Research Article

pubs.acs.org/acscatalysis

Defects do Catalysis: CO Monolayer Oxidation and Oxygen

Reduction Reaction on Hollow PtNi/C Nanoparticles
Laetitia Dubau,*,†,‡ Jaysen Nelayah,§ Simona Moldovan,∥ Ovidiu Ersen,∥ Pierre Bordet,⊥,# Jakub Drnec,∇
Tristan Asset,†,‡ Raphael̈ Chattot,†,‡ and Frédéric Maillard*,†,‡
†
Université Grenoble Alpes, LEPMI, F-38000 Grenoble, France
‡
CNRS, LEPMI, F-38000 Grenoble, France
§
Laboratoire Matériaux et Phénomènes Quantiques (MPQ), UMR 7162, CNRS & Université Paris-Diderot, Bâtiment Condorcet, 4
rue Elsa Morante, F-75205 Paris Cedex 13, France
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

∥
Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), UMR 7504, CNRS-Université de Strasbourg (UdS), 23 rue
du Lœss, Cedex 2 Strasbourg, France
⊥
Université Grenoble Alpes, Institut Néel, F-38000 Grenoble, France
#
CNRS, Institut Néel, F-38000 Grenoble, France
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∇
European Synchrotron Radiation Facility, ID 31 Beamline, BP 220, F-38043 Grenoble Cedex, France
*
S Supporting Information

ABSTRACT: The catalytic performance of extended and nanometer-

sized surfaces strongly depends on the amount and the nature of structural
defects that they exhibit. However, whereas the effect of steps or adatoms
may be unraveled with single crystals (“surface science approach”),
implementing reproducibly in a controlled manner structural defects on
nanomaterials remains hardly feasible. A case that deserves particular
attention is that of bimetallic nanomaterials, which are used to catalyze the
oxygen reduction reaction (ORR) in proton exchange membrane fuel cells
(PEMFC). Point defects (vacancies), planar defects (dislocations and
grain boundaries), and bulk defects (voids, pores) are likely to be
generated in alloy or core@shell nanomaterials based on Pt and a
transition metal due to the high lattice mismatch between the two
elements. Here, we report the morphological and structural trajectories of
hollow PtNi/C nanoparticles during thermal annealing under vacuum, N2,
H2, or air atmosphere by in situ transmission electron microscopy and synchrotron X-ray diffraction. We evidence atmosphere-
dependent restructuring kinetics, which enabled us to synthesize a set of catalysts with identical chemical compositions and
elemental distributions but different morphologies, crystallite sizes, and lattice strain. By combining the results of Rietveld and
pair-distribution function analyses and electrochemical measurements, we demonstrate that the structurally disordered areas
located at the interface between individual crystallites are highly active for two reactions of interest for PEMFC devices: the
electrochemical COads oxidation and the ORR. These results shed fundamental light on the effect of structural defects on the
catalytic performance of bimetallic nanomaterials and should aid in the rational design of more efficient ORR electrocatalysts.
KEYWORDS: proton exchange membrane fuel cell, oxygen reduction reaction, platinum−nickel alloy, hollow nanoparticles,
structural defects, grain boundary, vacancy

■ INTRODUCTION
In both gas-phase and liquid catalysis, the reactivity of extended
and nanometer-sized surfaces strongly depends on their
crystallographic orientation, the average coordination number
of the atoms, and the amount and type of structural defects that
they exhibit.1−4 In that respect, the structure sensitivity of
platinum (Pt) and platinum-based alloys (Pt-alloy) for the
electrochemical oxidation of COads is particularly illustrative.
This two-electron reaction can be performed either in the
absence of CO in solution (“COads stripping” experiments) or
in its presence (“bulk CO” electrooxidation experiments).
There are evidences that open, low-density Pt(110) and
Pt(100) facets are more active than the close-packed Pt(111)
surface in COads stripping experiments.5 The influence of
structural defects is well-established for this reaction: on
stepped Pt[n(111)x(111)] single crystals, the onset and the
peak potential of COads electrooxidation shift toward negative
potentials with an increase in the step fraction.6,7 This indicates
Received: April 18, 2016
Revised: June 2, 2016
Published: June 7, 2016

© 2016 American Chemical Society 4673 DOI: 10.1021/acscatal.6b01106

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that (i) steps are the “active sites” where water is dissociated
into oxygen-containing species (referred to as OHads in what
follows), which are necessary to complete the COads electro-
oxidation, and that (ii) adsorbed CO molecules diffuse rapidly
to these active sites. Note also that the structure sensitivity is
maintained in the presence of CO in the electrolyte.8
At the nanometer scale, and in contrast to what could be
expected on the basis of single-crystal studies, the onset and the
peak potential in COads stripping voltammograms shift toward
positive potential when the fraction of highly undercoordinated
atoms increases (that is, when the size of the Pt nanocrystallites
decreases).9−12 This is related to the decrease of the COads
diffusion coefficient and of the rate of the COads + OHads
recombination on Pt nanocrystallites with size less than 3−4
nm.9,13 Strikingly, the “negative” particle size effect levels off
upon nanoparticle aggregation. The kinetics of the CO
electrooxidation9−11,14 and of more complex molecules,
including formic acid,15 methanol,14−16 and ethylene glycol,17,18
is significantly enhanced on “multi-grained” nanostructures
formed by agglomerated Pt/C nanoparticles. The enhancement
in catalytic activity has been ascribed to the structurally
disordered areas formed at the interface between crystal grains
(also referred to as “grain boundaries” in what follows).
Interestingly, the same holds true when a more oxophilic metal,
such as Ru or Sn, is alloyed to Pt: “multi-grained” Pt-alloy
nanoparticles remain intrinsically more active than isolated Pt-
alloy nanoparticles for the electrooxidation of COads,19−22
methanol,20,23 and ethanol,18,24 confirming that grain bounda-
ries play a key, yet underestimated, role in electrocatalysis.
