreases to a certain extent. The dissociation
process gives rise to a current peak in the H-region
(Fig. 1), which can be observed only during the first
potential scan, i.e. when the surface is free from organic
residues. The experiment in this figure was performed
using the DEMS technique [11]. Briefly, in this techni-
que the electrode is a porous Pt layer on a PTFE
membrane, lying on a porous plate at the entrance of a
mass spectrometer. This setup allows the entrance of
any volatile product in the MS in fractions of a second
after being produced. During the experiment in Fig. 1,
the recording of mass signals did not show any volatile
product from methanol oxidation. As an example, the
Fig. 1. First potential scan for a porous polycrystalline Pt electrode in
0.1 M CH3OH/0.05 M H2SO4 solution (upper part) and simulta-
neouly recording of mass intensity for CO2 production (lower part); 10
mV s 1. Dashed lines: current and MS signals in supporting
electrolyte.
recording of mass (m /e/44) corresponding to CO2 is
given. Thus the current peak can only be due to
Faradaic processes occurring during methanol adsorp-
tion.
3. The nature of the adsorbed methanol species
formed during the adsorption of small organic mole-
number of studies over many years [10]. Except from a
study using gas chromatography [5] earlier papers were
mainly based in data of charge measurements during
adsorption of methanol and oxidation of the adsorbed
residue [2,4,12]. The use of analytical methods for the in
situ, ex situ and on line analysis of the electrode surface
began in the decade of 1980 [7]. Different adsorbed
species were suggested on the basis of data from infrared
spectroscopy [13,14], thermal-desorption MS [15] and
DEMS [7].
Infrared spectra obtained during methanol adsorption
at 0.35 V on polycrystalline Pt show well characterized
bands for linearly adsorbed CO at approximately 2040
cm 1 together with other bands in the 1200
/1300 cm 1
region, which have been interpreted in terms of the C /
OH stretching of an hydrogenated species (as, e.g. COH
[14] or HCOH). These bands were also observed in
spectra obtained on single crystal Pt(100) and Pt(111)
(see below).
Another approach to establish the nature of the
adsorbate was made by thermal desorption mass
spectrometry, performed on electrodes transferred into
UHV [15]. These results also confirmed the presence of
hydrogenated species after adsorption of methanol.
Moreover, these data have shown that the ratio between
the amount of CO and (hydrogenated) species depends
on methanol concentration [15]. It should be noticed
that large discrepancies of results among different
groups may lie, at least in part, in the experimental
approaches. The necessity of thoroughly eliminating
traces of oxygen from the solution and from the gas
atmosphere above the solution must be emphasized,
since adsorbed oxygen can interact with organic resi-
dues. Recall that O2 reduction on a Pt surface produces
adsorbed peroxide species, which can act as an oxidizing
agent for species present at the surface. Other sources of
discrepancies may originate in the fact that the reaction
is surface sensitive and, consequently, results for poly-
crystalline Pt may depend on the method of surface
pretreatment, electrode roughness and the time scale of
the experiments, since adsorbed species can undergo
slow transformations.
 T. Iwasita / Electrochimica Acta 47 (2002) 3663
/3674
4. Methanol oxidation products
The oxidation products of CH3OH are well known
since early works of Pavela [16] and Schlatter [17]. These
authors used long-term electrolysis at potentials between
0.5 and 0.6 V versus RHE and found CO2, HCHO,
HCOOH and HCOOCH3. The latter product, methyl
formate, originates in a reaction:
HCOOH CH3 OH HCOOCH3 H2 O
The yields of oxidation products depend on methanol
concentration, temperature, electrode roughness and
time of electrolysis [18,19].
The study of the products of methanol oxidation
during a potential scan was the first goal of on-line mass
spectrometry, DEMS [20]. In Fig. 2, the potentiody-
namic formation of CO2 and methyl formate on a Pt
electrode was followed during the potential scan by
recording the corresponding ion currents in the MS: (m /
e /44) and (m /e /60), respectively. No mass signals for
HCHO were observed, but a weak ion current for
methylal (CH2(OCH3)2), indicated its formation via
reaction of HCHO with CH3OH [7]. However, there
must be some problem with the volatility of formalde-
hyde or its hydration product in aqueous solution (gem
diol, CH2(OH)2), which makes somehow difficult its
direct detection using the DEMS technique [21]. These
difficulties extend to other modern analytical methods
like in situ FTIR as pointed out by Korzeniewski and
Fig. 2. DEMS experiment: current and mass signals (ion current) for
volatile products during methanol oxidation at porous polycrystalline
Pt, surface roughness: ca. 50; 0.1 M CH3OH/1 M HClO4; 20 mV s 1.
[7].
3665
Childers [22]. This could be the reason why formalde-
hyde remained almost disregarded in the methanol fuel
cell literature. Korzeniewski and Childers determined
formaldehyde yields fluorometrically after applying
different constant potentials on a smooth polycrystalline
Pt electrode, during 5 min in a micro cell. They report
for formaldehyde a yield of 38% under following
conditions: 0.25 V versus Ag/AgCl (ca. 0.48 V vs.
