ARTICLE

Received 4 May 2013 | Accepted 23 Oct 2013 | Published 18 Dec 2013 DOI: 10.1038/ncomms3817

Direct observation of the oxygenated species

during oxygen reduction on a platinum
fuel cell cathode
Hernan Sanchez Casalongue1,2, Sarp Kaya1,2, Venkatasubramanian Viswanathan1,3, Daniel J. Miller1,
Daniel Friebel1,2, Heine A. Hansen1,3, Jens K. Nørskov1,3, Anders Nilsson1,2,4 & Hirohito Ogasawara1,4

The performance of polymer electrolyte membrane fuel cells is limited by the reduction at the
cathode of various oxygenated intermediates in the four-electron pathway of the oxygen
reduction reaction. Here we use ambient pressure X-ray photoelectron spectroscopy,
and directly probe the correlation between the adsorbed species on the surface and the
electrochemical potential. We demonstrate that, during the oxygen reduction reaction,
hydroxyl intermediates on the cathode surface occur in several configurations with
significantly different structures and reactivities. In particular, we find that near the open-
circuit potential, non-hydrated hydroxyl is the dominant surface species. On the basis of
density functional theory calculations, we show that the removal of hydration enhances the
reactivity of oxygen species. Tuning the hydration of hydroxyl near the triple phase boundary
will be crucial for designing more active fuel cell cathodes.

1 SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, USA.
2 Joint Center for Artificial Photosynthesis (JCAP)Energy Innovation Hub, LBNL, 1 Cyclotron Road, MS 976-JCAP, Berkeley, California 94720, USA. 3 SUNCAT
Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, Stanford, California 95305, USA. 4 Stanford Synchrotron
Radiation Lightsource (SSRL), SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, USA. Correspondence and requests
for materials should be addressed to H.O. (email: [email protected]).

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ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms3817