Structural defects also influence the rate of electroreduction
reactions. On vicinal Pt surfaces, the kinetics of the oxygen
reduction reaction (ORR) increase with an increase in the step
density, irrespective of the step site symmetry.25−30 This effect
was recently rationalized by Bandarenka et al.,30 who postulated
that the OHads binding energy on (111) terraces is weakened
when the step density increases. Similarly to what was reported
for electrooxidation reactions, the catalytic activity for the ORR
is depreciated when going from bulk Pt surfaces to nano-
particles (the specific activity decreases by a factor of 4 going
from bulk Pt to 2 nm sized crystallites31,32). However, even if
the beneficial effect of steps and kinks on the ORR rate has
been documented for nanocatalysts,33,34 the impact of grain
boundaries, vacancies, and cavities remains understudied.
Recently, Wang et al.35 loaded carbon nanotubes with different
Pt mass fractions (in the range of 10−93 wt %). The authors
reported aggregation of the Pt/C nanoparticles at mass fraction
greater than 20 wt % concomitant with a positive shift of the
half-wave potential in ORR curves (enhanced catalytic activity).
However, these results should be taken with caution, since the
Pt loadings (the mass of Pt per geometrical surface area) were
not identical in the different experiments. Using the same
approach, Nesselberger et al.36−38 evidenced an increased
specific activity for the ORR on highly loaded Pt/C
nanoparticles. These findings were rationalized by considering
the overlap of the electrical double layers between adjacent Pt
nanoparticles and the associated change of the electrochemical
potential at the compact layer,36,39 but the possible link
between enhanced ORR electrocatalytic activity and grain
boundaries was not considered. In addition to grain boundaries,
recent ab initio calculations2,3,40 and experiments from Adzic’s
group41 and from the authors42−45 underlined the beneficial
effect of point (vacancies) and bulk defects (cavities; i.e., a
cluster of vacancies) on the ORR kinetics. By means of density
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functional theory (DFT) calculations, Calle-Vallejo et al.3
showed that cavities modify the average coordination number
of Pt atoms and enhance their catalytic activity for the ORR by
a factor close to 3 relative to a cavity-free Pt surface. This is in
line with the DFT findings of Callejas-Tovar et al.40 that
subsurface vacancies compress the Pt lattice parameter and
reduce the affinity for oxygenated species, thereby enhancing
the ORR kinetics on Pt-based catalysts.
Here, hollow nanoparticles composed of a PtNi shell
surrounding a hollow core were synthesized by a combination
of galvanic replacement and nanoscale Kirkendall effects (a
vacancy-mediated diffusion mechanism in binary alloys where
one species diffuses faster than the other). Using high-
resolution transmission electron microscopy (HR-TEM), we
show that the PtNi shell is highly disordered and composed of
nanocrystallites interconnected by structurally disordered areas
(“grain boundaries”). Thermal treatments under different
atmospheres (vacuum, N2, H2, or air) were used to heal
these structural defects in a controlled manner, resulting
eventually in the collapsing of the hollow nanoparticles. This
provided us with a set of catalysts featuring identical chemical
compositions and elemental distributions but different
crystallite sizes, lattice strains, and morphologies, which was
used to shed light on the structure sensitivity of the
electrochemical COads oxidation and the ORR.
■
RESULTS AND DISCUSSION
Synthesis and Characterization of Hollow PtNi/C
Nanoparticles. Hollow PtNi nanoparticles supported on
high surface area carbon with a Ni fraction of 15 at. % were
synthesized via a one-pot method first introduced by Bae et
al.46 During the synthesis, Ni/C or Ni-B/C nanoparticles are
believed to form first47 and then act as sacrificial templates for
the deposition of Pt2+ ions via galvanic replacement (a simple
and spontaneous electrochemical process where the oxidation
of Ni atoms provides electrons for the deposition of Pt2+
atoms). The continuous corrosion of Ni atoms progressively
creates a gradient in chemical potential between the core (rich
in Ni) and the external surface (where Ni atoms are leached
out) and acts as a strong driving force for Ni atoms to diffuse
outward. This in turn drives a flux of vacancies in the opposite
direction, which coalesce in the center of the material
(“nanoscale Kirkendall effect”) and ultimately results into
hollow PtNi/C nanoparticles with a cavity similar in size/shape
to that of the initial Ni or Ni-B/C nanoparticles.48−53 The
scenario described above is supported by the high angle annular
dark field in scanning transmission electron microscopy
(HAADF-STEM) images and the X-ray energy dispersive
spectroscopy (X-EDS) chemical maps displayed in Figure 1. In
particular, the presence of a central void in the as-synthesized
PtNi/C nanoparticles and the homogeneous distribution of Pt
and Ni atoms in the outer shell are clear evidences that the
nanoscale Kirkendall effect operated during the synthesis.
Figure 1 also shows the morphological changes of hollow
PtNi/C nanoparticles upon thermal annealing at T = 400 °C
under N2, H2, or air atmosphere. Some chemical and structural
parameters of the as-synthesized hollow and thermally annealed
PtNi/C nanoparticles, in particular the chemical composition
determined by X-EDS on hundreds of nanoparticles (low-
magnification TEM images) or on individual nanoparticles
(high-magnification STEM-XEDS images), are displayed in
Table 1.
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Figure 1. HAADF-STEM images, line scan analysis, and elemental
distribution in the hollow PtNi/C nanoparticles treated at 400 °C
under different atmospheres. A HAADF image is displayed in (a) and
STEM images in (b)−(d). In the elemental maps (middle) and in the
line scans (right), the Pt atoms are represented in red and the Ni
atoms in green. The X-EDS signals recorded at each point of the line
scan (blue line) are displayed on the right-hand side.
Morphological Changes of Hollow PtNi/C Nano-
particles during Thermal Annealing. Conventional TEM
images of the as-synthesized and thermally annealed PtNi/C
nanoparticles are displayed in Figure 2a−d. They show that the
fresh PtNi/C nanoparticles are polydisperse with respect to size
(10−15 nm) and shape (spherical to ellipsoidal). Details on the
average inner and outer diameters of the fresh hollow PtNi/C
nanoparticles may be found in Figure S3 of ref 44.