RHE), 15 mM CH3OH/0.1 M HClO4. The yield
decays at higher potentials [22]. On porous Pt electrodes,
Wang et al. found at 0.65 V versus RHE 50% of HCHO,
34% of HCOOH and only 16% of CO2. It is worth
noting that Ota et al. also found relatively high yields of
HCHO on platinized Pt electrodes at 0.6 V versus RHE
[19].
5. Structural dependence of methanol oxidation
5.1. Results of cyclic voltammetry
As shown by the cyclic voltammograms in Fig. 3 for
the three low index surfaces of platinum, adsorption and
oxidation of methanol present a strong sensitivity to the
surface structure [23]. The Pt surfaces in these experi-
ments were contacted with methanol at 0.05 V (a
potential where methanol adsorption is negligible) and
then the first potential sweep was recorded. From the
three surfaces, Pt(100) is the only one presenting a well
defined current peak at 0.35 V for methanol dissociative
adsorption. This process is superimposed on the current
for H-desorption (compare with Fig. 1). Almost no
activity towards methanol oxidation is observed until
the potential reaches approximately 0.72 V. Contrasting
with this result, no indication of dissociative adsorption
of methanol parallel to hydrogen desorption is observed
at Pt(111). On the other hand, at Pt(110) the lowering of
current in the H region may indicate that the methanol
adsorption begins already at the initial potential of the
voltammogram (0.05 V). This behavior is expected from
the low potential for H desorption in this surface. For a
comparison, the first part of the potential scan is
magnified in Fig. 4. Here, one sees that a CV for
Pt(111) shows up the highest oxidation current in the
potential range between 0.45 and 0.65 V, followed by
Pt(110) and Pt(100). However, before establishing a
ranking for the activity of the three surfaces, infrared
results should be taken into consideration, as we shall
do in the coming section.
5.2. Results of infrared spectroscopy
Infrared spectra during methanol adsorption and
oxidation are shown in Fig. 5, for Pt(111), Pt(100) and
Pt(110) [23]. Bands at approximately 2060 and 1850
cm 1 are assigned to linearly (COL) and bridge (COB)
3666 T. Iwasita / Electrochimica Acta 47 (2002) 3663
/3674
Fig. 3. First potential scan for methanol oxidation on Pt(hkl ); 1.0 M
CH3OH in 1.0 M HClO4; sweep rate: 50 mV s 1 [21].
bonded CO, respectively. The band at 1260 cm 1 was
assigned to some H containing intermediate, possibly
COH [14]. Other H-containing adsorbate may be
responsible for the feature at 2950 cm1 in the spectra
for Pt(100). This band, which can be assigned to the C /
H stretching of a CH2 group appears already at 0.2 V
and becomes better defined at more positive potentials.
All spectra exhibit a band at 2341 cm 1, due to the
oxidation product CO2. Although not shown here, a
weak band at 1230 cm 1 has been observed on Pt(111)
at potentials above 0.45 V, which was assigned to the
C /O /C stretching of methyl formate [23].
Surface sensitive effects become more evident when
analyzing the integrated band intensities for CO and
CO2 for all three surfaces shown in Fig. 6a and b. In
comparing these results with those of the cyclic voltam-
mograms, one has to be aware that the time scale for the
spectra is much larger than for the CV. Thus, the
voltammetric curves in Fig. 4 were taken at 50 mV s 1,
i.e. 0.02 s mV 1). On the other hand, spectra collection
requires about 70 s at each potential and considerable
adsorption can take place during this time. The behavior
Fig. 4. Comparison of current for methanol oxidation on Pt(hkl ).
Conditions as in Fig. 3.
of Pt(111) and Pt(110) highlights some interesting
features of the mechanism of methanol oxidation. We
let at first Pt(100) out of consideration because of the
complication of presenting two forms of adsorbed CO
(on top and bridge), thus making it difficult to estimate
relative coverages on the basis of band intensities [24]. In
the case of Pt(111) the intensity of the band for COB is
so small that we shall simply neglect it in the following
discussion.
Measurable amounts of CO are observed at Pt(110)
already at 0.1 V. The CO signal rapidly grows with
potential and reaches a maximum at around 0.3 V. At
Pt(111), the initial adsorption can be extrapolated to
around 0.2 V, judging from the band for linear bonded
CO. This feature grows somewhat slower than that for
Pt(110). Also, a weak band for bridge bonded carbon
monoxide is apparent at potentials above 0.35 V. But
the most important observation here, is that the
dissociative adsorption of methanol at Pt(111) takes
place at potentials within the H region. Therefore we
can conclude that the lack of methanol adsorption in the
H-region during the potential scan at 50 mV s 1 (Fig. 3)
is due to a kinetic limitation of the adsorption process at
Pt(111) which is not observed on the other two surfaces.
