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Oxygen reduction reaction on smooth single crystal electrodes

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Oxygen reduction reaction on smooth single crystal
electrodes
P. N. Ross Jr
Volume 2, Part 5, pp 465–480

in

Handbook of Fuel Cells – Fundamentals, Technology and Applications

(ISBN: 0-471-49926-9)

Edited by

Wolf Vielstich
Arnold Lamm
Hubert A. Gasteiger

 John Wiley & Sons, Ltd, Chichester, 2003

Chapter 31
Oxygen reduction reaction on smooth single crystal
electrodes
P. N. Ross Jr
University of California, Berkeley, CA, USA
1 INTRODUCTION
In spite of many attempts in the last decade by researchers
and fuel cell developers to create a nonPt catalyst for
low temperature (<200 ◦ C) air cathodes, Pt remains the
catalyst of choice at least for acid-based fuel cells. There-
fore, much of the art and science of catalyst develop-
ment for the oxygen reduction reaction (ORR) rely on
both the fundamental understanding of the reaction at
the Pt-electrolyte interface[1–4] and the optimization of
the catalytic properties of the Pt surface.[5, 6] In prin-
cipal, fundamental understanding can be used to create
tailormade surfaces with improved catalytic activity. The
optimization of the most promising catalysts must incor-
porate both noncatalytic and catalytic factors. Examples
of noncatalytic factors are partial replacement of nonsur-
face Pt atoms, i.e., ‘buried’ Pt atoms, with an inexpen-
sive metal, or the maximization of the Pt surface area
while exposing the most active microstructures. These fac-
tors will minimize the amount (and cost) of catalysts
required for a given level of activity. The most impor-
tant catalytic factor is the modification of the intrinsic
activity of Pt surface atoms, usually by making bimetal-
lic surfaces. The enhancement of catalytic properties by
the second metal may occur through the change of the
local bonding geometry (structure effects), the distribution
of active sites (ensemble effects) or directly by modify-
ing the reactivity of platinum surface atoms (electronic
Handbook of Fuel Cells – Fundamentals, Technology and Applications, Edited by Wolf Vielstich, Hubert A. Gasteiger, Arnold Lamm.
Volume 2: Electrocatalysis.  2003 John Wiley & Sons, Ltd. ISBN: 0-471-49926-9.
effects). In real systems, all of these factors will, in gen-
eral, operate simultaneously, and separating these effects
and assessing their relative importance in the catalytic
activity and reaction mechanism is a very challenging
problem.
The situation in alkaline electrolyte is rather different
from acid electrolyte. Here there are many opportunities for
nonPt catalysts for the ORR.[2, 3] Materials that have little
or no measurable activity for oxygen reduction in acid have
substantial, even commercially practical, levels of activity
in alkaline solution.[3] Although this fact has been known
for some time, the fundamental reason for this remarkable
pH effect has never been fully explained. I present here,
for the first time, a simple thermodynamic rationale based
on the energetics of the O2 /O2 − (superoxide radical anion)
redox couple.
In this chapter, I will summarize recent progress in
understanding the role of surface structure in the kinetics
of the ORR on well-defined metal surfaces in both acid
and alkaline electrolyte. In acid, the focus will be on the
low index Pt single crystals, and relationship between the
Pt surface structure on the kinetics of the ORR in order to
create a fundamental link between the specific activity of
Pt (rate per unit area) and the particle size (for various
nanoparticle shapes) of supported catalysts. In alkaline
electrolyte, the focus is on the low index single crystal
surfaces of Au in addition to Pt. Au is discussed as a
prototype electrode material for a nonPt catalyst with weak
adsorption of O2 − .
466 Part 5: The oxygen reduction/evolution reaction
2 OXYGEN REDUCTION REACTION
PATHWAY/MECHANISM
In order to discuss the structure sensitivity of the ORR on
metal surfaces and to attribute effects to specific surface
chemistry, it is convenient to formulate the discussion in
terms of a reaction pathway/mechanism. Oxygen reduction
reaction is a multi-electron reaction that may include a
number of elementary steps involving different reaction
intermediates. In his excellent recent review, Adzic[3] has
summarized the many proposed paths and intermediates
and discussed their merits and deficiencies with respect to
various electrode materials and the available experimental
data. For the purpose here of discussing the reaction on
different metals at different pH in a common framework, a
more generalized and simplified scheme is more useful than
the more complex schemes discussed by Adzic. The overall
scheme valid for both acid and base and all the electrode
materials discussed here is the following:
k1
k2 k3
O2 O2, ad H2O2, ad H2O
k4
k5
H2O2
Based on this reaction scheme, O2 can be electrochemi-
cally reduced either directly to water with the rate constant
k1 without intermediate formation of H2 O2,ad (so-called
‘direct’ 4e− reduction) or to H2 O2,ad with the rate con-
stant k2 (‘series’ 2e− reduction). The adsorbed peroxide
can be electrochemically reduced to water with the rate
constant k3 (‘series’ 4e− pathway), catalytically (chemi-
cally) decomposed on the electrode surface (k4 ) or desorbed
into the bulk of the solution (k5 ). The direct 4e− reduc-
tion requires dissociation of oxygen prior to the transfer
of the first electron.[7] The dissociation energy of O2 is
quite large (498.3 kJ mol−1 ), meaning that dissociation is
energetically unfavorable unless the M–O bond is very
strong, e.g., >250 kJ mol−1 . Metals with very strong M–O
bond strengths have poor activity for the ORR[5] because
the reaction stops with the formation of surface OH, i.e.,
reaction becomes desorption rate limiting. The more ener-
getically favored path is the superoxo/peroxo path, with
transfer of the electron to the oxygen molecule. The dis-
sociation energy of O2 − and/or O2 2− is much lower than
that of O2 (by 98.7 kJ mol−1[8] ), resulting in a more facile
reaction path without a strong M–O bond.
In recent studies on Pt surfaces from our laboratory,[9–11]
we have interpreted the results assuming the series pathway
via an (H2 O2 )ad intermediate, and I will use that pathway
for the discussion here. The surface peroxide intermediate
may or may not be further reduced to water depending on
the relative values of k4 and k5 . In either case, the rate-
determining step appears to be the addition of the first
electron to O2,ad to form the adsorbed superoxide radical
anion, žO2,ad −
O2,ad + e− −−−→ žO2,ad − (1)
The rate expression is then,[2, 12]
i = nF KcO2 (1 −
ad )x exp(−βF E/RT )
× exp(−γr
ad )/RT (2)
where n is the number of electrons, K is the chemical
rate constant, cO2 is the concentration of O2 in the solu-
tion,
ad is the total surface coverage by all adsorbed
species, x is either 1 or 2 depending on the site require-
ments of the adsorbates, i is the observed current, E is
the applied potential, β and γ are the symmetry factors
(assumed to be 1/2) and r (the so-called Frumkin or Temkin
parameter) is a parameter characterizing the rate of change
of the free energy of adsorption of the rate-determining
intermediate with the surface coverage by (all) adsorbing
species. Assuming that the coverage of ORR intermediates
is low under reaction conditions,[12] for most cases only two
adsorbed species need to be considered, OHad and specif-
ically adsorbing anions like (bi)sulfate or halides. In the
following sections, we will use this reaction pathway and
rate expression to analyze the effects of various factors on
the kinetics of the ORR on Pt(hkl) surfaces.
One particular limiting case is of special interest, that
where the free energy of adsorption of the rate-determining
intermediate, žO2,ad − , is unaffected by the co-adsorption
of the spectator anions like (bi)sulfate or halides, r = 0.
Under this assumption, the second exponential term is a
potential independent constant and the so-called Tafel slope,
(∂ log i/∂E)−1 , is −2 × 2.3 RT /F mV/decade of current.
3 ORR AT Pt(hkl) SURFACES IN ACIDIC
ELECTROLYTE
Interest in the role of the local symmetry of Pt surface atoms
in electrocatalysis has risen steadily over the last three
decades. Ever since the pioneering work of Will,[13] one
of the major themes in electrochemical research has been
the study of the relationship between the electrochemical
reactivity and surface structure, a functionality generally
termed ‘structural sensitivity’.[4] The recent advance in the
in-situ methods of surface X-ray scattering (SXS)[14] and
 Oxygen reduction reaction on smooth single crystal electrodes 467

scanning tunneling microscopy (STM)[15] have made it

100
possible to establish the true surface structure of Pt single
25 °C

Ir (µA)
crystal surfaces in electrolyte as a function of potential. 50
This advance enables one to determine with confidence the
true relationship between the kinetics of electrochemical 0.0
reactions and structure of the surface.[4]
It is now well established that the structure sensitivity of
the ORR on Pt(hkl) surfaces depends critically on the nature 0.5