The HR-TEM images of Figure 2 indicate that the PtNi shell
of the as-synthesized hollow nanoparticles is composed of
individual nanocrystallites ca. 2−3 nm in size featuring different
crystallographic orientations and being interconnected by
structurally disordered regions. This polycrystalline nanostruc-
ture suggests that multiple Pt nucleation centers formed on the
initial Ni or Ni−B/C nanoparticles grew and then contacted
each other. It is important to stress that the structural disorder
is not limited to the grain boundaries: the PtNi lattice is also
distorted in the individual crystallites, therefore prohibiting any
clear indexation of the lattice planes present (Figure 3). The
interplanar distance measured for different crystallites was on
average 2.18 ± 0.06 Å, suggesting (111) planes in a face-
centered cubic (fcc) PtNi structure (Figure 3d,e). This distance
is shorter than that in pure solid Pt nanocrystallites of the same
Table 1. Chemical and Structural Parameters of the Electrocatalysts Evaluated in This Worka
X-EDS
at. comp (%) from analyses on hundreds of
nanoparticles (low magnification)
solid Pt/C Pt100Ni0
bulk Ni (PDF card no.
00-004-0850)
fresh hollow PtNi/C Pt86±2Ni14±2
hollow PtNi/C after thermal Pt87±2Ni13±2
annealing under N2
hollow PtNi/C after thermal Pt87±2Ni13±2
annealing under H2
hollow PtNi/C after thermal Pt88±2Ni12±2
annealing under air
a
The atomic composition (at. comp) was determined by X-EDS on hundreds of nanoparticles (low-magnification TEM images) or on individual
nanoparticles (high-magnification STEM-XEDS images).
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size, indicating that the Pt atoms strained to accommodate the
lattice of the Ni-rich/C sacrificial template.
Post-synthesis thermal treatments were performed to control
the concentration of these structural defects, following the
approach described by Wang et al.54 for Pt3Co/C nanoparticles.
The authors reported that (i) surface atoms relaxed at 300 < T
< 400 °C and (ii) Pt and Co atoms segregate in the topmost
and second surface layers at T > 400 °C. Similar results by
other groups validated the thermal-annealing approach for
various Pt-based alloys.54−58 Figure 4 illustrates the morpho-
logical changes of hollow PtNi/C nanoparticles upon annealing
under vacuum.
Minor changes in morphology were noticed for T < 400 °C.
A nanoscale secondary void (indicated by arrows in Figure 4d)
formed at T ≥ 400 °C, concomitant with a change in size and
shape of the central cavity. This void then interdiffused to the
outer surface at 500 °C and annihilated at 600 °C, in agreement
with the Kirkendall theory.48,49 The hollow PtNi/C nanostruc-
tures collapsed between 600 and 700 °C, resulting in the
formation of solid PtNi/C nanoparticles. During this process,
the number of individual grains was divided roughly by a factor
of 3, in agreement with the ex situ HR-TEM images displayed
in Figure 2.
The restructuring kinetics were found to be strongly
dependent on the size of the central void: the hollow PtNi/C
nanoparticles featuring the smallest central void collapsed at
temperatures lower than those with larger voids (this is clearly
visible if one compares Figure 4 and Figure S1 in the
Supporting Information, where another series of STEM-
HAADF images is displayed). This suggests that the
restructuring of hollow nanoparticles is thermodynamically
driven (as the passage from two to one surface minimizes the
total surface energy of the nanoparticle) but is kinetically
limited by the amount of vacancies contained in the central
void (that is, the size of the hollow core). Keeping the same
idea in mind, we emphasize that the kinetic Monte Carlo
simulations of Gusak et al.59 showed that the time to collapse
for a hollow nanoparticle depends also on the temperature, the
radius of the collapsed nanoparticle, the surface tension of the
metal(s) considered, their atomic volume, and their inter-
diffusion coefficients.
In addition, we noticed a significant influence of the gas
atmosphere on the restructuring kinetics. As shown by Figure 5,
the rearrangement of PtNi atoms initiated at 210 °C in the
presence of oxygen and was complete at 280 < T < 350 °C.
XRD
lattice lattice param
at. comp (%) from analyses on individual param contraction vs Pt/C
nanoparticles (high magnification) (nm) (%)
Pt100Ni0 0.3933 0
0.3524 10.4
Pt88±2Ni12±2 0.3869 1.6
Pt88±5Ni12±5 0.3908 0.6
Pt90±1Ni10±1 0.3886 1.2
Pt89±1Ni11±1 0.3902 0.8
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Figure 2. Conventional TEM and aberration corrected HR-TEM images of the as-synthesized and thermally annealed PtNi/C nanoparticles: (a−d)
assemblies and (e−h) HR-TEM images of the as-synthesized PtNi/C nanoparticles and after thermal annealing at 400 °C under different
atmospheres. Zoom-in images of the fine nanostructure of the PtNi shell are shown in (i−l). The boundaries between the individual PtNi
nanocrystallites are highlighted in color.
This result is ascribed to the decrease of the surface energy
upon chemisorption and the enhanced diffusivity of Pt atoms
under hydrogen or oxygen coverage. As shown on Pt single
crystals, the motions of Pt surface atoms are much faster under
a gas atmosphere,60,61 and facilitate the restructuring of the bulk
of the nanoparticles.62 Convincing evidence of enhanced
restructuring of Pt nanoparticles under gas atmosphere may
also be found in the study by Cabie et al.63 The authors showed
that exposure of cubic Pt nanoparticles to an O2 or H2
atmosphere promotes the development of (001) or (111)
facets, respectively. The shape changes were found to be
reversible and were also observed for Cu,64 Rh,65 and Pd66
nanoparticles.