In Fig. 6b is presented the integrated band intensity
for the CO2 observed in the potential region below 0.8
V. We can state that in this region CO2 production
proceeds with almost the same intensity at both Pt(111)
and Pt(110) and is much lower at Pt(100). Both former
surfaces have almost the same catalytic activity for CO2
production, at least at potentials below approximately
0.7
/0.75 V. However, the relative oxidation currents
 T. Iwasita / Electrochimica Acta 47 (2002) 3663
/3674
Fig. 5. Infrared spectra in 1.0 M CH3OH in 0.1 M HClO4 at Pt(100), Pt(111) and Pt(110). Reference spectra collected at 50 mV; sample spectra
collected at the indicated potentials [21].
observed in the voltammograms of Fig. 4 for Pt(110)
and Pt(111) indicate a higher activity of the latter
towards methanol oxidation. We can thus conclude,
that in the interval of potentials between, say, 0.4 and
0.6 V, the potenciodynamic current at Pt(111), origi-
nates to a large extent from the dissociative adsorption
of methanol and/or from the parallel pathway men-
tioned in the Introduction, ending in other products
than CO2. Our present knowledge of the yields of
HCOOH and/or HCHO at single-crystal electrodes is
insufficient for establishing the extent to which these
parallel pathways contribute to the current. Also Pt(100)
presents evidences for high yields of other products via a
parallel reaction: the pronounced increase of current at
0.7 V (Fig. 4), contrasts with the moderate variation of
the CO2 band intensity in Fig. 6b.
6. On the mechanism of methanol oxidation
The mechanism of methanol oxidation is an issue
which can be considered to be at its very beginning. The
3667
slow progress along many years can be easily under-
stood in the light of the difficulties created by the
existence of parallel reaction paths with yields depend-
ing on potential, time, surface structure, etc. At present,
only two global processes are distinguishable as already
said in the Introduction namely, adsorption of methanol
molecules and oxidation of adsorbed residues. Analizing
the IR results presented above it is possible to follow the
pathway leading to CO2 via formation of adsorbed CO
and to identify for this pathway, whether adsorption of
methanol or removal of CO is the rate determining
process.
Due to the fact that the interface components of the
respective Pt surfaces depend on potential and admitting
the necessity of oxygen donor species at the surface, for
oxidation of the adsorbed residues, discussing the total
oxidation is only meaningful at potentials above 0.4 V
or higher. However, what the adsorption process con-
cerns, we should start the discussion by considering the
methanol adsorption at potentials below 0.4 V. It is well
known that methanol cannot displace adsorbed hydro-
gen from the Pt surface. This is a well known phenom-
3668 T. Iwasita / Electrochimica Acta 47 (2002) 3663
/3674
Fig. 6. Integrated band intensities from IR spectra at Pt(111) and
Pt(100) and Pt(110) in 1.0 M CH3OH in 0.1 M HClO4. (a) Linear
(COL) and bridge (COB) bonded carbon monoxide; (b) carbon dioxide.
enon and is now documented by the data in Fig. 6a,
where the structure and potential dependence of metha-
nol adsorption can be analyzed from the band intensity
for adsorbed CO.
The above data were obtained by applying potential
steps of approximately 70 s of duration, i.e. they are
neither stationary nor dynamic, but since the procedure
for collecting spectra was the same for all surfaces, it
should be valid to compare with the band intensities in
order to have an idea of the rate of methanol adsorption
in the low potential region. Thus, it can be stated that
adsorption of methanol occurs at a higher rate at
Pt(110) than at Pt(111) (Fig. 6a). While COL coverage
at Pt(110) rapidly increases reaching a saturation value
between 0.3 and 0.4 V, the band for COL at Pt(111)
grows more slowly and does not present a real max-
imum but a sudden falling of intensity at a potential of
0.6 V. Additionally, in the whole range of potentials the
CO band intensity is substantially higher on Pt(110)
than on Pt(111). More about the methanol adsorption
process can be learnt by analyzing in parallel the band
intensity for CO in Fig. 6a and the hydrogen coverage
according to the voltammograms of these surfaces
measured in HClO4 (Fig. 7). Thus, e.g. for Pt(110) at
0.2 V, uH /0.2 and the band intensity for CO is large
(about 80% of its maximum value). On the other hand,
for the same uH at Pt(111), (E /0.29 V), the band
intensity is much lower. In fact, it grows slowly even
beyond 0.4 V, where the surface is totally free from
adsorbed hydrogen. It can thus be stated that the
differences in methanol adsorption rate for these two
surfaces originates in some property inherent to the
surface itself and not in the availability of H-free sites:
adsorption of methanol is intrinsically a slow process at
Pt(111).
We proceed now to discuss the potential region above
0.4 V, where CO2 is produced. Considering that
independent of the respective CO coverage, the rate of
CO2 formation is the same for both surfaces, we can
state that the reaction rate for CO2 formation is the
same for both surfaces Pt(111) and Pt(110). The most
simple interpretation of this result is that the oxidation
of the adsorbed residue is the rate determining process.