Id (mA)
of the supporting electrolyte. Within the limited scope of
this report, it will not be possible to review all of these
1.0
results. Rather I will show, using representative examples,
the kind of information that can be used to improve our
understanding of the role of the symmetry of Pt surface 1.5
atoms in the O2 reduction reaction. The most outstanding 100
conclusions from this body of work is: (i) that the structural Pt(111)

Ir (mA)
Pt(100) 60 °C
sensitivity is dramatically affected by the adsorption of 50
anions from the supporting electrolyte, e.g., HSO4(ad) , Clad , Pt(110)
and Brad , and (ii) that the structure sensitivity in the solution 0.0
containing bisulfate or halide anion is determined entirely
by the (1–
ad ) coverage dependent pre-exponential term.
0.5
Two representative sets of polarization curves for Pt(hkl)
Id (mA)

in 0.05 M H2 SO4 (pH = 1) are shown in Figure 1 for two

different temperatures. The polarization curves clearly show
that the ORR in H2 SO4 increases in the sequence Pt(111) <
Pt(100) < Pt(111). An exceptionally large deactivation is
observed at the Pt(111) surface. A full description of the
polarization curves for the ORR on Pt(111) in pure sulfuric
acid solution is given in our previous publications.[10, 16]
The exceptionally large deactivation is due the strong
adsorption of the (bi)sulfate anion from the symmetry match
between the fcc (111) face (see insert of Figure 1) and the
C3v geometry of the oxygen atoms of the sulfate anion.[17]
The fact that the activity of all three low-index platinum
planes is significantly higher in HClO4 [4] does, however,
suggest that adsorption of (bi)sulfate anions affects the
kinetics of the ORR on all three surfaces, but is particularly
strong on Pt(111). It should be noted that, although bisul-
fate adsorption onto Pt(hkl) surfaces inhibits the reduction
of molecular O2 , most likely by blocking the initial adsorp-
tion of O2 , it does not affect the pathway of the reaction,
since no H2 O2 is detected on the ring electrode for any of
the surfaces in the kinetically controlled potential region.
Tafel plots of the mass-transfer corrected kinetic currents
showed[10] that the Tafel slope has the ‘ideally’ temper-
ature dependent value of −2 × 2.3 (RT /F ) on all three
surfaces. The activation energy was also independent of
crystal face, having the value of 42 kJ mol−1 (extrapolated
to the reversible potential). Since the energetic terms in the
rate expression (2) are all independent of crystal face, the
structure sensitivity of the ORR in sulfuric acid must arise
entirely from the pre-exponential term, (1 −
ad ), i.e., a
purely site-blocking effect of the adsorbed (bi)sulfate anion.
1.0
1.5
0.0 0.2 0.4 0.6 0.8 1.0
E (V)
Figure 1. (a) Oxygen reduction on Pt(hkl) in 0.05 M H2 SO4
at 298 K (20 mV s−1 , 900 rpm); lower part, disk currents; upper
part, ring currents. (b) Oxygen reduction on Pt(hkl) at 333 K
250 mV s−1 , 900 rpm): lower part, disk currents; upper part, ring
currents. (From Ref. [10].)
The family of polarization curves for the ORR on Pt(hkl)
in 0.05 M H2 SO4 + 10−3 M Cl− are shown in Figure 2.
The polarization curves for the ORR in pure 0.05 M H2 SO4
solutions is shown for one rotation rate as a reference. In
the presence of Cl− , the catalytic activity increases in the
order (100) < (110) < (111).[9] Figure 2a shows that the
ORR on the Pt(111) surface in 0.05 M H2 SO4 + 10−3 M
Cl− is strongly inhibited, with an activity in a solution
containing Cl− being orders of magnitude lower than in
0.1 M HClO4 ,[4, 9] and about the same inhibition as in Cl−
free 0.05 M H2 SO4 . If one were to examine just the ORR
polarization curve alone, one might conclude that the (111)
surface is hardly affected by the presence of Cl− in solution
due to the already strong adsorption of (bi)sulfate. But in
fact the base voltammetry in O2 free electrolyte makes it
clear that Cl− displaces (bi)sulfate anions entirely from the
surface throughout the potential region shown.[18] Unlike
Pt(111), the ORR on Pt(110) (Figure 2b) and Pt(100)
468 Part 5: The oxygen reduction/evolution reaction

2Ir /N
xH2 O2 = (3)
Id + Ir /N
50
Ir (µA)

is almost constant and is close to 25% (note in this relation,

0
N denotes the collection efficiency of the ring-disk configu-
ration, Id and Ir are the disk and ring currents, respectively).
Id (mA cm−2)

−2
At potentials below 0.3 V, the surface coverage with Clad is
−4 reduced substantially, but the O2 reduction currents sharply
−6
Pt(111) decrease to diffusion limiting currents for ca. 2e− per O2
molecule at the negative potential limit. In the same poten-
(a) tial region, the O2 reduction currents on the disk electrode
are accompanied quantitatively by the H2 O2 oxidation cur-
Id (mA cm−2) Ir (µA), H2O2 (%)

rents on the ring electrode, reaching maximum peroxide

2 production of ca. 90% at 0.075 V. In Cl− -free solution,
0
however, a 3e− reduction is observed at the same potential
limit.[16] This may suggest that Clad is co-adsorbed with
−2 Hupd on the (100) surface, and thus the concentration of
empty Pt-pair sites required for the breaking of the O–O
−4 bond is significantly reduced so that the ORR proceeds
Pt(110) entirely through the 2e− peroxide pathway. The amount
−6
of peroxide formed on the Pt(110) surface is substantially
smaller (Figure 2b) ca. 2.5%, and no increase in peroxide
(b) formation was observed in the Hupd region.
The re-ordering of the structure sensitivity of the ORR
0.05 M H2SO4 + 10−3 M Cl− in the presence of Cl− versus (bi)sulfate can be explained
Id (mA cm−2) Ir (µA), H2O2 (%)