Interestingly, slight segregation of Ni or Pt atoms to the
surface and subsurface layers was observed upon thermal
annealing under air or H2 atmosphere by electron energy loss
spectroscopy (EELS) elemental maps (Figure S2 in the
Supporting Information) or local X-EDS analyses (Figure S3
in the Supporting Information). A slight enrichment in Pt in
the surface and near-surface layers was observed upon thermal
annealing under H2 by local X-EDS analyses (Figure S3), in
agreement with the findings of refs 67−69. Similarly, after
thermal annealing under an air atmosphere, the surface of the
PtNi/C nanoparticles was slightly enriched in Ni, in agreement
with refs 56 and 70. Note, however, that surface enrichments
detected by X-EDS remained within the incertitude bar of the
analyses (±1−2 at. %; see Table 1) and that X-EDS and EELS
cannot provide quantitative insights into the composition of the
surface and near-surface layers (these are bulk techniques). To
better quantify the surface composition resulting from thermal
annealing, X-ray photoelectron (XPS) measurements were
performed. The results displayed in Figure S4 showed that the
Ni content and the oxidation state of Pt and Ni atoms located
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in the surface and near-surface region increased upon thermal
annealing under hydrogen, most impressively after thermal
annealing under air. We rationalized this by considering that,
due to the acid leaching step performed in the last step of the
synthesis, the fresh hollow PtNi/C nanoparticles feature a
“skeleton” structure composed of a 2−3 monolayer thick Pt
shell covering the mother PtNi alloy. Therefore, thermal
annealing at T = 400 °C led to a more homogeneous
distribution of Pt and Ni atoms, resulting in an increased Ni/Pt
ratio at the surface (Figure S4A) with (Ni/Pt)air > (Ni/Pt)H2 >
(Ni/Pt)fresh. Moreover, we found that thermal annealing under
air atmosphere facilitated the formation of Pt and Ni oxides
(Figure S4B,C), in agreement with former reports of Menning
et al.71 and Ahmadi et al.56,70 on the PtNi system and of Xin et
al.72 on PtCo nanoparticles, respectively. However, it is
important to note that the electrocatalytic activity of the
PtNi/C nanoparticles is only mildly affected by chemical
changes in the surface and near-surface layers. Indeed, in acidic
electrolyte and especially under ORR conditions, Ni atoms are
leached out from the first 2−3 monolayers. This is clearly
visible in Figure 1 if one compares the X-EDS line-scan profiles
for Pt and Ni atoms. Convincing evidence was also provided by
Durst et al.69 with the help of aberration-corrected scanning
transmission electron microscopy (HR-STEM) and EELS
elemental mapping that Co atoms are removed from the
second and third atomic layers of Pt3Co/C nanoparticles upon
exposure to an acidic environment. The change in structure was
fast and independent of the configuration of the starting Pt3Co/
C nanoparticles: Pt3Co/C alloy or Pt skin nanostructure (Pt
skin refers to a configuration in which the outermost surface
layer is Pt rich, while the second layer is Ni rich). In other
words, the surface and near-surface composition of the fresh or
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Figure 3. Lattice distortions in the shell of the as-synthesized hollow PtNi/C nanoparticles: (a) HR-TEM image, (b, c) zoom-in images of the PtNi
shell. The white boxes with dotted line indicate the regions over which the interplanar distances displayed in (d, e) have been measured. These
distances are expressed in angströms.
thermally annealed PtNi/C electrocatalysts under operando
conditions is assumed to be Pt rich.
Structural Changes of Hollow PtNi/C Nanoparticles
during Thermal Annealing under Different Atmos-
pheres. To gain insights into the structural changes occurring
on the hollow PtNi/C nanoparticles during thermal annealing
under different atmospheres, in situ laboratory X-ray diffraction
(XRD) experiments were performed (the in situ XRD spectra
taken at different holding temperatures are displayed in Figures
S5−S7 in the Supporting Information), and the thermally
annealed samples were then analyzed ex situ with synchrotron
XRD radiation. A pronounced narrowing of the XRD peaks
(signaling the growth of the PtNi crystallites) was observed
during thermal annealing under H2 or air (Figure 6), thereby
confirming the electron microscopy findings obtained under
the same experimental conditions. A contrario, the XRD peaks
remained broad for the fresh hollow PtNi/C nanoparticles
before/after thermal annealing under N2. Along with these
changes, the XRD patterns systematically shifted toward smaller
2θ angles upon thermal annealing: i.e., the PtNi lattice relaxed,
whatever the gas atmosphere. Similarly to what was found for
the changes in morphology, the relaxation of the PtNi lattice
was gas dependent, being maximum under N2, less pronounced
under air, and minimum under H2. Since the Ni content and
the elemental distribution remained identical in the fresh and
the heat-treated PtNi/C nanoparticles, this result is ascribed to
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atmosphere-dependent healing of point (vacancies), surface
planar (grain boundaries), and bulk defects (voids, cavities).
To separate the effects of crystallite size and microstrain
(inhomogeneous interplanar distance) on the broadening of
the XRD peaks, the synchrotron XRD patterns were refined
with the Rietveld method after accounting for the instrumental
broadening (Figure 6). Complementary to Rietveld refinement,
an atomic pair distribution function (PDF) analysis of the
synchrotron data was carried out. The measured and fitted
XRD patterns may be found in Figures S8 and S9 in the
Supporting Information, and the parameters used for the
Rietveld and PDF analyses are given in Tables S1 and S2 in the
Supporting Information, respectively.