Or, with other words, at all potentials above 0.4 V, there
is enough adsorbed methanol on both surfaces as to
reach the maximum rate of oxidation at the respective
potential. Also Gasteiger et al. [25] suggested that
oxidative removal of CO is the rds in this potential
region. Following a somewhat different approach,
Christensen et al. [26] arrived to the same conclusion
for polycrystalline Pt. Summarizing, oxidation of ad-
sorbed CO and not adsorption of methanol is likely to
be the rate determining process in the potential region
between, say 0.5 and 0.70 V.
It has been shown that interaction of water with the
Pt surface increases as the potential is made more
positive [27] and competition of methanol with water
for adsorption sites becomes important. Therefore, at
high potentials (above, say, 0.7 V) methanol adsorption
becomes again rds [28] and for this reason the reaction
rate passes through a maximum and then decays.
For the pathway analyzed here, leading to CO2
formation via adsorbed CO, we can state that CO is
Fig. 7. Potentiodynamic current
/potential response for between 0.05
and 0.5 V vs. RHE for Pt(111) and Pt(100) in 0.1 M HClO4; sweep rate
50 mV s 1.
 T. Iwasita / Electrochimica Acta 47 (2002) 3663
/3674
an intermediate of the reaction and the role of surface
poison usually ascribed to COad should be revised.
Inspection of Fig. 6 indicates that CO indeed accumu-
lates on the surface at low potentials (see the result for
Pt(110)), however, the reason for the lack of CO2
formation lies in the inability of Pt to dissociate water
and not in the degree of surface blocking by CO.
Otherwise it would be difficult to understand that two
surfaces covered with CO to different extent produce
CO2 at identical rates.
Concerning the nature of the oxygen donor, it was
originally suggested by Gilman that it is an adsorbed
OH species coming from water dissociation [29]. But,
according to Wieckowski et al. [30] the oxygen donor is
simply some activated water molecule adsorbed on the
Pt surface. For oxidative stripping of CO adlayers on
platinum, Koper et al. [31] have shown that the
dissociation of water is a necessary step in order to
harmonize experimental data with results of Monte
Carlo simulations. Although the real nature of the
oxygen donor for the oxidation of COad was not
demonstrated via spectroscopic methods, we are in-
clined to accept the more or less general consensus that
it is OHad formed through the dissociation of water.
6.1. Supporting electrolyte effects on the rate of methanol
oxidation
Perchloric and sulfuric acids are the commonly used
supporting electrolytes for studies of methanol electro-
oxidation. It is, however noteworthy, that methanol
oxidation can be affected by the anion of the supporting
electrolyte used. This is clearly the case for Pt(111) and
Pt(100) electrodes, where cyclic voltammograms of
methanol exhibits much larger currents in HClO4 than
in H2SO4 [32,33]. The difference was justified by the
specific adsorption of sulfate species at Pt electrodes,
which partially hinder methanol oxidation. Kita et al.
[32] observed for Pt(111) a factor of ten higher current in
HClO4 than in H2SO4, while for Pt(100) the enhance-
ment factor was about two. The different behavior can
be rationalized in terms of a stronger specific anion
adsorption at Pt(111) than at Pt(100) [34]. No difference
between HClO4 and H2SO4, was observed at Pt(110)
[32].
7. Catalyst promoters for methanol oxidation
Several binary and ternary catalysts were proposed
for methanol oxidation, most of them based in mod-
ifications of Pt with some other metal. This metal must
fulfill the requirement of forming O-containing surface
species at low potentials. Among others, Sn, Re, Ru, Ge
and Mo, were suggested [7,25,35
/54]. There are, of
course, several practical factors limiting the choice of the
3669
metal. Many O-adsorbing metals can produce negative
effects, e.g. inhibit methanol adsorption or may be not
sufficiently stable for long-term use, as required for a
fuel cell. At present, there is a general consensus that
PtRu offers the most promising results. Methanol
oxidation on PtRu binary catalysts has been the matter
of a number of papers [25,35
/54]. The catalytic effect
has been observed using different kinds of PtRu
materials, such as PtRu alloys, PtRu electrodeposits,
Ru evaporated on Pt, Ru adsorbed on single-crystal
Pt(hkl ), etc. and on technical (carbon supported electro-
des) as well [54,55].
When discussing the reason for the catalytic effect of
PtRu, the bi-functional mechanism is often invoked [41].
The term was suggested to give emphasis on the joint
activities of both metals, Pt being the one adsorbing and
dissociating methanol and Ru, the one oxidizing the
adsorbed residues at low potentials. This description of
the mechanism is based in the observation that at
potentials below 0.4 V, Pt is a good catalyst for
methanol adsorption, but not for water dissociation
while Ru is able to dissociate water but it cannot adsorb
methanol. However, establishing a role for each metal as
in the bi-functional mechanism is of limited use, since it
is well known that at high potentials Pt dissociates water
and, as shown in refs. [43,53] at high temperatures (60,
80 8C) Ru adsorbs methanol. Moreover, even for
conditions where methanol adsorption occurs only on
Pt, CO can move on the surface and occupy sites on Ru
atoms. Altogether, several adsorbed species could be
involved in the oxidation process at the PtRu catalyst,
namely, Pt(CO)ad, Ru(CO)ad, Ru(OH)ad and Pt(OH)ad.