T
he performance of polymer electrolyte membrane (PEM)
fuel cells is limited by the sluggish kinetics of the oxygen e– –
e
e– –
reduction reaction (ORR) at the platinum (Pt) cathode. An e e– –
e– e
improved understanding of catalytic steps of the ORR is thus x-ray e–
e– e–
essential for overcoming these limitations. Through electroche- e–
mical measurements, the ORR has been inferred to occur through e– e–
e– O2
a hydroxyl (OH) intermediate1,2. Indeed, based on density
functional theory (DFT) simulations of the oxygenated
intermediates of the ORR, it has been proposed that the Pt–OH e–
bond strength could be a key descriptor of ORR activity and
could therefore guide catalyst design3–5. However, recent Cathode V
experiments have observed unusual ORR activity in the H+
H +
presence of various ions6,7, in dehydrated environments8 and A
H+
on stepped surfaces with limited terrace widths9,10. These indicate Nafion H+
Anode e–
that experiments to observe and characterize OH species directly
during the ORR are essential.
As most in situ experimental methods cannot detect oxyge-
nated adsorbed species, the identification of OH is especially
challenging. For example, Pt L-edge X-ray absorption spectro- H2, H2O
scopy, which probes the Pt substrate11, is typically sensitive to
changes in the Pt oxidation state but cannot distinguish OH from Figure 1 | Electrochemical cell for photoelectron spectroscopy. Schematic
other oxygenated species adsorbed on the surface12. The drawing of a PEM fuel cell set-up for APXPS investigations: the
application of vibrational spectroscopy is also limited by electrochemical cell has a Nafion membrane coated on both sides with a
the strong absorbance of both the electrolyte solution and the mixture of Nafion and carbon-supported Pt nanoparticles with catalyst
electrolyte membrane, which makes the weak vibrational loading of 4 mg cm  2 (particle size 10–20 nm), which serve as anode and
signature of the OH species virtually undetectable13,14. X-ray cathode. The cathode side of the assembly was exposed to the APXPS gas
photoelectron spectroscopy (XPS), which probes all oxygenated cell, which was filled with oxygen gas. The anode chamber was filled with
surface species with equal sensitivity, has been used to study Pt humidified forming gas (95% N2/5% H2, saturated H2O). The voltmeter
single-crystal electrodes15,16 in ultra-high vacuum. The challenge and galvanometer used for measurements are denoted by V and A,
with these ex situ measurements is to minimize decomposition respectively. By connecting both electrodes to an external voltmeter or
and contamination during sample transfer, as surface water galvanometer, we can simultaneously record both XPS and either cell
species on Pt all desorb above 200 K in ultra-high vacuum17. voltage or cell current.
Here we report in situ identification of oxygenated inter-
mediates on a Pt cathode during the ORR using ambient pressure
XPS (APXPS), which enables measurements under high gas different positions on the sample do not differ strongly, which
pressures (o100 Torr)18,19. We are able to identify the indicates that the electrochemistry is not localized but occurs
oxygenated intermediates of the ORR through their specific O throughout the surface. This suggests that only a few layers of
1s chemical shifts. Using XPS studies of well-defined model interfacial water are needed to conduct protons across the
systems as spectroscopic references, we differentiate two types of interface; recent studies of photocatalytic water splitting reached a
OH intermediates whose population depends on cell voltage: similar conclusion21.
hydrated and non-hydrated OH. We also establish that non- First, we establish the relationship between the electrochemical
hydrated OH is the dominant surface species on a Pt cathode potential and surface species at the cathode. Both the electro-
during the ORR at high partial pressures of O2(g). With the chemical potential and the work function of a surface describe
assistance of DFT calculations, we show that the reduction of how strongly it binds electrons. It has been demonstrated that
non-hydrated OH requires less overpotential than that of shifts in the XPS-binding energies (BE) of gaseous molecules,
hydrated OH. This indicates that tuning OH hydration through when referenced to the Fermi level in the vicinity of the
cathode or electrolyte design will be crucial for enhancing ORR surface20,22, can be used to determine changes in the work
activity. function; accordingly, changes in the electrochemical potential
can be inferred from XPS. Guided by that principle, we measured
the O 1s XPS spectra of oxygen molecules in the vicinity of the
Results cathode (Fig. 2b). From the shifts in the gas-phase peak, we were
Photoelectron spectroscopy measurements. We designed a PEM able to correlate changes in the work function with those in the
fuel cell compatible with our APXPS system (Fig. 1). To date, cathode electrochemical potential (Fig. 2c). As these two sets of
APXPS has been applied to the study of high-temperature solid- shifts closely agree, the observed changes in electrochemical
oxide fuel cells20 but not to PEM fuel cells. In Fig. 2a, we show potential at the cathode must arise from changes in surface
the O 1s spectra and potentials of the cathode before and after speciation.
the introduction of 0.4 Torr of O2(g) under open-circuit To understand the relationship between electrochemical
conditions. The evolution of cell voltage as a function of time potential and surface species at the cathode, we compared our
is further explained in Methods: Evolution of cell voltage results with previously assigned XPS features of various
and Supplementary Fig. S1. Anodic charging following the oxygenated adsorbates on Pt. We compare our results to
introduction of O2(g) causes the electrochemical potential at the Pt(111), as our system contains nanoparticles 10–20 nm in size
cathode to increase from 0.1 to 0.9 V. The latter voltage of 0.9 V (see Methods) the close-packed terrace sites will dominate23. In
represents the maximum electrochemical potential available at Fig. 2d,e, we display O 1s spectra and corresponding schematic
the cathode in our set-up; the deviation from the Nernst potential illustrations for four oxygenated adsorbate systems on Pt(111):
of the ORR at the 0.4-Torr O2 pressure (1.182 V) is attributed to multilayer H2O24; adsorbed H2O (H2O(ad))24; co-adsorbed
kinetic losses3. For a given potential, the spectra recorded at H2O and OH (H2O-OH)25; co-adsorbed OH and O (OH–O).

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NATURE COMMUNICATIONS | DOI: 10.1038/ncomms3817 ARTICLE

USHE (V) 1.0

USHE (V)

0.9
0.9
0.8

USHE (V)
Intensity (a.u.)
Intensity (a.u.)
0.8
0.75
0.7 0.6

0.5 0.6

0.1 0.1 0.4 0.6 0.8 1.0 1.2

Work function
change (eV)
540 538 536
Binding energy (eV)

529.9 eV 531eV
OH-O OH-O
Intensity (a.u.)