The results of the Rietveld analysis indicated that the
coherent domain size varied by a factor of 3 during thermal
annealing (Figure 6b) but always remained between 3.3 and
10.1 nm, i.e., much smaller than the diameter of the hollow
nanoparticles. This confirms the HR-TEM images showing that
the hollow PtNi/C nanoparticles are formed by several
crystallites (grains), which have no structural coherence
between them. In all of the samples, the PtNi nanocrystallites
featured anisotropic shapes and were found elongated along the
[111] direction. The anisotropy (difference between the
longest and shortest directions) was close to ∼6−7 nm,
independent of the average crystallite size. Finally, the Rietveld
analysis revealed that microstrain significantly contributes to
the broadening of the XRD peaks for the fresh and the N2-heat-
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Figure 4. In situ snapshots of the structural changes occurring on hollow PtNi/C nanoparticles during thermal annealing under vacuum: (a, c)
aberration-corrected HAADF-STEM and (b, d) bright-field-STEM (BF-STEM) images. The heating rate was 20 °C min−1. Thirty minute steps were
performed at each temperature of interest. Note that the scale bar is different in the sixth column (700 °C) of (c, d) relative to the other columns. In
these images, the magnification was changed to illustrate that the collapsed PtNi nanoparticles remained polycrystalline upon thermal annealing.
Arrows indicate the formation, interdiffusion, and annihilation of a nanoscale secondary void at T ≥ 400 °C.

treated hollow PtNi/C samples and is reduced upon thermal
annealing under H2 or air (Figure 6d), during which the
average crystallite size increased markedly.
The results of the PDF analysis were remarkably similar
(note, however, that anisotropic size effects are not taken into
account by this analysis, therefore explaining why it systemati-
cally yields smaller crystallite sizes). The PDF refinements
showed that the thermally annealed PtNi/C nanoparticles
maintained an fcc structure but that the lattice parameter
relaxed significantly under the different gas atmospheres. We
also noticed that the values of the atomic displacement
parameter Uiso (determined by PDF refinement) and of the
microstrain (determined by Rietveld analysis) were linearly
correlated. Since Uiso reflects the distribution of interatomic
distances from their average values and thus incorporates the
effects of microstrain, this result confirms the variations of the
microstrain for the different samples.
As illustrated in Figure S10 in the Supporting Information, a
large part of the microstrain arises from the nanometric
dimension of the metal crystallites. This should be correlated to
the 4υmγ/d term in the Gibbs−Thomson equation,73 which
quantifies the increase of the chemical potential for nanoma-
terials relative to the bulk (υm is the molar volume, γ is the
surface tension, and d is the crystallite size). However, due to
the large concentration of structural defects in the hollow PtNi/
C nanocrystallites, the microstrain is more pronounced in
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hollow nanoparticles relative to solid nanoparticles with
identical crystallite size (Figure S10).
Finally, we emphasize that no direct relation exists between
the PtNi lattice relaxation and the microstrain broadening. This
is because the microstrain represents the local deviation from
the average lattice parameter (i.e., Δa/a, where a is the lattice
parameter) caused by the structural defects. An illustration of
this may be found in Figure 6c,d: the PtNi/C nanoparticles
which were thermally annealed under an H2 atmosphere feature
a more compressed lattice constant (by 1.2%) in comparison to
those thermally annealed under air (0.8%), but both catalysts
have similar microstrain. The same holds true for the PtNi/C
nanoparticles in the fresh state and after thermal annealing
under N2 (similar microstrains but different lattice constants).
Structure−Catalytic Activity Relationships. Motivated
by these very different structural characteristics, we investigated
the catalytic activity of the fresh and thermally annealed PtNi/C
nanoparticles for two reactions of interest for PEMFC devices:
the electrochemical COads oxidation and the oxygen reduction
reaction. Figure 7 shows a clear relationship between the
concentration of structural defects and the catalytic activity of
the PtNi/C nanoparticles for the COads electrooxidation. Two
oxidation prepeaks at 0.66 < E < 0.70 V vs RHE dominate the
reactivity of the fresh and the N2-annealed hollow PtNi/C
nanostructures. In contrast, a peak located at 0.80 < E < 0.82 V
vs RHE predominates in the COads stripping voltammograms
performed on the solid Pt/C and the solid PtNi/C nano-
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Figure 5. In situ monitoring of the structural changes occurring on hollow PtNi/C nanoparticles during thermal annealing under oxygen at
atmospheric pressure: aberration-corrected (a, c) HAADF and (b, d) STEM images. The heating rate was 30 °C min−1.
Figure 6. Structural parameters of the fresh and the heat-treated
hollow PtNi/C nanoparticles and the reference Pt/C material used in
this study: (a) synchrotron XRD spectra after linear heating from
room temperature to 400 °C at a rate of 2 °C min−1; (b) average
crystallite size; (c) lattice parameter; (d) microstrain estimated by
Rietveld analysis of the XRD spectral pattern.
particles (which were thermally annealed in H2 or in air). The
contribution of the COads electrooxidation prepeaks to the total
electrooxidation charge was maximum for the fresh and the
heat-treated under N2 hollow PtNi/C nanoparticles (featuring a
high concentration of grain boundaries) and minimum for the
PtNi/C nanoparticles thermally annealed under H2 or air and
the reference solid Pt/C material.
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Figure 7. Electrocatalytic activity of the hollow and solid PtNi/C and
the reference solid Pt/C nanoparticles for the electrochemical COads
oxidation: iR-corrected (a) base and (b) COads stripping voltammo-
grams measured on the hollow and the solid PtNi/C nanoparticles and
the reference Pt/C material. Conditions: Ar-saturated 0.1 M HClO4; v
= 0.020 V s−1; 25 ± 1 °C; no rotation of the electrode; Pt loading 20
μgPt cm−2geo.
A second structure−activity relationship appears if the
catalysts are sorted into two distinct groupsthe hollow
PtNi/C nanoparticles (fresh and thermally annealed under N2)
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Figure 8. Electrocatalytic activity of the hollow and solid PtNi/C and the reference Pt/C nanoparticles for the oxygen reduction reaction. (a) Linear
sweep voltammograms. (c) Tafel plots of ohmic and mass transport corrected linear sweep voltammograms displayed in (a). (b) and (d) are the
specific and mass activities (MA0.95) for the ORR determined at E = 0.95 V vs RHE. Conditions: O2-saturated 0.1 M HClO4: potential sweep rate
0.005 V s−1; ω = 1600 rpm; positive-going potential sweep from 0.20 to 1.05 V vs RHE; temperature 25 ± 1 °C; Pt loading 20 μgPt cm−2geo. The
error bars are the standard deviation of at least three independent measurements.