In a simplified manner, we shall describe the bi-
functional mechanism as follows [25].
The first step of the reaction is adsorption of
methanol:
CH3 OH(sol) 0 (CO)ad 4 H 4 e (1)
(CO)ad represents an adsorbed CO species either on Pt
or on Ru. Then, both Pt and Ru dissociate water to
form adsorbed OH:
RuH2 O 0 (OH)ad H e (2)
PtH2 O 0 (OH)ad H e (3)
Finally, following a Langmuir
/Hinschelwood me-
chanism adsorbed CO reacts with adsorbed OH to
give CO2:
(CO)ad (OH)ad 0 CO2 H e (4)
For CO adlayers obtained via adsorption of dissolved
CO on PtRu, Koper et al. [56] analyzed reaction (4) for
all possible species mentioned above and found that an
enhanced effect is only possible if the final oxidation
step occurs between CO adsorbed at Pt and OH
adsorbed at Ru. Therefore, reaction (4) can be specifi-
cally written as
3670 T. Iwasita / Electrochimica Acta 47 (2002) 3663
/3674

Pt(CO)ad  Ru(OH)ad 0 CO2 H e (5)

Moreover, as a necessary condition for the

Langmuir
/Hinschelwood mechanism, CO must diffuse
on the surface to the places where the OHad partner is
formed. Koper et al. [56] suggested that the relative rate
of CO diffusion on the surface must be high.
Besides the promoter effect of Ru through reaction
(5), there are experimental evidences of additional
effects of Ru on the reaction. Thus, the potentiodynamic
curves (first sweep) of Fig. 8, obtained at PtRu electro-
deposits in the course of DEMS experiments, show a
negative shift of the dissociative adsorption of methanol
depending on the Ru content of the electrodes. Further
evidence of the earlier adsorption was obtained via
infrared spectroscopy as shown in Section 5.1.
The catalytic effect of PtRu materials is usually
presented in the form of current
/time plots at constant
potential, as observed in Fig. 9, [46,50,51]. Similar
responses have been reported by other authors under
comparable conditions [43,47]. In order to measure the
data represented in this plot Pt(111)/Ru electrodes were
prepared by adsorption of Ru onto Pt(111) [46] and
alloys were cleaned by sputtering and heating in UHV
following the pre-treatment technique suggested by
Gasteiger et al. [56]. This is a reliable method for
producing smooth surfaces of identical composition as Fig. 9. Current
/time curves for comparing the catalytic activity of
the bulk. The quality of having a low roughness factor Pt(111) and PtRu alloys, towards methanol oxidation in 0.5 M
can be easily checked via comparison of the current in CH3OH/0.1 M HClO4. Potential 0.5 V vs. RHE. Room temperature,
voltammograms in base electrolyte measured with the electrodes surfaces cleaned in UHV.
alloy with those obtained using Pt(111)/Ru electrodes
[46].
As observed in Fig. 9, when smooth PtRu materials
are polarized at constant potential in methanol solu-
tions, the current decays continuously indicating a
pronounced loss in activity. The current does not reach
a stationary state even after several hours. Two different
origins of this effect causing electrode deactivation have
been identified. One of these is reversible and seems to

Fig. 8. First potential scan in 1.0 M CH3OH/0.5 M H2SO4, starting
at 50 mV (RHE); scan rate 1 mV s 1. Porous electrodes prepared by
depositing Pt and Ru at 0.2 V vs. RHE up to a total charge of 1200
mC, from solutions containing x mM RuCl3 and y mM H2Cl6 Pt in
0.5 M H2SO4. The x /y ratios are indicated in each curve.
Fig. 10. Plot of the current density for methanol oxidation as function
of Ru coverage, taken from current
/time curves at 0.5 V as in Fig. 9.
Data for UHV prepared PtRu alloys, measured after 20 min; data for
Pt(111)/Ru formed by spontaneous adsorption, measured after 5 min.
Solutions: 0.5 M H2SO4/0.5 M CH3OH (data form ref. [43]), 0.5 M
CH3OH/0.1 M HClO4 [46].
 T. Iwasita / Electrochimica Acta 47 (2002) 3663
/3674 3671

active as oxygen donors for CO oxidation. The electrode

Fig. 11. Current densities for methanol oxidation at 0.4 V in 0.5 M
CH3OH/0.5 M H2SO4 vs. Ru surface composition of sputter cleaned
Pt /Ru alloys. Electrode immersion at 0.075 V for 3 min prior to
stepping to the indicated potential. Dashed lines are arbitrarily drawn
smooth curves to connect the experimental data points. Data from ref.