OH-O
531.6 eV 530.1 eV
OH-H2O H2O-OH
OH-H2O
532.2 eV
H2O(ad)
H2O(ad)
Multilayer H2O

534 532 530 528

Binding energy (eV)

Figure 2 | Identification of oxygenated species on Pt cathode. (a) O 1s XPS spectra of a fuel cell cathode. The incident photon energy was 670 eV. Dots
and solid lines correspond to experimental results and smoothened curves (first-order binomial), respectively. Spectra between 0.5 and 0.9 V were
collected while exposing the anode to 600 Torr of humidified forming gas and the cathode to 0.4 Torr O2. The spectrum at 0.1 V was taken in the absence of
oxygen. (b) O 1s XPS spectra of oxygen gas in the vicinity of the cathode. The electrochemical potential of the cathode quoted against standard hydrogen
electrode (SHE), USHE, was measured simultaneously against the anode. The observed multiplet splitting is due to the coupling between the unpaired
spins in the valence and core levels in a paramagnetic oxygen molecule33. (c) Plot of the measured cathode potential versus the change in work
function. The bottom and top of bar correspond to the cathode electrochemical potential measured at the beginning and end of XPS data accumulation,
respectively. (d) O 1s XPS spectra of oxygenated surface species on Pt(111). Bottom to top: multilayer H2O24; H2O(ad)24; adsorbed H2O-OH25; adsorbed
OH-O measured in 0.05 Torr O2 and 0.05 Torr H2 at 450 K. (e) Schematic models and BE for oxygenated species: H2O(ad) (orange, 532.2 eV),
H2O-OH (red, 531.6 eV), H2O-OH (blue, 530.1 eV), O-OH (cyan, 531 eV) and O-OH (green, 529.9 eV).

These reference spectra indicate that features at 533 and 532.2 eV ranges from 531 eV for non-hydrated OH to 530.1 eV for fully
are assigned to multilayer H2O and H2O(ad), respectively. The hydrated OH—as well as from the heterogeneity of the Pt
co-adsorbed H2O-OH layer, in which both OH and H2O nanoparticles in the sample.
are hydrogen bonded to each other, yields O 1s features at We now shift our focus to the role of adsorbates on the cathode
531.6 and 530.1 eV arising from adsorbed water (H2O-OH) when a current is extracted. Figure 3a shows the O 1s spectra of
and OH (H2O-OH), respectively. The co-adsorbed OH–O the cathode surface collected while the cell is generating current
layer, in contrast, gives rise to an OH feature at 531 eV (OH-O) (‘closed circuit’ conditions). These spectra were stable under
and a second feature at 529.9 eV that is assigned to adsorbed constant O2 pressure (p(O2), and their profiles were reversible
O on Pt(111)25 (OH-O); that the BE of OH is 0.9 eV higher with respect to variations of (p(O2). At low oxygen pressures
in OH-O (non-hydrated OH) than in H2O-OH (hydrated OH) is (p(O2)o0.15 Torr), multilayer H2O and H2O(ad) features
attributed to the absence of hydrogen bonding in the former dominate; the spectra recorded at oxygen pressures of 0 and
phase. 0.15 Torr are similar to the 0.1 and 0.5 V spectra shown in Fig. 2a
Turning to Fig. 2d, with spectra measured in situ under open- obtained under open-circuit conditions (the elucidation of the
circuit conditions, we see that water-related spectral features cathode potential is described in Methods: Comparison of XPS
dominate at lower potentials (0.1 and 0.5 V). Under these spectra and Supplementary Fig. S2). As the O2 pressure increases
conditions, we clearly resolve a low-binding energy shoulder (p(O2)40.5 Torr), the current output increases and the spectra
arising from a hydrogen-bonded network of co-adsorbed OH and develop a major feature at a BE corresponding to non-hydrated
H2O species (H2O-OH). At high potentials (0.75 and 0.9 V), the OH species. Figure 3b illustrates this point by showing a spectral
dominant feature at 531 eV cannot be explained solely by deconvolution of the surface species at an oxygen pressure of
hydrated OH, even when considering the 0.3 eV BE variation 0.8 Torr. Although this spectral decomposition is not unique
due to different facets16. Thus, we assign it to non-hydrated because of the numerous species involved and the multiple
OH with small contribution from OH-O. The broadness of the degrees of hydrogen bonding available to the OH species, all fits
spectra recorded at high potentials arises from the existence of agree that the most prominent spectral feature arises from non-
OH species with differing degrees of hydration—the BE of OH