0.05 M H2SO4 qualitatively by analyzing the relative strengths of the

50
0 breaking and/or bond making. In particular, due to the
−2
−4
Pt(100)
−6
0.2 0.4 0.6 0.8
(c) E (V vs. RHE)
Figure 2. Ring and Disk currents for the ORR in 0.05 M
H2 SO4 + 10−3 M Cl− on (a) Pt(111), (b) Pt(110) and (c) Pt(100)
at different rotation rates (full lines). The respective polarization
curves on Pt(hkl) in 0.05 M H2 SO4 are shown as a reference
(dotted line). The gray circles represent the fraction of peroxide
formed during the ORR; 50 mV s−1 , 293 K. (From Ref. [27].)
(Figure 2c) in Cl− containing solution is accompanied by
peroxide formation, implying that within the same potential
limits H2 O2 is formed as an intermediate on the Pt(110) and
Pt(100) electrodes covered with Clad , but not on Pt(111)
covered by (bi)sulfate. On Pt(100) the fraction of H2 O2
(current efficiency) produced between 0.25 < E < 0.6 V
during the ORR, calculated from Figure 2(c) using[19]
Pt–Clad interaction, the specific type of sites for Clad , and
the effect of Clad at these sites on the rate of O–O bond
strong interaction of Clad with Pt(100), the ORR between
0.3 and 0.75 V is inhibited and the number of platinum sites
required for adsorption of O2 and the breaking of O–O bond
are reduced, which is in accord with the peroxide formation
in the same potential region. In the case of Pt(110), although
the interaction of Clad with Pt(110) is as strong as with
(100) sites, Clad is most likely adsorbed in the ‘troughs’
of the surface (insert of Figure 1), thus leaving the top
sites available for O2 adsorption and the cleavage of the
O–O bond. Apparently, the Pt(111)–Clad system has the
same effect on the ORR as (bi)sulfate anions, which is
somewhat surprising given the differences in ionic radii
of these anions, e.g., Cl− is about 75% that of sulfate or
bisulfate.[20]
Very similar results are observed for the Pt(hkl)/Br− sys-
tem as for Cl− , but in fact this system is even better under-
stood, since the Brad coverages have been measured quan-
titatively using a combination of SXS[21] and the rotating
ring-disk electrode (RRDE) current-shielding method.[18]
Examples are shown in Figures 3 and 4 for Pt(111) and
(100), respectively. Figure 3(a) shows cyclic voltammo-
grams for the Pt(111) surface in pure 0.1 M HClO4 solution
and in 0.1 M HClO4 + 10−4 M Br− under a rotation rate of
 Oxygen reduction reaction on smooth single crystal electrodes 469

900 rpm Pt(100)

20 µA
10 µA 0

0.5
0.4

θBr (ML)
0.4 0.3
0.2 0.1 M HClO4
0.3
0.1 +10−4 M Br−
θBr (ML)

(a) 0.0

0.2 60 2500
Pt(111)

Ir (µA)
30
0.1 M HCIO4
0.1
0.1 M HCIO4 + 8 × 10−3 M Br 0 ω (rpm)
H ads/des on Pt(111)/Br 400
0.5 900
(a) 0 Pt(111)/Br
1600
1.0 2500
Id (mA)

1.5
150 2500
1600 2.0
Ir (µA)

100 900
400 −0.4 −0.2 0.0 0.2 0.4 0.6
50
(b) E (V vs. SCE)
rpm
0
400 Figure 4. (a) Cyclic voltammetry of Pt(100) in the RRDE
assembly in oxygen-free electrolyte: ( ) 0.1 M HClO4 +
−Id (mA)