[43], published with permission.
be caused by the oxidation of the Ru surface [50,51],
forming oxides like RuO2 and RuO3, which are not
activity is thus partially recovered by applying a
potential step towards more negative values, where the
ruthenium oxide species are reduced. The other factor
causing the decay of current is, apparently, a blockage
of the surface by some organic residue, which is slowly
formed and can only be oxidized at high anodic
potentials. No spectroscopic proofs are yet available
on the nature of such blocking species.
The results of i
/t curves obtained at room tempera-
ture for the two types of materials (alloys and Pt(111)/
Ru) are collected in Fig. 10, where the current after 20
min of polarization at 0.5 V versus RHE is plotted as a
function of the Ru:Pt surface composition. It is note-
worthy that in spite of the fact that the data for the
alloys in this figure were measured in two different
laboratories [43,46], they nicely fit together. Also,
methanol oxidation at PtRu alloys seems not to be the
same for both supporting electrolytes H2SO4 and HClO4

Fig. 12. Comparison of in situ FTIR spectra for Pt(111), Pt(111)/Ru 39% and PtRu alloy (85:15) in 0.5 M CH3OH/0.1 M HClO4. Potentials as
indicated on each spectrum; reference spectrum taken at 0.05 V (from [46] with added spectra at 0.55 V).
3672 T. Iwasita / Electrochimica Acta 47 (2002) 3663
/3674

used. Two main points can be extracted from this plot:

(i) PtRu alloys are better catalysts than Pt(111)/Ru, and
(ii) both materials present a wide maximum (between ca.
10 and 40% Ru for the alloys and ca. 15 and 50% for the
Pt(111)/Ru electrodes) at room temperature.
In terms of the bi-functional mechanism, these max-
ima indicate that a Ru percentage of approximately 10
/
45% on the surface is enough to provide an efficient
oxidation of adsorbed methanol residues. Within this
range one has a possibility of studying the influence on
the reaction of other parameters (like e.g. methanol
concentration) and possibly, the kinetic of the reaction.
The upper limit of Ru coverage, is given by the necessity
of having enough Pt sites for adsorbing and dissociating
methanol. This limit is somewhat higher for adsorbed
Ru than for the alloy (observe the wider maximum).
This and the higher currents observed on the alloys
may be related to the fact that the latter present a
more homogeneous distribution of Ru atoms than the
Pt(111)/Ru electrode [57]. STM data of Pt(111)/Ru show
that Ru tends to form aggregates (islands) on the surface
of Pt [46,58]. Thus, for the same Ru percentage, wider
Ru patches can be found on the Pt(111)/Ru surface than
on the alloy. It is noteworthy that the maximum of the
j
/uRu plot for the alloy is shifted to higher uRu values at Fig. 13. DEMS experiment on PtRu porous electrode in 1.0 M
CH3OH/0.5 M H2SO4; v : 20 mV s 1. Electrode prepared by
higher temperatures (Fig. 11) [43]. This effect probably
electrodepositing Pt and Ru during 7 min at 0.05 V, on a gold
originates from the fact that at higher temperatures (e.g. substrate. Solution composition: 10 mM RuCl3/10 mM H2Cl6Pt in
60 8C), Ru becomes active for adsorbing methanol and 0.5 M H2SO4 [45] published with permission.
oxidizing the residue (see the value of current for pure
Ru in Fig. 11). production and also a high CO coverage (near satura-
tion) at 80 8C.
It is noteworthy that, although no features for other
8. Spectroscopic results of methanol oxidation on PtRu intermediates or soluble products were observed under
materials the conditions for taking the spectra on the PtRu
materials shown in Fig. [12], DEMS experiments in 1.0
Infrared spectra using Pt(111), Pt(111)/Ru and a PtRu M CH3OH using PtRu electrodes do exhibit a potential
alloy [46] are presented in Fig. 12. PtRu alloy electrodes dependent mass signal for HCOOCH3 (Fig. 12) [45]. As
were UHV cleaned, as for the experiments of Fig. 9. The pointed out before, the yields of different products on a
bands observed on both Pt(111)Ru and PtRu (85:15) Pt electrode depend on several experimental parameters
alloy correspond to CO2 (2341 cm 1) and COL (2050 such as methanol concentration and electrode roughness
cm 1). At Pt(111) a band at approximately 1820 cm 1 [19]. This condition seems to extent to PtRu materials.
is due to bridge adsorbed (COB) (Fig. 13). So far, IR spectra on well prepared PtRu alloys in
The PtRu alloy electrode presents the highest produc- concentrated methanol solutions (above 0.5 M) have not
tion of CO2 at a given potential (note the differences in been published and the question on the parallel paths on
scale). It is also noteworthy, that although the CO2 band PtRu should be let open to further discussion.
markedly grows with potential and also the highest band
intensity for linear bonded CO. At PtRu the CO feature
remains approximately constant in the range of poten-
tials between 0.3 and 0.55 V, indicating that the 9. Concluding remarks
intermediate CO reaches a stationary coverage balan-
cing the rates of formation and oxidation. In the last years, considerable progress has been made
In a recent paper [53], methanol oxidation was studied in the knowledge of methanol electrooxidation reaction
on two PtRu alloys having 10 and 90% Ru, in the range and on its catalysis.
of temperatures between 25 and 80 8C. For the 90% Ru As for other small organic molecules, parallel path-
alloy, this study shows a negligible activity towards ways occur during methanol oxidation. In addition to
methanol oxidation at 25 8C but an appreciable CO2 CO2 which is the major product, formic acid (methyl
 T. Iwasita / Electrochimica Acta 47 (2002) 3663
/3674
formate) and formaldehyde are formed, their yields
depending on experimental conditions such as surface
roughness and methanol concentration and time of
electrolysis.