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ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms3817

OH-O
p (O2) Icell USHE OH-H2O
(Torr) (μA) (V)

24 0.9 H2O(ad)
2
OH-H2O

Multilayer H2O
0.8 20 0.9
OH-O

0.5 15 0.75

0.15 10 0.5

0 0 0.1

536 534 532 530 528 536 534 532 530 528
Binding energy (eV) Binding energy (eV)

Figure 3 | XPS spectra of cathode under operating conditions. (a) O 1s XPS spectra obtained for an operating (closed circuit) fuel cell cathode. The
incident photon energy was 670 eV. Spectra were collected under 600 Torr of humidified forming gas at the anode and varying O2 pressures at the cathode,
as shown. The resulting current outputs, Icell, and the elucidated cathode potential, USHE, measured using XPS (see Methods: Comparison of XPS
spectra and Supplementary Fig. S2) are indicated. Dots correspond to experimental results and solid lines correspond to smoothened curves (first-order
binomial). The spectral changes were reversible with respect to p(O2). The blue dotted lines correspond to the model structures on Pt(111) discussed in
Fig. 2b. (b) Peak-fitted O 1s XPS spectrum in 0.8 Torr oxygen. The spectra were deconvoluted using Gaussian-broadened Doniach–Šunjić functions.
Because of the large number of species and parameters, this peak fitting is more qualitative than quantitative in its nature, guiding the reader’s eye to the
different surface species: multilayer H2O (purple), H2O(ad) (orange), H2O-OH (red), OH-O (cyan), H2O-OH (blue) and OH-O (green).

hydrated OH. These results clearly identify that non-hydrated evaluate their reactivity for the reduction of oxygen by
OH species is a key surface species of ORR. constructing a free-energy diagram at a potential of 0.9 V based
on DFT calculations (Fig. 4c). In the hydrated pathway, the
limiting step is associated with the removal of OH(ad) on Pt(111).
Theoretical simulations. Using DFT and Monte Carlo simula- In the non-hydrated pathway, the removal of hydration enhances
tions, we have calculated the coverages of adsorbed water the reactivity of OH(ad) but creates a thermodynamic barrier to
(H2O(ad)), OH (OH(ad)) and O (O(ad)) as a function of computed the activation of O2(g) as adsorbed OOH (OOH(ad)) because of a
electrochemical potential (Fig. 4a). We emphasize that the cov- combination of weakening interactions from dehydration and
erages are averaged quantities. At low potentials, below 0.65 V,
repulsive adsorbate–adsorbate interactions with O(ad). Therefore,
H2O(ad) is the dominant species. Above 0.65 V, OH(ad) begins to at 0.9 V, the thermodynamic barrier associated with the overall
appear from the oxidation of H2O(ad). Passing the reversible
ORR process is 0.07 eV in the non-hydrated pathway, corre-
potential of this reaction at 0.76 V (ref. 26), the coverage of OH sponding to the conversion of O2(g) to OOH(ad). On the other
(y(OH(ad)) becomes greater than that of H2O(ad) (y(H2O(ad)).
hand, in the hydrated pathway, this barrier becomes 0.15 eV for
Higher potentials lead to further oxidation of OH(ad) into O(ad), the removal of hydrated OH(ad). This analysis suggests that
which becomes the dominant surface species at potentials above
extending the stability range of the non-hydrated phase will prove
the reversible potential of 0.95 V (ref. 26). Representative beneficial in improving the overall ORR activity.
snapshots of the adsorbate layer at two different potentials (0.8
The importance of non-hydrated OH for the ORR at high
and 0.95 V) are shown in Fig. 4b. First, we find that at 0.8 V, all potentials explains the enhanced ORR activity of Pt in
OH(ad) have hydrogen bonds to H2O(ad) indicating only hydrated
hydrophobic ionic liquids8, in the presence of certain aqueous
OH is present on the surface. On the other hand, we find OH(ad) ions6,7 and on stepped surfaces with narrow terrace width9,10.
both with and without hydrogen bonds to H2O(ad) at 0.95 V. This
The last is unexpected as step sites strongly bind OH, as indeed
is consistent with the XPS results (Fig. 2a), which show that observed with a reduced activity for small Pt nanoparticles27.
adsorbed water and hydrated OH prevail at low potentials,
However, whereas adsorbed H2O and OH form an extended
whereas non-hydrated OH appears at high potentials. The hydrogen-bonding network on wide terraces25, that process is
emergence of OH(ad) without hydrogen bond is correlated with
hindered on narrow terraces because of limited space and thus
the appearance of O(ad)-rich domains, which displace H2O(ad) the amount of non-hydrated OH is increased. In general,
because of repulsive interactions between O(ad) and H2O(ad).
dehydrated environments8 will by their very nature limit the
Through this insight, we explain that the hydrated and non- hydration of any OH intermediates. Finally, as hydrogen bonding
hydrated OH observed in Fig. 3b co-exist in localized domains.
of H2O to OH can compete with direct ion–OH interactions28,
specific ions in the electrolyte could limit the hydration of OH6,7.
Discussion This new insight into the subtle interplay between non-covalent
Our studies not only confirm the presence of OH(ad) during ORR hydrophobic and hydrophilic interactions can inspire the design
conditions but, most importantly, also demonstrate that there are of new catalysts, not only for the ORR but also for other relevant
two phases of OH, hydrated OH and non-hydrated OH, co- electrochemical reactions.
existing under operating conditions. This distinction led us to