1.0
2500
2.0
−0.2 0 0.2 0.4 0.6
(b) E (V)
Figure 3. (a) Cyclic voltammetry of Pt(111) in the RRDE
assembly in oxygen-free electrolyte: ( ) 0.1 M HClO4 +
8 × 10−4 M Br− and (- - - -) 0.1 M HClO4 at a sweep rate of
50 mV s−1 ; ( . . . . ) deconvolution of the contribution from hydro-
gen adsorption/desorption; (-·-·-·) Brad adsorption isotherm; (b)
Disk (Id ) and ring (Ir ) currents during oxygen reduction on Pt(111)
in 0.1 M HClO4 (- - - -) and in 0.1 M HClO4 + 8 × 10−4 M Br−
( ) at a sweep rate of 50 mV s−1 (ring potential = −0.95 V).
(From Ref. [18b].)
900 rpm. The bottom section of Figure 3(a) shows the
adsorption isotherm for Br− on the Pt(111) surface. For
coverages above about 0.33 ML (1 ML = 1 Brad per Pt),
the Brad adlayer forms a series of ordered structures that
are interesting in themselves but not relevant to the present
topic. The interested reader is referred to other publications
specifically about these structures.[21] A close inspection of
1 × 10−4 M Br− and (- - - -) 0.1 M HClO4 at a sweep rate of
50 mV s−1 ; (-Ž-Ž-) Brad adsorption isotherm; (b) Disk (Id ) and
ring (Ir ) currents during oxygen reduction on Pt(111) in 0.1 M
HClO4 (- - - -) and in 0.1 M HClO4 + 8 × 10−4 M Br− ( )
at a sweep rate of 50 mV s−1 (ring potential = −0.95 V).
the Brad isotherm reveals that at the negative potential limit,
the Brad coverage goes to zero and the saturation coverage
by Hupd is identical to that in the Br− free electrolyte. To
confirm this, the hydrogen adsorption/desorption currents
were deconvoluted from the total disk currents (the total
disk charge Qtd ≈ 265 µC cm−2 ) by subtracting the bromide
flux measured with the ring-shielding experiments (details
of this deconvolution were reported previously[18] ). We
found that at 0.55 V the charge associated with adsorption
−2
of bromide, QBr d , is ≈100 µC cm , equivalent to a cover-
age ≈0.42 ML Brad per Pt for fully discharged atoms. This
is close to saturation coverage based on the van der Waals
radius of Br atoms and the surface density of Pt atoms. The
−2
difference between Qtd and QBr d amounts to 170 µC cm or
−2
to ≈160 µC cm if corrected by a double-layer capacitance
of ≈20 µF cm−2 . This is essentially equal to the pseudoca-
pacitance in the 0–0.3 V region of the Pt(111) surface in
470 Part 5: The oxygen reduction/evolution reaction
Br− - free solution, thus this charge is attributed to Hupd .
The resulting potentiodynamic curve for Hupd on Pt(111) in
solution containing Br anions is shown in Figure 3a (dot-
ted line), and demonstrates the reduced potential region of
stability of Hupd on Pt(111) in the presence of Br− due to
competitive adsorption.
Figure 3(b) summarizes a family of polarization curves
for the ORR on Pt(111) in 0.1 M HClO4 + 10−4 M Br−
along with a representative polarization curve recorded in
a solution free of Br− anions. In all experiments, the ring
was potentiostated at 0.95 V, where oxidation of peroxide
arriving at the ring is under diffusion control. In pure per-
chloric acid, starting at ca. 0.6 V and sweeping the disk
potential negatively to 0.0 V, the ring currents negligible,
implying that even on the surface covered with reversible
adsorbed OHad (the so-called ‘butterfly region’) oxygen
reduction proceeds without the production of peroxide in
solution. The appearance of peroxide oxidation currents on
the ring electrode begins at potentials negative of 0.0 V
saturated calomel electrode (SCE), and parallels with the
adsorption of hydrogen on Pt(111). At the negative poten-
tial limit the limiting current corresponds to an exactly
two-electron reduction of O2 . Figure 3(b) shows that the
ORR on the Pt(111) surface is strongly inhibited by Brad ,
with an activity orders of magnitude lower than in pure
perchloric acid. Figure 3(b) shows that the O2 reduction at
the Pt(111)–Br interface starts at ca. 0.3 V (θBr ≈ 0.4 ML
and θOH ≈ 0.0 ML in Figure 1(a)) and is under com-
bined kinetic-diffusion control in the wide potential region,
0.1 < E < 0.3 V. Figure 3(b) also shows that peroxide was
detected on the ring electrode in the same potential region,
indicating that the H2 O2 is formed as an intermediate on
the electrode covered with θBr ≈ 0.4–0.35 ML. At poten-
tials more negative than E = 0.1 V the surface coverage
with Br decreases substantially, e.g, from θBr ≈ 0.35 ML
to θBr ≈ 0.25 ML, and the O2 reduction currents increase
to a diffusion limiting current for 3e− per O2 molecule.
In the same potential region, the O2 reduction currents are
accompanied quantitatively by the H2 O2 oxidation currents
on the ring electrode. It is clear that Brad simultaneously
suppress the initial adsorption of the O2 molecule and the
formation of pairs of platinum sites needed for the breaking
of the O–O bond. As in the case of Pt(111) in 0.1 M HClO4 ,
however, below ca. −0.05 V the diffusion limiting currents
fall to a value for the 2e− reduction, reflecting that in this
potential region there is an additional inhibiting effect of
Hupd on the kinetics of the ORR.
SXS analysis indicated that Brad does not form an ordered
structure on Pt(100) at any potential. This is probably
due to the fact that Pt(100) is intrinsically an atomi-
cally rougher surface than (111) due to lifting of the
‘hex’ reconstruction[22] when the flame annealed or ultra
high vacuum (UHV) annealed crystal is immersed in elec-
trolyte. However, the Brad coverage has been measured
using the current-shielding RRDE method, and the adsorp-
tion isotherm along with the base voltammetry is shown
in Figure 4(a). As with Pt(111), the potential region for
Hupd is dramatically reduced by competitive adsorption of
Brad , but unlike the (111) surface Brad is present on the
(100) surface at and negative to the H2 electrode potential
(−0.244 V versus SCE). The ORR polarization curves are
shown in Figure 4(b). There is no observable rate of O2
reduction until the coverage by Brad is about 90% of the
saturation coverage, i.e., 10% of the Brad is desorbed. Brad
causes the half-wave potential to be shifted negatively by
about 0.5 V, about the same as on the (111) surface, and
the reaction proceeds entirely through the production of
peroxide intermediate in solution. Unlike the effect of Clad ,
however, Brad results in virtually no structure sensitivity for
the ORR, with the reaction proceeding with nearly identical
polarization curves on both the (111) and (100) surfaces.
4 IMPLICATIONS OF Pt(hkl) RESULTS
FOR FUEL CELLS
The structure sensitivity of the ORR in sulfuric acid found
using Pt(hkl) electrodes provides some new insight into the
‘particle size effects’ reported for the ORR using supported
Pt catalysts. Unfortunately, the observations of structure
sensitivity of the ORR are not at present as useful as
they might be because the experimental conditions, e.g.,
temperature and electrolyte, used in most ORR kinetic mea-
surements with supported catalysts are not those employed
in the RRDE measurements with single crystals. There is
only one out of the many particle size effect studies that
have employed exactly the same conditions as those used
here for single crystals: the study by Peukart et al.,[23] who
reported results in dilute sulfuric acid at ambient tempera-
ture. Fortunately, this was a very carefully done study using
well-characterized supported Pt catalysts with (average)
crystallite sizes ranging from 11.7 nm down to 0.78 nm.
As shown by Kinoshita,[6] the crystallite size dependence
in the data of Peukart et al., are essentially perfectly fit
by a model which assumes: (i) that only the (100) face is
active for the ORR; and (ii) that the Pt particles are perfect
cubo-octohedra. Below about 6 nm, the fraction of the sur-
face having (100) facets drops rapidly, and actually goes to
zero below 1.8 nm; particles below 2 nm are formed almost
entirely from (111) facets and their intersections (edges and
corners).[6] Our ORR data from single crystal Pt in sulfu-
ric acid fully support this model, since we have observed
that the (100) face is more active by two orders of mag-
nitude versus the (111) face (in the model calculations, a
 Oxygen reduction reaction on smooth single crystal electrodes 471
factor of 100 between the two faces is sufficient to fit the
data[6] ). By inference then, the crystallite size effect for
the ORR on supported Pt in sulfuric acid at ambient tem-
perature would be due to the structure sensitive adsorption
of (bi)sulfate anions, this adsorption effectively eliminating
the contribution of the (111) facets to the overall rate.
Kinoshita demonstrated that the ORR data for supported
catalysts in hot, concentrated H3 PO4 (180 ◦ C, 97–98%
acid) reported in three different studies were also fit by
this model.[6] Since the physical basis for the crystallite
size effect in sulfuric acid is anion adsorption, it would
be a reasonable to suggest that the same physical basis
applies to this crystallite size effect in H3 PO4 , i.e., struc-
ture sensitive anion (phosphate) adsorption. There are other
indications that this is the case. Anion adsorption in dilute
phosphoric has very similar structure sensitivity as sulfate
adsorption.[24] Sattler and Ross[25] reported a similar crys-
tallite size dependence of the ORR on supported Pt in dilute
phosphoric acid at ambient temperature as that found in hot,
concentrated acid with the same catalysts. But it is unclear
whether similar adsorption chemistry would exist in the
extreme conditions of hot, concentrated phosphoric acid.
With differences in activity between crystal faces of only
a factor of five or less for oxygen reduction in perchloric
acid,[26] the particle models of Kinoshita indicate that there
(111)
(100)
0.90
0.85
E (V vs. RHE)
0.80
0.75
0.70
0.65
0.60
0.1 1 10 100
(a) ik (mA cm−2)
Figure 5. (a) Tafel plots for the ORR on a Pt/carbon black catalyst in 0.5 M HClO4 (open circles) and after addition of 10−4 M Cl−
(black diamonds), 10−3 M Cl− (gray triangles) and 10−2 M Cl− . (b) Current efficiency for peroxide formation during ORR in the
presence of Cl− (concentrations as in a). Top shows transmission electron micrograph of a typical particle in the catalyst and a model
of the microstructure. (From Ref. [27].)
would little or no crystallite size effect for the ORR in a
nonadsorbing acid, such as, e.g., trifluoromethane sulfonic
acid or Nafion .
The effects of Cl− on the ORR with a Pt/carbon fuel
cell catalyst have been reported in a recent work from our
laboratory.[27] Figure 5(a) shows the current versus potential
curve for the ORR on Pt/Vulcan in 0.5 M HClO4 with and
without chloride. In accordance with the ORR on Pt(hkl),
the onset for the ORR is shifted to higher overpotentials
with increasing chloride concentration in the solution. Com-
pared to the ORR in the absence of Cl− the activity at
constant potential decreases roughly one order of magni-
tude for each order of magnitude increase in chloride anion
concentration. In addition, considerable H2 O2 currents on
the ring electrode (Figure 5b) are observed in solutions con-
taining Cl− , e.g., with increasing Cl− concentration, the
fraction of peroxide increases up to 10% at cCl− = 10−3 M
and 14% at cCl− = 10−2 M around 0.6 V, respectively. The
effect of Cl− on the ORR on supported catalysts can be fully
explained by applying the single crystal results to the rela-
tionship between particle size and the different surface sites
(crystal faces, edges and corners).[6] Based on a high reso-
lution transmission electron microscopy (HRTEM) analysis
of the catalyst used in this study, the structure of typical
Pt particle (mean particle size ca. 3.7 ± 1 nm) illustrated in
20
16
xH2O2 (%)
12
8
4
0
0.0 0.2 0.4 0.6 0.8
(b) E (V vs. RHE)
472 Part 5: The oxygen reduction/evolution reaction