and the solid PtNi/C nanoparticles (thermally annealed under

air or H2)and compared pairwise. Within both groups, the
PtNi/C nanocatalysts featuring relaxed lattice parameters better
catalyze the COads monolayer electrooxidation, as deduced
from the shift of the onset and the peak potential to lower
potential value (Figure 7b). These results can easily be
understood in view of the higher affinity of relaxed PtNi
lattices for OHads species,74,75 which are required to complete
the electrooxidation of the COads monolayer. From a more
global perspective, the results indicate that the CO ads
monolayer electrooxidation is a fast and effective way to
check the affinity of bimetallic Pt-alloy nanocatalysts for
oxygenated species.
An opposite structure−catalytic activity relationship was
found for the ORR (Figure 8). In agreement with the
literature,75,76 the electrocatalysts featuring the more com-
pressed PtNi lattice were catalytically more active for the ORR.
This may again be easily rationalized in the frame of the d band
theory,77−79 which states that a compression of the Pt lattice
results in a downshift of its average energy with respect to the
Fermi level. This downshift in turn weakens the binding energy
of ORR intermediates (OHads and OOHads) and accelerates the
ORR kinetics.
Strikingly, for nanocatalysts featuring similar lattice constants,
the ORR rate was strongly enhanced in the presence of grain
boundaries and vacancies (Figure 9). Since (i) no Ni was lost
and (ii) the chemical composition of the topmost and near-
surface layers remains Pt rich under operando conditions
(acidic electrolyte), the better electrocatalytic activity of the
hollow PtNi/C nanocatalysts can only be related to their
unique structural arrangement: i.e., to their hollow nanostruc-
ture. In our last paper,44 we ascribed the enhanced ORR
kinetics on hollow PtNi/C nanoparticles relative to solid PtNi/
C nanoparticles to a combination of strain and ensemble effects
and to their porous architecture. The present study shows that
4680
Figure 9. Dependence of the specific activity for the ORR measured at
E = 0.95 V vs RHE on the lattice parameter and the nanostructure/
concentration of grain boundaries and atomic vacancies of/in the
nanoparticles.
structural defects, such as grain boundaries and vacancies, also
contribute to the catalytic enhancement. We rationalize our
findings in the framework of the recent DFT “coordination-
activity” plots of Calle-Vallejo et al.,3 which evidenced that the
presence of subsurface cavities on a Pt(111) surface locally
increases the mean coordination number of the surface atoms
and enhances their ORR activity. Our results show for the first
time that grain boundaries and vacancies are beneficial defects
for ORR catalysis. We argue that the lattice distortions and
different atomic packing densities in (or in close proximity to)
these structural defects modify the electronic structure of Pt
atoms and optimize the binding of ORR intermediates. In this
framework, the synchrotron XRD results presented in this
study unequivocally show that microstrain provides catalytic
sites with compressed lattice constants, leading to ORR activity
ascending toward the apex of the Sabatier volcano plot (PtNi
catalysts with Ni fraction less than 25 at. % are located on the
DOI: 10.1021/acscatal.6b01106
ACS Catal. 2016, 6, 4673−4684
ACS Catalysis
strong-binding side of the volcano plot).55,75,76 Hence, the
combination of a hollow nanostructure and of a Pt-alloy/C
nanocatalyst is beneficial to ORR catalysis: first because the
hollow-induced large microstrain allows accessing a large set of
Pt−Pt bond distances and second because microstrain is stable
unless a high-temperature annealing procedure is employed
(Figures 4 and 5). This is in contrast with (but complementary
to) conventional Pt-alloy/C catalysts for which strain/ligand
effects are progressively vanishing due to dissolution of the
alloying element in the harsh operating conditions of a
PEMFC, leading ultimately to depreciated ORR ki-
netics.42,76,80−89
■
CONCLUSION
In conclusion, using thermal annealing under different gas
atmospheres, we synthesized a series of PtNi/C nanoparticles
with identical chemical compositions and elemental distribu-
tions but different nanostructures (hollow vs solid), crystallite
sizes, and lattice strains. By combining synchrotron XRD, in
situ TEM, and electrochemical measurements, we provided
experimental evidence that structural defects such as grain
boundaries and vacancies enhance the kinetics of two reactions
of interest for PEMFC electrocatalysis: the electrochemical
COads monolayer oxidation and the ORR. Our results shed
fundamental light on the effect of structural defects on the
catalytic performance of bimetallic nanomaterials and should
ultimately aid in the rational design of electrocatalysts with
enhanced activity for the sluggish ORR, the reaction limiting
the electrical performance of PEMFC devices.
■
MATERIALS AND METHODS
Reference Electrocatalyst. A Pt/Vulcan XC72 catalyst
with a weight fraction (wt %) of 20% was purchased from E-
TeK and used as reference material without any treatment. The
number-averaged Pt nanoparticle size was 2.9 ± 0.6 nm.
Synthesis of Hollow PtNi/C Nanoparticles. The hollow
PtNi/C nanoparticles were synthesized by mixing 0.154 g of
Pt(NH3)4Cl2.H2O (Alfa Aesar, Specpure) and 0.180 g of NiCl2
(Fluka, >98.0%) with 0.3 g of Vulcan XC72R (Cabot), 10 mL
of ethanol, and 140 mL of deionized water (Millipore). An
aqueous solution of NaBH4 (Aldrich 99.99%; 5.5 mmol, 0.22
M) was then added at a rate of 5 mL min−1 and the mixture
stirred for 1 h with magnetic stirring at room temperature (20
± 2 °C). The resulting mixture was filtered, thoroughly washed
with deionized water, and dried for 45 min at 110 °C. The
catalyst powder was then acid-treated for 22 h in a stirred 1 M
H2SO4 solution at 20 °C.