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NATURE COMMUNICATIONS | DOI: 10.1038/ncomms3817 ARTICLE

USHE = 0.8 V USHE = 0.95 V

OH(ad)
O(ad) Non-hydrated
0.3
H2O(ad)

Coverage ()
0.15

0
Hydrated
0.5 0.6 0.7 0.8 0.9 1
USHE (V)

USHE = 0.9 V

Hydrated Non-hydrated
1.5 OOH(ad) OOH(ad)
O2(g) O2(g)

1.0
ΔG (eV)

0.5 O(ad)+H2O

OH(ad)+H2O

2H2O 2H2O
0 O(ad)+H2O OH(ad)+H2O

Reaction coordinate

Figure 4 | DFT and Monte Carlo simulations. (a) Calculated coverages of adsorbed oxygen, OH and water as a function of computed electrochemical
potential, USHE, obtained from DFT and Monte Carlo simulations. The regions marked are separated by the emergence of O(ad) at 0.85 V. (b) Representative
snapshots of the surface at 0.8 and 0.95 V from the Monte Carlo simulations exemplify the two regimes shown in a, with H2O(ad) (red and white
circles), hydrated OH(ad) (blue and white circles), non-hydrated OH(ad) (cyan and white circles) and O(ad) (green circles) shown on a Pt (grey circles)
surface. The adsorbate layer between 0.85 and 1 V consists of co-existing localized domains of both hydrated and non-hydrated OH, which we have marked
in the corresponding schematic. (c) Free-energy diagrams for the ORR, based on DFT calculations for both hydrated and non-hydrated pathways,
at a potential of USHE ¼ 0.9 V. The change in Gibbs free energy, DG, along the reaction coordinate shows that the thermodynamically limiting step in
the hydrated phase is the removal of adsorbed OH. In the non-hydrated phase, the limiting step is the activation of O2 as OOH(ad).