Figure 5 show clearly that the cubo-octahedral Pt nanopar-
ticles close to the edge of the carbon support is facetted,
exposing (111) and (100) crystal facets and edges and cor-
ner sites with (110) symmetry. As on the Pt(111) crystal, at
the (111) facets, Clad blocks O2 adsorption without enhanc-
ing the formation of H2 O2 . In addition to inhibiting the
adsorption of O2 , the breaking of the O–O bond at the (100)
facets and (110) corner/edge sites and not as facile and the
production of peroxide on a supported Pt catalysts, ca. 15%,
is close to the average value of H2 O2 produced on Pt(100)
(ca. 25%) and Pt(110) (ca. 2.5%) single crystal surfaces.
As shown in the aforementioned sections, even trace
amounts of chloride (i.e., 10−4 M Cl− or ca. 4 ppm) dras-
tically change both the activity and the reaction path-
way of the ORR on Pt catalysts. Although these results
were obtained in liquid electrolyte, similar effects can
be expected on electrodes in a solid-polymer electrolyte
as present in a polymer electrolyte membrane fuel cell
(PEMFC). In this case, chloride impurities on the level
of a couple of ppm, either due to incorporation into the
membrane electrode assembly (MEA) during preparation
or due to contamination of the humidified fuel cell feed
streams, e.g., salt in the air feed, will strongly affect the
MEA performance. Based on the data in Figure 5, chlo-
ride contamination on the order of 4 ppm would result in
a fuel cell voltage loss of ca. 50 mV. These results indi-
cate in general the high purity conditions required for MEA
preparation and the humidified feed streams for PEMFCs.
In addition to the kinetic effect of Cl− adsorbed on the
supported metal catalyst particles, its enhancement of the
H2 O2 production will be deleterious to the stability of per-
fluorinated membranes and ionomers in the catalyst layers
(e.g., Nafion membranes and ionomers), which are known
to degrade in the presence of peroxide radicals.
5 ORR ON Pt(hkl) IN ALKALINE
ELECTROLYTE
The polarization curves for the ORR on Pt(111) at
293 K and 333 K (1600 rpm, 50 mV s−1 ) are illustrated in

80

40
40

i (µA cm−2)
30 293 K
Iring (µA)

0
20

10 −40
333 K
(c) 0 Pt(111)
0 −80
0.0 0.2 0.4 0.6 0.8 1.0
−1 (a) E (V vs. RHE)
Pt(111), 0.1 M KOH
1600 rpm, 50 m V s−1
1.0
−2
i (mA cm−2)

−3
E (V vs. RHE)

−4 293 K 0.9

333 K
−5
313 K
333 K
293 K
−6
0.0 0.2 0.4 0.6 0.8 1.0
E (V vs. RHE) 0.8
0.1 1 10 100
(b) (d) ik (mA cm−2)

Figure 6. (a) Base voltammetry (50 mV s−1 ) of Pt(111) at 276 K (solid line) and 333 K (dashed line) in 0.1 M KOH. (b) ORR polarization
curves (50 mV s−1 , 1600 rpm) on Pt(111) at 293 K (dashed line) and 333 K (solid line). (c) Ring currents for the detection of peroxide
formed during the ORR on Pt(111) at 293 K (dashed line) and 333 K (solid line). (d) Tafel plots for the ORR on Pt(111) at 293 K (white
triangles), 313 K (gray squares) and 333 K (gray circles) deduced from the polarization curves at 1600 rpm.

Figure 6b. In short, the region of mixed kinetic-diffusion
control (0.8 V < E < 1 V) is followed by the diffusion
limited current densities below ca. 0.8 V. At E < 0.4 V,
i.e., in the Hupd region, a deviation of the diffusion
limited currents to lower values can be observed. This
deviation can be quantitatively related to the formation of
HO2 − as demonstrated by the HO2 − detection on the ring
electrode,[4, 11] see Figure 6c. A more detailed discussion
of the ORR in the Hupd region on Pt(hkl) can be found
in our previous papers.[4, 11] At lower overpotentials, i.e.,
in the mixed kinetic-diffusion region, no peroxide can be
observed. A comparison of the ORR polarization curves
at 293 and 333 K indicates that as expected considerably
higher reaction rates are observed at 333 K, pointing
to the fact that the ORR in KOH is a significantly
activated process. The apparent activation energy, H = ,
is 47 kJ mol−1 determined at constant overpotential, η =
0.35 V in an Arrhenius analysis, (values summarized in
Table 1) according to a procedure described in Ref. [28].
A similar value was previously found in 0.05 M H2 SO4
extrapolated to the reversible potential,[10] as discussed
in the previous Section. The log i/E-relationships (so-
called Tafel plots) at 293, 313, and 333 K are plotted
in Figure 6d. The log i/E-relationships at the different
temperatures were fitted by straight lines in order to
determine the Tafel slopes. Decreasing Tafel slopes from
ca. 86 to ca. 57 mV dec−1 were found when going from
293 to 333 K, as summarized in Table 1. In contrast to
Pt(hkl) in sulfuric acid solution,[10] the Tafel slopes are
not proportional to RT /F . Figure 7 illustrates the Tafel
plots and the ring currents for HO2 − formed during the
ORR on Pt(100) and Pt(110), respectively. In contrast to
Pt(111), some HO2 − is detected in the potential region
above 0.4 V, and there is generally a decrease of peroxide
formation by increasing temperature, an increase in activity
by increasing temperatures, and again decreasing Tafel
slopes when going from 293 to 333 K. It is noteworthy,
that on Pt(100) and Pt(110) apparent activation energies of
Table 1. Summary of the Tafel slopes (Pt(hkl) and Au(hkl) and the apparent energies of activation (Pt(hkl) in 0.1 M
KOH.
293 K [mV dec−1 ]
lcd/hcda
Pt(111) –/86
Pt(100) –/112
Pt(110)(1 × 2) 92/190
Au(111) 60/185
Au(100) 47/119
Au(110) 44/127
a Tafel slopes determined at low (lcd) and high (hcd) current densities.
b Determined at E = 0.35 V.
Oxygen reduction reaction on smooth single crystal electrodes 473
ca. 42 and 37 kJ mol−1 , respectively were similar to that on
Pt(111). Based on the polarization curves and the Tafel plots
at the different temperatures, the ORR activity increases
in the order P(110)(1 × 2) < Pt(100) < Pt(111). However,
in a previous study in KOH at room temperature, also
from this laboratory,[11] a slightly different order was found,
namely Pt(111) > Pt(110) > Pt(100). The discrepancy can
be explained by the differences in preparation and in surface
structure of the Pt(110) crystal. In the present study, we
carefully prepared the reconstructed Pt(110)(1 × 2) surface,
versus the unreconstructed (1 × 1) surface used in the
previous study.[11] Therefore, the lower activity in the
present case can be ascribed to the fact that the very ‘open’
Pt(110)(1 × 2) surface adsorbs OH more strongly than
(1 × 1) surface in the previous study, i.e., the adsorption
sites for molecular oxygen are significantly blocked by
adsorbed OH (see discussion below).
6 ORR ON Au(hkl) IN ALKALINE
ELECTROLYTE
The study of Au(hkl) surfaces is complicated by the fact
that the flame annealed and/or the UHV annealed surfaces
of all three low index crystals of Au are reconstructed and
do not have the expected (1 × 1) bulk truncation structures.
Fortunately, the stability of these surface reconstructions
has now been well-studied by our group in alkaline
electrolyte using in-situ SXS.[29] Figure 8 highlights the
first sweep after emersion at ca. 0.1 V of the flame annealed
Au(100) crystal at 293 and 333 K, respectively. Directly
after flame annealing, the Au(100) surface is hexagonally
reconstructed forming a (5 × 27) unit cell.[30] Coming from
the negative emersion potential, upon sweeping through
the OHad region, this so-called (hex) reconstruction is
lifted due to adsorption of hydroxyl species, i.e., positive
of the peak at ca. 1.025 V at 293 K the Au surface has
the unreconstructed (1 × 1) surface. At 333 K, due to the
313 K [mV dec−1 ] 333 K [mV dec−1 ] H = [kJ mol−1 ]b
lcd/hcda lcd/hcda
–/72 –/57 47
–/78 –/60 42
80/120 –/83 37
– 72/150 –
– 50/85 –
– 37/86 –
474 Part 5: The oxygen reduction/evolution reaction

60 5

50 4
40
Iring (µA)