Laboratory X-ray Diffraction Measurements. The
synthesized and reference electrocatalysts were analyzed using
a PANalytical X’Pert Pro MPD vertical goniometer/diffrac-
tometer equipped with a diffracted-beam monochromator using
Cu Kα mean radiation (λ = 0.15418 nm) operating at 45 kV
and 40 mA. The 2θ angle extended from 10 to 125° and varied
using a step size of 0.033°, accumulating data for 525 s. In situ
XRD spectra on the hollow PtNi/C nanoparticles were
recorded during thermal annealing from room temperature to
400 °C at a heating rate of 2 °C min−1. The heating assembly
(Anton-Paar DHS 1100) consisted of a chemically resistant
ceramics heating plate and a homemade stainless-steel crucible
(sample holder). A domed-shape X-ray transparent window
made of graphite, which was fixed on the heating assembly,
allowed control of the gas atmosphere.
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Synchrotron X-ray Diffraction Measurements. The
synchrotron XRD measurements were performed at the ID31
beamline at the European Synchrotron Radiation Facility
(ESRF) in Grenoble, France. Radiation from one undulator was
monochromatized with a multilayer monochromator (band-
width 0.3%) to the final energy of 60.0 keV (λ = 0.207 Å). The
X-ray beam was focused with two transfocators to the final size
of 5 μm × 20 μm (vertical × horizontal relative to the plane of
the accelerator ring), and the flux at the sample position was 5
× 1012 photons s−1. The data were collected using a
PerkinElmer 2D detector and azimuthally integrated using
the pyFAI software package.
The Rietveld refinements were carried out using FullProf.90
The XRD pattern of a CeO2 sample was used to determine the
instrument resolution function. The refinements were based on
the structure of a cubic close-packed metal (Fm3̅m, a ≈ 3.9 Å),
including a polynomial description of the background. The best
agreements were obtained with a description of peak shape
using the TCH function,91 including an isotropic description of
microstrain and a uniaxial anisotropic description of particle
sizes, with the [111] direction as main axis. The refined
parameters and agreement factor values are summarized in
Table S1 in the Supporting Information and the refined plots in
Figure S9 in the Supporting Information. The PDFs were
obtained from the same patterns using PDFGetX3.92 The data
were considered up to Qmax = 23 Å−1. The pattern from a
capillary containing only the carbon phase used in the
nanoparticle samples was subtracted from the data. The PDF
of the CeO2 standard was used to determine the instrumental
parameters (damping and broadening of PDF peaks due to
experimental resolution), which were then fixed during the
PDF refinements, carried out with PDFgui.93 The refinements
were carried out for 1 ≤ r ≤ 40 Å on the basis of the same
metal structure as for the Rietveld refinements. The refined
parameters were a scale factor, the a cubic cell parameter, the δ
parameter taking into account linear atomic correlations, the
isotropic overall atomic displacement parameter (adp) Uiso, and
the parameter D corresponding to the diameter of the isotropic
coherent domain size. The results are shown in Table S2 in the
Supporting Information, and the refinement plots are shown as
Figure S8 in the Supporting Information.
X-ray Photoelectron Spectroscopy Measurements.
The XPS measurements were acquired in an ultra-high vacuum
chamber (10−10 mbar base pressure, 10−8 mbar during the
measurements) equipped with a hemispherical analyzer (VSW
H100) and monochromatic X-ray source (SPEC XR-50)
operating at 270 W (13.5 kV, 20 mA). The hemispherical
analyzer was working in the constant pass energy mode (44
eV). Analyses were carried out at an angle of 60° between the
sample surface and the analyzer axis. The XPS data signals were
taken in increments of 0.25 eV with dwelling times of 10 s. The
PtNi/C electrodes were prepared by depositing a nonquantified
amount of powder on carbon scotch, which was then glued
onto a molybdenum block and introduced into the XPS
chamber within 3 h before the measurements. The XP spectra
were analyzed using the CasaXPS software from CasaSoftware
Ltd. using the Shirley background corrections, asymmetric peak
shapes for Pt 4f doublets, and blend of Lorentzian and Gaussian
peak shape for Ni 2p doublets. The reference was a partially
oxidized Ni foil.
Conventional TEM Measurements and X-EDS Map-
ping. The electrocatalysts were examined with a JEOL 2010
TEM instrument operated at 200 kV with a point to point
DOI: 10.1021/acscatal.6b01106
ACS Catal. 2016, 6, 4673−4684
ACS Catalysis
resolution of 0.19 nm. The X-EDS elemental maps were
acquired using a JEOL 2100F microscope operated at 200 kV
and equipped with a SDD Centurio retractable detector. The
X-EDS spectra were recorded on individual nanoparticles by
scanning the beam in a square region adjusted to the particle
size. The quantitative analyses were performed on Pt L and Ni
K lines using the K factor provided by the JEOL software.
In Situ TEM Measurements. The in situ measurements
under vacuum or O2 environment were performed using a
JEOL 2100F TEM/STEM electron microscope equipped with
a Cs probe corrector. The images were acquired in the STEM
mode using simultaneously both the HAADF (high angle
annular dark field) and BF (bright field) detectors. For the in
situ measurements under vacuum, a Gatan heating holder was
used, and the PtNi/C electrocatalysts were deposited on a
classical TEM grid covered by a carbon membrane. The sample
was heated from room temperature to 700 °C at a rate of ca. 20
°C min−1, and held for 30 min at each temperature. For the in
situ measurements under oxygen, a Protochips Atmosphere
Gas environmental cell was used. The PtNi/C electrocatalysts
were deposited on the Si3N4 membrane in contact with the SiC
heating ceramic device (E chips) submitted to a pure oxygen
environment at atmospheric pressure. The specimen was
heated from room temperature to 450 °C at a rate of ca. 30
°C min−1 and held for 30 min at each temperature.