Methods spectra, we show the C 1s and F 1s XPS before and after the introduction of oxygen
Experimental details. The electrochemical cell assembled on a poly- as the inset of Supplementary Fig. S3, which indicate no increase of oxidized
etheretherketone (PEEK) polymer framework has a Nafion 115 membrane coated carbon- or fluorine-containing species.
on both sides with Pt nanoparticles, which serve as anode and cathode, supported
on a Nafion/carbon-black mixture with catalyst loading of 4 mg cm  2 from the Evolution of cell voltage. Supplementary Figure S1 shows the evolution of the
Fuel Cell Store, Inc (Boulder, CO; particle size 10–20 nm). The cathode was cathode potential as a function of time under the open-circuit potential conditions
exposed to the APXPS gas cell, which was filled with oxygen gas. The anode in which the O 1s XPS spectra shown in Fig. 2a were collected. The anode was
chamber was filled with humidified forming gas (95% N2/5% H2) to provide supplied with 600 Torr of humidified forming gas, which also humidified the
hydrogen fuel and membrane humidification. For open-circuit measurements, the cathode through the diffusion of water across the Nafion membrane. At time
anode was used as a hydrogen electrode. All reported potentials are referenced
  to t ¼ 0 min, we introduced 0.4 Torr of oxygen gas to the cathode chamber. After the
2F pðH2 Þ
the standard hydrogen electrode. Using the Nernst equation,  RT ln p0 , the introduction of the oxygen, the cathode potential increased, eventually maintaining
anode potential is calculated to be 0.065 V against standard hydrogen electrode. a constant value of B0.9 V. The development of cell voltage correlates well with the
Here F is the Faraday constant, R is the universal gas constant, T is the tem- O 1s changes in XPS of the cathode, as illustrated in the accompanying spectra
perature, p(H2) is the partial pressure of hydrogen in the anode chamber and p0 is (t ¼ 5, 12, 130 and 177 min are also shown in Fig. 2a). We note that no spectral
the standard pressure. change was observed after the cell potential reaches the constant value of 0.9 V.
The XPS measurements were performed by placing the electrochemical cell into
the gas cell of the APXPS system on beamline 13-2 at the Stanford Synchrotron Comparison of XPS spectra. Supplementary Figure S2 compares the O 1s XPS
Radiation Lightsource19. Water vapour and hydrogen were introduced through spectra shown in Fig. 3a measured under closed-circuit conditions and the O 1s
small tubes while the cathode side exposed in the gas cell was pressurized via XPS spectra shown in Fig. 2a measured under open-circuit conditions. The cathode
variable leak valves. The XPS BE is referenced to the Fermi level through operating at O2 pressure of 0.15 Torr exhibits the same surface species as a cathode
measurements of the valence band under the corresponding experimental at an open-circuit potential of 0.1–0.5 V. On the other end, on the cathode at O2
conditions. Supplementary Figure S3 shows an overview XPS spectrum of the pressure above 0.8 Torr exhibits the same surface species as those observed at an
cathode surface together with inserts showing the detailed F 1s and C 1s spectra open-circuit potential of 0.9 V. We used this information to elucidate the cathode
before and after the introduction of oxygen to the cathode. In addition to Pt and potential under closed-circuit reaction conditions.
adsorbed oxygenated species, there are spectral features from water and fluorinated
carbon in Nafion binder and carbon black. The sulphur spectral contributions from
the Nafion region are small compared with the carbon-black region ruling out the Computational details. The simulation of the reaction kinetics is accomplished
involvement of sulphur-containing oxygenated species in the spectral changes. To through a combination of equilibrium and dynamic Monte Carlo methods using
rule out the contributions of either polymer or oxidized carbon black in the O 1s kinetic and thermodynamic parameters calculated from DFT. The DFT

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ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms3817

calculations were performed using the DACAPO and ASE codes (https://www.wiki. 16. Wakisaka, M., Udagawa, Y., Suzuki, H., Uchida, H. & Watanabe, M. Structural
fysik.dtu.dk). The ionic cores were described using ultrasoft pseudopotentials29 and effects on the surface oxidation processes at Pt single-crystal electrodes studied
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FTIR study of oxygen reduction at the Pt/Nafion interface. Phys. Chem. Chem. Reprints and permission information is available online at http://npg.nature.com/
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polycrystalline Pt electrodes by photoelectron spectroscopy. Langmuir 25, species during oxygen reduction on a platinum fuel cell cathode. Nat. Commun. 4:2817
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