Iring (µA)
3
30
2
20
1
10

0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0 1.2
(b) E (V vs. RHE) (d) E (V vs. RHE)

333 K
313 K 0.9
293 K
0.9

E (V vs. RHE)
E (V vs. RHE)

0.8

0.8

0.7

0.7
0.1 1 10 100 0.1 1 10
(a) ik (mA cm−2) (c) ik (mA cm−2)

Figure 7. (a) Tafel plots for the ORR on Pt(100) at 293 K (white triangles), 313 K (gray squares) and 333 K (gray circles) deduced
from the polarization curves at 1600 rpm. (b) Ring currents for the detection of peroxide formed during the ORR on Pt(100) at 293 K
(white triangles), 313 K (gray squares) and 333 K (gray circles). (c) Tafel plots for the ORR on Pt(110)(1 × 2) at 293 K (white triangles),
313 K (gray squares) and 333 K (gray circles) deduced from the polarization curves at 1600 rpm. (d) Ring currents for the Figure 5:
magnification of the first voltammetric sweep after immersion at ca. 0.1 V of a flame-annealed Au(100) crystal in 0.1 M KOH solution
at 293 K (solid line) and 333 K (dashed line). 50 mV s−1 .

adsorption of OHad species at more negative potentials, the 80

lifting of the reconstruction is also shifted to more negative 333 K
potentials. The hex reconstruction reforms, albeit slowly,
60
upon holding the potential < ca. 0.4 V.[29] There is a similar Au(100)
lifting of the reconstructed surfaces of Au(111) and (110), 1st positive sweep
i (µA cm−2)

formed during flame annealing, when the potential is 40

scanned above ca. 1.1 V. For the results summarized here,
we used only the current potential curves recorded on 20
the cathodic sweep from 1.1 V, whereby all the surfaces
are known to have the (1 × 1) unreconstructed surface
0
structures throughout the potential region of interest.
Figure 9 summarizes the representative ORR polariza- 293 K
tion curves on Au(hkl) at 293 and 333 K (50 mV s−1 , −20
0.6 0.7 0.8 0.9 1.0 1.1
2500 rpm, lower panels in Figure 6) along with the cor-
responding ring currents for the oxidation of peroxide Figure 8. First voltammetry for a flame annealed Au(100) single
formed during the ORR (upper panels). The polarization crystal after immersion in 0.1 M KOH at 0.6 V. 50 mV s−1 , at 298
curves on Au(hkl) at 293 K are in agreement with previous and 333 K as shown.
results reported in the literature, whereas, to our knowl-
edge, it is the first time that ORR polarization curves on of the i –E curves on Au(hkl) are qualitatively similar
Au(hkl) at elevated temperature are reported. The shape to those described above for Pt(hkl). The region of mixed

120 Ring
I (µA)
80
40
0 0
0 0
−2
i (mA cm−2)
293 K
293 K
−4
333 K
−6 2500 rpm, 50 mV s−1
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2
(a) E (V vs. RHE) (b)
Figure 9. ORR polarization curves (lower panel) along with the ring currents for peroxide detection (upper panel) at 293 K (dashed
lines) and 333 K (solid lines) on (a) Au(111), (b) Au(110) and (c) Au(100). 0.1 M KOH, 50 mV s−1 , 2500 rpm.
kinetic-diffusion control (ca. 0.7 < E < 1 V) is followed
at lower potentials by a region where the reaction is
mainly under mass-transport control. However, in the
region of diffusion limited current densities, no clear cur-
rent plateaus for a 4e− process are observed as was the
case on Pt(hkl). Deviations from the diffusion limited cur-
rent for the 4e− reduction to OH− can be quantitatively
related to the formation of peroxide species, as indicated
by the ring currents in the upper panels. As in the case
of Pt(hkl), less peroxide is formed by increasing the tem-
perature to 333 K. It is clear that the ORR on Au(hkl)
is a strongly structural sensitive process in the temper-
ature range between 293 K and 333 K, with the kinetics
increasing in the order Au(111) < Au(110)  Au(100).
The Tafel slopes of the ORR on Au(hkl) at the differ-
ent temperatures are summarized in Table 1. The values
at room temperature are consistent with previously pub-
lished Tafel slopes[31] with only the value for Au(111)
deviating slightly. This discrepancy may be attributed to
some arbitrariness in drawing the tangent through the data
points that appear to be a straight line. Nevertheless, as on
Pt(hkl), we observe decreasing Tafel slopes with increasing
temperature.
Although well known in the literature,[31–33] I want to
emphasize the exceptional behavior of Au(100) (Figure 9c)
towards the ORR. Coming from the positive potential limit,
oxygen reduction occurs in essentially a 4e− process to
form OH− . At potentials negative of the so-called catalytic
peak, a transition to an almost 2e− process is observed, as
Oxygen reduction reaction on smooth single crystal electrodes 475
Ring Ring 120
I (µA)
80
40
−2
i (mA cm−2)
293 K
−4
333 K
−6
333 K
0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
E (V vs. RHE) (c) E (V vs. RHE)
seen from the polarization curve at 293 K in Figure 9(c).
Interestingly, at 333 K the reaction takes place via a 4e−
process in a much wider potential range, and only below
ca. 0.45 V are significant amounts of peroxide formed. In
order to get further insight into the reaction intermediate,
e.g., solution phase HO2 − , we studied the reduction of
oxygen in a solution containing a known amount of solution
peroxide, as summarized in Figure 10. The temperature-
dependent ORR curves without solution phase peroxide
are shown in Figure 10(a), the corresponding ring currents
for the oxidation of intermediate peroxide species are
shown in Figure 10(b), and, finally the oxidation/reduction
in 0.1 M KOH + 2 × 10−3 M HO2 − shown in Figure 10c.
The results in Figures 10(a, c) for Au(100) are similar to
those reported previously by Adzic and co-workers.[31] This
figure clearly demonstrates that the ORR closely follows
the reduction of HO2 − . The activity of Au(100) for HO2 −
reduction peaks at ca. 0.2–0.8 V and above this potential
only negligible amounts of peroxide are detected on the
ring electrode in ORR. Below ca. 0.6 V, the activity for
HO2 − decreases, and in the ORR there is a corresponding
increase in HO2 − production and reduction in the diffusion-
limiting current. This behavior clearly points to a serial
ORR mechanism through the formation of solution phase
HO2 − (2 + 2e− reaction, k2 , k3 pathway in the reaction
scheme). As one can also see from the polarization curves
in Figure 10, the temperature dependence in the kinetically
controlled potential regions, i.e., E > 0.8 V, is relatively
slight, much less than on Pt(hkl). In this narrow temperature
476 Part 5: The oxygen reduction/evolution reaction

4 (O2 − )ad + H2 O −−−→ (HO2 − )ad + OHad (5)

3 − −
(HO2 )ad −−−→ HO2 (6)
2
(HO2 − )ad −−−→ Oad + OHad
i (mA cm−2)

1
(7a)
− −
0 Oad + H2 O + 1e −−−→ OHad + 2OH (7b)
293 K
−1 − −
313 K OHad + 1e −−−→ OH (×2) (8)
−2 333 K
−3
For Pt surfaces, steps (4a, b) are generally considered
(c) −4 to be rate-determining, and are often written as a single
150 reaction in which (O2 )ad does not appear explicitly. But
such a reaction is not an elementary step, and writing
0.1 M KOH
100 2500 rpm such a reaction simply means that the elementary steps
Ir (µA)