In spite of noticeable structural effects of the Pt
surface, which are reflected on the amount and rate of
surface coverage by CO, comparable ‘quasi-stationary’
rates of CO2 production are observed at Pt(111) and
Pt(110) in the potential region between approximately
0.4 and 0.75 V. This result indicates that the rate
determining process is more likely the oxidation of the
adsorbed species and not the adsorption of methanol.
At room temperature PtRu alloys having a Ru
content between 10 and 40% are, at present, the best
catalysts for the reaction. This is probably due to a good
distribution of Pt and Ru atoms as compared with other
materials where the atoms tend to segregate forming
patches of pure Ru or Pt, thus physically separating the
bi-functional partners. Experimental data show that in
addition to the bi-functional action of both metals, the
promoter effect of Ru may also lie in other effects, such
as lowering the potential for methanol adsorption.
Some deactivation effects are observed during polar-
ization at constant potential, the origin of these being
probably, the formation of inactive ruthenium oxides of
and blockage of the surface by organic residues of
unknown nature.
Acknowledgements
Financial support from FAPESP and CNPq, Brazil
and DFG, Germany, is gratefully acknowledged
References
[1] W. Vielstich, Fuel Cells, Wiley Interscience, Bristol, 1965.
[2] M.W. Breiter, Electrochemical Processes in Fuel Cells, Springer-
Verlag, Berlin, 1969.
[3] O.A. Petrii, B.I. Podlovchenko, A.N. Frumkin, H. Lal, J.
Electroanal. Chem. 10 (1965) 253.
[4] V.S. Bagotzki, Y. Vassileiv, Electrochim. Acta 12 (1967) 1323.
[5] M. Breiter, Electrochim. Acta 12 (1967) 1213.
[6] V.S. Bagotzki, Y.B. Vassiliev, O.A. Kazova, J. Electroanal.
Chem. 81 (1977) 229.
[7] T. Iwasita, in: H. Gerischer, C. Tobias (Eds.), Advances in
Electrochemical Science and Engineering, vol. 1, Verlag Chemie,
1990, p. 127.
[8] R. Parsons, T. Van der Not, Electroanal. Chem. 257 (1988) 1.
[9] S. Wasmus, A. Küver, J. Electroanal. Chem. 461 (1999) 14.
[10] A. Hamnett, in: A. Wieckowski (Ed.), Interfacial Electrochem-
istry. Theory, Experimental and Applications, Marcel Dekker,
New York, 1999, p. 843.
[11] B. Bittins-Cattaneo, E. Cataneo, P. Königshoven, W. Vielstich,
in: A.J. Bard (Ed.), Electroanalytical Chemistry a Series of
Advances, Marcel Dekker, 1991, p. 181.
[12] T. Biegler, J. Phys. Chem. 72 (1968) 1571.
3673
[13] B. Beden, C. Lamy, A. Bewick, K. Kunimatsu, J. Electroanal.
Chem. 121 (1981) 343.
[14] T. Iwasita, F.C. Nart, J. Electroanal. Chem. 317 (1991) 291.
[15] S. Wilhelm, T. Iwasita, W. Vielstich, J. Electroanal. Chem. 238
(1987) 383.
[16] T.O. Pavela, Ann. Acad. Sci. Fenn. Ser. K A2 (1954) 1.
[17] M.J. Schlachter, in: G.Y. Yong (Ed.), Fuel Cells, Reinhold, New
York, 1963, p. 199.
[18] M. Breiter, Disc. Faraday Soc. 45 (1968) 79.
[19] Y. Ota, M. Nakagawa, Takahashi, J. Electroanal. Chem. 179
(1984) 179.
[20] (a) O. Wolter, C. Giordano, J. Heitbaum, W. Vielstich, Proceed-
ings of Symposium on Electrocatalysis, The Electrochemical
Society, Pennington, 1982, p. 235;
(b) O. Wolter, J. Heitbaum, J. Electrochem. Soc. 132 (1985) 1635.
[21] H. Wang, T. Löffler, H. Baltruschat, J. Appl. Electrochem. 31
(2001) 759.
[22] C. Korzeniewski, C. Childers, J. Phys. Chem. B 102 (1998) 489.
[23] X.H. Xia, T. Iwasita, F. Ge, W. Vielstich, Electrochim. Acta 41
(1996) 711.
[24] I. Villegas, M.J. Weaver, J. Chem. Phys. 101 (1994) 1648.
[25] H. Gasteiger, N. Markovic, P.N. Ross, E.J. Cairns, J. Phys.
Chem. 97 (1993) 12020.
[26] P.A. Christensen, A. Hamnett, G.L. Troughton, J. Eletroanal.
Chem. 362 (1993) 207.
[27] X.H. Xia, T. Iwasita, J. Electroanal. Chem. 411 (1996) 95.
[28] T. Iwasita, X.H. Xia, H.-D. Liess, W. Vielstich, J. Phys. Chem. B
101 (1997) 7542.
[29] S. Gilman, J. Phys. Chem. 68 (1964) 70.
[30] H. Kim, I. Rabelo de Moraes, G. Tremiliosi-Filho, R. Haasch, A.
Wieckowski, Surf. Sci. 474 (2001) L203.
[31] M.T.M. Koper, A.P.J. Jansen, R.A. van Santen, J.J. Lukkiens,
P.A.J. Hibers, J. Chem. Phys. 109 (1998) 5061.
[32] H. Kita, Y. Gao, H. Hattori, J. Electroanal. Chem. 373 (1994)
177.
[33] N. Markovic, P.N. Ross, J. Electroanal. Chem. 330 (1992) 499.
[34] (a) F.C. Nart, T. Iwasita, M. Weber, Electrochim. Acta 39 (1994)
961;
(b) T. Iwasita, F.C. Nart, M. Weber, Electrochim. Acta 39 (1994)
2093.
[35] K.J. Cathro, J. Electrochem. Soc. 116 (1969) 1608.
[36] M.M.P. Jansen, J. Moolhuysen, J. Catal. 46 (1977) 289.
[37] O.A. Petrii, B.I. Podlovchenko, A.N. Frumkin, H. Lal, J.
Electroanal. Chem. 10 (1965) 253.
[38] H. Binder, A. Köhling, G. Sandstede, in: G. Sandstede (Ed.),
From Electrocatalysis to Fuel Cells, University of Washington,
Seatle, 1972.
[39] M. Watanabe, S. Motoo, J. Electroanal. Chem. 69 (1976) 429.
[40] T. Iwasita, F.C. Nart, W. Vielstich, Ber. Bunsenges Phys. Chem.
94 (1990) 1030.
[41] M. Watanabe, S. Motoo, J. Electroanal. Chem. 60 (1975) 267.
[42] N. Gasteiger, Markovic, P.N. Ross, Electrochim. Acta 41 (1996)
2587.
[43] H.A. Gasteiger, N. Markovic, P.N. Ross, E.J. Cairns, J. Electro-
chem. Soc. 141 (1994) 1795.
[44] N. Markovic, H.A. Gasteiger, P.N. Ross, L. Villegas, M.J.
Weaver, Electrochim. Acta 40 (1995) 91.
[45] M. Krausa, W. Vielstich, J. Electroanal. Chem. 379 (1994) 307.
[46] T. Iwasita, H. Hoster, A. John-Anacker, W.F. Lin, W. Vielstich,
Langmuir 16 (2000) 522.
[47] W. Chrzanowski, A. Wieckowski, Langmuir 14 (1998) 1967.
[48] W. Chrzanowski, W.H. Kim, A. Wieckowski, Catal. Lett. 50
(1998) 69.
[49] G. Tremiliosi-Filho, H. Kim, W. Chrzanowski, A. Wieckowski,
B. Grzybowska, P. Kulesza, J. Electroanal. Chem. 467 (1999) 143.
[50] H. Hoster, T. Iwasita, H. Baumgärtner, W. Vielstich, Phys. Chem.
Chem. Phys. 3 (2001) 337.
3674 T. Iwasita / Electrochimica Acta 47 (2002) 3663
/3674

[51] H. Hoster, T. Iwasita, H. Baumgärtner, W. Vielstich, J. Electro-
chem. Soc. 148 (2001) A496.
[52] A. Kabbaby, R. Faure, R. Durand, B. Beden, F. Hahn, J.-M. [55]
Leger, C. Lamy, J. Electroanal. Chem. 444 (1998) 41.
[53] D. Kardash, C. Korzeniewski, N. Markovic, J. Electroanal. [56]
Chem. 500 (2001) 518.
[54] W.H. Lizcano-Valbuena, E.C. Bortholin, A. Oliveira Neto, V.A. [57]
Paganin, E.R. González, 200th Meeting of the Electrochemical [58]
Society, 52nd ISE Meeting Ext. Abstract 330, San Francisco,
2001.
A.O. Neto, J. Peres, W.T. Naporn, E. Ticcianelli, E. González, J.
Braz. Chem. Soc. 11 (2000) 39.
M.T.M. Koper, J.J. Lukkien, A.P.J. Jansen, R.A. van Santen, J.
Phys. Chem. B 105 (1999) 5522.
H. Gasteiger, P.N. Ross, E.J. Cairns, Surf. Sci. 293 (1993) 67.
E. Herrero, J. Feliu, A. Wieckowski, Langmuir 15 (1999) 493.