50 m V s−1 (4a, b) proceed at the same rate. Likewise (7a, b) are

50 often combined to yield a single 1e− step in which Oad
does not appear explicitly, but again this would not be
(b) 0 an elementary step. With (4a) and (4b) rate-determining,
0 steps (5–8) are at equilibrium. Careful comparisons of
voltammetry on Pt surfaces with and without O2 in solution
have shown that at all potentials the coverage by OHad
−2
i (mA cm−2)

is unchanged by the presence of O2 , i.e., it is determined

entirely by the equilibrium constant of step (8). This implies
−4 that the equilibria for steps (7a, b) and (8) are shifted
strongly to the right hand side, and that the coverage by
Au(100)
−6 (HO2 − )ad in particular is low, as is the amount of HO2 −
in solution. The mechanism is very useful in establishing
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
the role of OHad in the structure sensitivity of the reaction
(a) E (V vs. RHE)
on Pt(hkl). Stronger adsorption of OHad causes the rate
Figure 10. (a) ORR polarization curves on Au(100), (b) ring cur- of (4a, b) to ‘back up’ due to the accumulation of
rents for the detection of peroxide and (c) oxidation and reduction OHad on the surface, blocking sites for electron transfer
of ca. 2 × 10−3 M HO2 − on Au(100) at 293 K (solid line), 313 K to O2 . The structure sensitivity then follows the relative
(dashed-dotted line) and 333 K (dashed line), respectively. 0.1 M strengths of adsorption of OHad and the OHad adsorption
KOH, 50 mV s−1 , 2500 rpm. isotherm, (110) > (100) > (111),[11, 34] with the reaction
rates then varying in reverse proportion, (111) > (110) >
range of 293–333 K, it was difficult to obtain an accurate (100). However, examination of the kinetic parameters for
measure of the activation energy, and thus no activation the ORR in Table 1 reveals that this analysis might be
energies are reported for Au(hkl). At potentials below 0.8 V, an oversimplification, and does not necessarily capture all
kinetics of HO2 − reduction are significantly increased, of the factors that contribute to the structure sensitivity.
nearly eliminating the catalytic peak at ca. 0.7 V and Although the apparent activation energies for all low-
producing 2 + 2e− reduction to much lower potentials. index Pt(hkl) surfaces are very similar, between 37 and
47 kJ mol−1 , the Tafel slopes are different on all three
surfaces. In line with the OHad site blocking effect discussed
7 MECHANISM OF THE ORR ON Pt AND
above, it should be noted that above a certain OHad
Au(hkl) IN ALKALINE ELECTROLYTE coverage not enough adsorption sites are present on the
surface, and, hence, a change in the rate-determining step
I will discuss the results on Pt(hkl) and Au(hkl) in terms of from reaction (4b), the first electron transfer, to the O2
the elementary steps derived from the generalized reaction adsorption step, reaction (4a), might be expected. That
scheme for oxygen reduction given in the previous section this may indeed be the case is seen in the results for
but now applied specifically to alkaline electrolyte: Pt(110) electrode, the least active surface, where the ORR
proceeds on a surface highly covered by oxygenated species
O2 −−−→ (O2 )ad (4a)
with a high Tafel slope, e.g., above 130 mV dec−1 (see
− −
(O2 )ad + 1e −−−→ (O2 )ad (4b) Table 1) which implies a chemical rate-determining step,
 Oxygen reduction reaction on smooth single crystal electrodes 477
as in reaction (1).[35] However, a full explanation of the
structure sensitivity of the ORR on Pt(hkl) in alkaline
electrolyte will await a more quantitative kinetic model than
we can offer at this time.
Relative to the Pt surfaces, if we assume the same
mechanism and rate-determining step for Au surfaces, the
difference in activity could qualitatively be attributed to
the much weaker interaction of OHad and Oad on the Au
surface, causing an accumulation of HO2 − both on the
surface and in solution. The base voltammetry shown in
Figures 6, 7 and 9 clearly shows that indeed there is a much
weaker adsorption energy for OHad and Oad on the Au(hkl)
surfaces than for the Pt(hkl) surfaces, with the onset of
OH formation shifted by more than +0.4 V for each crystal
face. Au(100) is the exception in terms of ORR activity,
having ‘Pt-like’ activity in the potential region above 0.8 V,
without the production of any peroxide in solution, i.e.,
4e− reduction. Taylor et al.[10] pointed out that the Pt-like
behavior is dependent on the electrode pre-history, and is
observed only on the negative-going sweep from potentials
above ca. 1.1 V. They postulated two possible explanations:
(a) the (100) surface is un-reconstructed above 1.1 V and
becomes reconstructed upon reducing the potential below
ca. 0.6 V, this transition causing the catalytic peak in the
polarization curve around 0.7 V; (b) surface oxide produced
at potentials above 1.1 V are actually catalytic for the ORR
and their reduction from the surface below ca. 0.6 V causes
the catalytic peak. In a later study from this laboratory,[27]
we found from in-situ SXS that there is no structural
transition on the Au(100) surface on the negative going
sweep from 1.1 V in the potential region around 0.6–0.8 V,
i.e., the surface remains in the unreconstructed (1 × 1)
geometry. A catalytic effect of the (relatively) irreversible
oxide formed above 1.1 V is against chemical intuition, and
furthermore at 333 K there is essentially no ‘oxide’ left
on the surface at 0.8–0.9 V (Figure 9b) but the region of
4e− reduction is extended to even lower potentials. So an
explanation for the unique behavior of the Au(100) for the
ORR in alkaline solution remains elusive.
The temperature dependence of the Tafel slopes on
Pt(hkl) and Au(hkl) as summarized in Table 1 are worth
more detailed discussion. Most notably, independent of the
exact value of the Tafel slopes, one trend can clearly be
observed: on both Pt(hkl) and Au(hkl) the Tafel slopes
always decrease with increasing temperature. This result
is in the contrast to Pt(hkl) in acid electrolyte, where
the Tafel slopes increase with the temperature, viz., from
116 mV dec−1 at 293 K to 132 mV dec−1 at 333 K as
expected.[4, 5] One explanation for decreasing Tafel slopes
with increasing temperature is a temperature dependence
of the apparent transfer coefficient, α, as discussed and
summarized by Adzic.[3] It is also possible to derive
anomalous temperature dependence in the Tafel slope even
when α is not temperature dependent. Returning to the
rate expression derived in the first Section, since the rate-
determining step (rds) is the same in alkaline as in acid,
and neither the proton nor water appear in the rds, the rate
expression is exactly the same according to[2, 19, 35]


−αF E
i = nF KcO2 · (1 −
OH ) · exp
RT


−γrOH
OH
× exp (9)
RT
There are no other anions besides OH− to consider, so
we need consider only the potential dependent coverage
of OHad . If one includes only the coverage dependence of
the pre-exponential term (i.e., rOH = 0), OH adsorption is
assumed to follow a Langmuir isotherm; if rOH = 0, the
adsorption proceeds according to a Frumkin isotherm with
lateral interactions of the adsorbates. The Tafel slopes at
constant temperature, say 293 K, expected from this model
should deviate from the 116 mV dec−1 towards smaller val-
ues depending the value of rOH (under both Langmuirian
and Frumkin conditions). That means, in order to model
decreasing Tafel slopes with increasing temperatures, the
(1–
OH ) term and/or the Frumkin-term must overcom-
pensate the Butler–Volmer term. Consequently, in order
to fit the experimental Tafel slopes using the experimen-
tal OHad adsorption isotherms (in the absence of O2 [17] ),
mathematically one has to include rOH values that increase
with the temperature. Recall that higher rOH values describe
stronger repulsive interactions of the adsorbates (=lower
free energy of adsorption at given coverage), and increas-
ingly stronger interactions with increasing temperature (via
increased mobility) is consistent with chemical intuition.
Nonetheless, the effect of decreasing Tafel slopes with
increasing temperature still need further theoretical mod-
eling in order to reach unambiguous conclusions.
Finally, I conclude with a new discussion of the effect of
pH on the kinetics of oxygen reduction. It has been known
for some time that there are certain electrode materials that
are useful, even practical, catalysts for oxygen reduction
in alkaline electrolyte, but not in acid electrolyte.[4] While
in many cases the pH effect may be attributed simply
to corrosion, e.g., transition metals are corroded in acid
but not in alkaline solution, that is not case for the two
materials I will focus on here, carbon and Au. Both these
materials are corrosion resistant in the 0–1 V potential
range in both strong acid and strong base solution even
at elevated temperatures. The case of glassy carbon, as
illuminated in the recent study by Yang and McCreery,[36] is
particularly interesting in this regard. Figure 11 reproduces
two polarization curves from this study, the one at pH = 0
and the one at pH = 14. At each pH, different surface
478 Part 5: The oxygen reduction/evolution reaction

80 the standard equilibrium potential for (1c) to be −0.31 V

pH 14 versus SHE (pH = 0), which puts the half-wave potential
60
(E1/2 ) at −0.15 V versus SHE or −0.36 V versus Ag/AgCl.
As expected, the outer sphere reaction is pH independent,
Current (µA)

and E1/2 remains at the same potential versus the Ag/AgCl

40
reference E1/2 . What is unexpected is that E1/2 for the
inner sphere electron transfer also remains at the same
AC/IPA cleaned
20 potential, shifted positively from the outer sphere potential
Polished by ca. 0.15 V independent of pH. Yang and McCreery
0 suggest the inner sphere reaction is the same as above for
MP derivatized Pt and Au surfaces,
−20
0.0 −0.2 −0.4 −0.6
(b) Potential (V vs. Ag/AgCl) O2 −−−→ (O2 )ad (4a)
− −
70 (O2 )ad + 1e −−−→ (O2 )ad (4b)

60 pH 0
Note that these reaction steps are also independent of pH,
50 so that inner sphere transfer is also pH independent, as
Current (µA)

40 Polished
30
20 AC/IPA cleaned
10
MP modified
0 transfer rate between an inner sphere and an outer sphere
−10
0.2 0.0 −0.2 −0.4
(a) Potential (V vs. Ag/AgCl)
Figure 11. ORR polarization curves on a glassy carbon electrode
in 1 M KOH (a) and 0.5 M H2 SO4 (b) with different surface mod-
ifications. Curves recorded potentiodynamically at 200 mV s−1 .
Note the potential scale uses a reference electrode that is pH
independent. (From Ref. [36] with permission.)
preparations were used to generate different fundamentally
different behavior: preparations such as polishing to prepare
a ‘clean’ surface, and modification with a covalently bonded
monolayer of methylphenyl groups. The methylphenyl
groups are designed to act as a charge transfer layer that
prevents the O2 molecule from interacting directly with the
carbon surface, but allows outer sphere electron transfer to
occur to form the superoxide radical anion,
O2 + 1e− −−−→ O2 −
The lifetime of solution phase O2 − is greater in the absence
of protons (pH = 14), and thus the oxidation of superoxide
on the reverse sweep is absent at low pH. Otherwise the
curves are virtually identical at both pH 0 and 14 for
both conditions of the surface. In agreement with other
studies in nonaqueous solvent, Yang and McCreery find
observed experimentally. The reactions following (4b) and
(4c), e.g., protonation to form HO2 − , are pH dependent,
but as long as (4b) or (4c) are rate-determining, the
E1/2 values will be pH independent. For glassy carbon,
the ca. 0.15 V shift in E1/2 is essentially just the so-
called Frumkin (double-layer) correction to the electron
reaction.[37] At, pH = 14, the standard potential for oxygen
−0.6 −0.8 reduction to peroxide is −0.144 V versus SHE or −0.35 V
versus Ag/AgCl, which means that both inner sphere
and outer sphere electron transfer of O2 to superoxide
occurs close to the thermodynamic potential for 2e−
reduction of oxygen to peroxide, and, by definition at low
overpotential (for 2e− ). This is shown more graphically
in the modified Pourbaix diagram for hydrogen peroxide
in Figure 12. The conventional Pourbaix diagram[38] is
modified to show the equilibria for reaction (4c). Hence,
at pH = 14 carbon surfaces reduce oxygen to peroxide
at low overpotentials, but at pH = 0 the overpotential
is very large, increased by essentially 0 .059 × 14 or
ca. 0.84 V because the thermodynamic potential has shifted
by 0.84 V positively but the E1/2 for the rate-determining
step (4b) has not. Because of the overlap in the equilibrium
potentials of peroxide and superoxide at pH = 14, nearly
any electronically conducting electrode material can be
(4c) used to reduce oxygen to peroxide, no specific chemical
interaction of O2 (or O2 − ) is required. However, at pH = 0
only surfaces with strong chemical interaction with O2 (or
O2 − ) can reduce oxygen to peroxide at low overpotential,
and even stronger interaction to reduce oxygen to water
at low overpotential. These are fundamental facts of nature
which lie at the heart of the difficulty in finding alternatives
to Pt as the catalyst for ORR in acidic electrolyte.
 Oxygen reduction reaction on smooth single crystal electrodes 479

2.2
2.0 1′
1.8 2 H2O2 HO2−
1.6 0
−2
1.4 −4
1.2 b log(H2O2) = −6

1.0

0.8 −6 3 0
4 −4 −2
−) = −6−4
0.6 −2 log(HO2
(H2O2)
0.4 log =0
PO2 (HO2−)
E (V)

0.2
log =
PO2
−6
−6
0.0 5 −4
−2
−4
−2 0
−0.2
6 0
−0.4 (O2−)
log = a
PO2
−0.6
−0.8
−1.0
−1.2
−1.4
−1.6
−1.8
−2 −1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
pH

Figure 12. Pourbaix diagram[38] for hydrogen peroxide with the equilibria for the superoxide/oxygen reaction (labeled 6 in the diagram)
added. Other notations for equilibria as in Ref. [38].

8 CONCLUSIONS In acid electrolyte, the ORR polarization curves on Au

The structure sensitivity of the oxygen reduction reaction on
Pt and Au surfaces has been examined using single crystal
electrodes and modern methods of surface preparation and
characterization. For Pt in sulfuric and phosphoric acid
electrolytes, the structure sensitivity is dominated by the
inhibiting effects of anion adsorption, which is strongly
structure sensitive. In nonadsorbing acids like perchlorate
or triflate, the structure sensitivity is weak, probably due
to the single-site nature of the rate-determining step, i.e.,
electron transfer to form adsorbed superoxide radical anion.
Thus, a particle size effect is not expected for supported
Pt catalyst in a PEMFC cathode if the geometric change
in particle shape with size is the only factor contributing,
i.e., absent electronic effects such as quantum confinement.
For Au in alkaline electrolyte, oxygen reduction is strongly
structure sensitive, with the (100) surface the only Au
surface with direct 4e− oxidation at potentials near 0.9 V.
There is no explanation available for the unique catalytic
activity of Au(100) for the ORR in alkaline electrolyte.
surfaces are shifted negatively [on a reference hydrogen
electrode (RHE) scale] by hundreds of mV, and the
reaction becomes structure insensitive. The large effect of
pH on the overpotential for ORR on Au is due to the
absence of chemisorption of either O2 or O2 − . The rate-
determining step on Au is inner sphere electron transfer
to O2 form O2 − , and this reaction step is independent
of pH, i.e., the reaction occurs at a fixed potential on a
SCE scale, so the overpotential (on an RHE scale) changes
with pH.
ACKNOWLEDGEMENTS
This work was supported by the US Department of Energy,
the Office of Science, Basic Energy Sciences, Materials Sci-
ences Division, and the Office of Advanced Transportation
Technologies, Fuel Cell Systems, under contract DE-AC03-
76SF00098.
480 Part 5: The oxygen reduction/evolution reaction
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