Aberration-Corrected HR-TEM and Spectrum-Imaging
EELS. Aberration-corrected HR-TEM images and two-dimen-
sional spatially resolved EELS elemental maps were acquired
with a JEOL-ARM 200F (JEOL) transmission electron
microscope equipped with a cold-field emission gun operated
at 200 kV and a CEOS aberration corrector of the objective
lens.94 For the TEM studies, the PtNi nanoparticles were
dispersed in dry conditions on holey film copper TEM grids
(Agar Scientific Ltd.). The TEM investigations were under-
taken on nanoparticles lying over the holes of the thin holey
carbon films to eliminate the contribution of the latter to the
HR-TEM and EELS signals.
For spatially resolved EELS, the microscope was operated in
STEM mode with the probe size setting “5c” and convergence
and collection angles set at 32 and 100 mrad, respectively. EEL
spectra were acquired using a Gatan Quantum ER imaging filter
fitted with a fast CCD camera with a selected energy dispersion
of 0.5 eV per pixel and a vertical binning of ×26. To analyze the
Pt and Ni distribution within the nanoparticles, core-loss
spectra over a large energy domain (∼300−1500 eV)
containing both Pt-N3 (518 eV) and Ni-L2,3 (855 eV) were
acquired in the spectrum-image (SI) mode. In this mode, the
EELS data are captured sequentially in space by scanning in a
controlled way the focused electrons at the surface of the
sample and acquiring the loss signal over the energy range of
interest at each probe position. In the present study, the core-
loss EEL spectra were acquired over square or rectangular areas
enclosing the nanoparticles with an acquisition time of 0.7−1 s
per spectrum. To compensate for spatial drift of the sample
during EELS acquisition, a drift correction was applied at the
end of each row of the SI. Spectral drifts in the core-loss spectra
were monitored and corrected by acquiring, in parallel to each
core-loss SI, the corresponding SI of the zero-loss peak (with an
acquisition time of 1 μs per spectrum) using the dual EELS
capability of the imaging filter. Elemental maps were
constructed by analyzing the intensities under the Pt-N3 and
Ni-L2,3 edges after background subtraction using a power-law
model. Prior to the generation of the elemental maps, each SI
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Research Article
was denoised using standard principal component analysis
implemented in the hyperspectral data analysis toolbox
HyperSpy.95
Electrochemical Measurements. All the glassware
accessories used in this study were first cleaned by soaking in
a H2SO4/H2O2 mixture for at least 12 h and thoroughly
washing with ultrapure water. The 1 M H2SO4 solution used for
acid leaching was prepared with Milli-Q water (Millipore, 18.2
MΩ cm, total organic compounds <3 ppb) and H2SO4 96 wt %
(Suprapur, Merck).
The electrochemical measurements were conducted using an
Autolab PGSTAT302N instrument in a custom-made four-
electrode electrochemical cell thermostated at 25 ± 1 °C. Fresh
electrolyte solution (0.1 M HClO4) was daily prepared with
Milli-Q water (Millipore, 18.2 MΩ cm, total organic
compounds <3 ppb) and HClO4 96 wt % (Suprapur,
Merck). The counter electrode was a glassy-carbon plate and
the reference electrode a commercial reversible hydrogen
electrode (Hydroflex, Gaskatel GmbH) connected to the cell
via a Luggin capillary. A Pt wire connected to the reference
electrode was used to filter the high-frequency electrical noise.
More details on the dual-reference system used in this work can
be found in ref 96.
To prepare the working electrodes, a suspension containing
10 mg of Pt/C from the fresh or the heat-treated hollow PtNi/
C nanoparticles, 54 μL of 5 wt % Nafion solution (Electro-
chem. Inc.), 1446 μL of isopropyl alcohol, and 3.6 mL (18.2
MΩ cm) of deionized water (MQ-grade, Millipore) was made.
After sonication for 15 min, 10 μL of the suspension was
pipetted onto a glassy-carbon disk that was then sintered for 5
min at 110 °C to ensure evaporation of the Nafion solvents,
yielding a loading of ca. 20 μgPt cm−2geo. Prior to any
electrochemical experiment, the working electrode was
immersed into the deaerated electrolyte at E = 0.40 V vs
RHE (Ar >99.999%, Messer). One hundred cyclic voltammo-
grams were then recorded in Ar-saturated electrolyte between
0.05 and 1.23 V vs RHE with a potential sweep rate of 0.500 V
s−1 (electrochemical activation), three cyclic voltammograms at
v = 20 mV s−1 under the same potential conditions, and one
COads stripping measurement to determine the electrochemi-
cally active surface area. In the last experiment, the CO
saturation coverage was established by bubbling CO for 6 min
and purging with Ar for 34 min, while the electrode potential
was kept at E = 0.1 V vs RHE. The real surface area was
estimated by assuming that the electrooxidation of a COads
monolayer requires 420 μC cm−2 of Pt. The electrocatalytic
activity for the ORR was measured in an O2-saturated 0.1 M
HClO4 solution (20 min of purging by oxygen >99.99%,
Messer) by linearly sweeping the potential from 0.20 to 1.05 V
vs RHE at a potential sweep rate of 5 mV s−1 and at different
rotational speeds (400, 900, 1600, and 2500 rpm). The ORR
specific/mass activity was determined by normalizing the
current measured at E = 0.95 V vs RHE, after correction
from the oxygen diffusion in the solution and the Ohmic drop,
to the real surface area/mass of deposited Pt determined by
COad stripping voltammetry, respectively.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acscatal.6b01106.
DOI: 10.1021/acscatal.6b01106
ACS Catal. 2016, 6, 4673−4684
ACS Catalysis
In situ TEM images showing the morphological and
structural changes during thermal annealing, local X-EDS
analyses, XPS, laboratory, and synchrotron XRD spectra,
and results of the Rietveld refinements and PDF analysis
(PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail for L.D.: laetitia.dubau@lepmi.grenoble-inp.fr.
*E-mail for F.M.: frederic.maillard@lepmi.grenoble-inp.fr.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was performed within the framework of the Centre
of Excellence of Multifunctional Architectured Materials
“CEMAM” No. ANR-10-LABX-44-01. The authors acknowl-
edge the French CNRS and CEA-METSA network and
financial support from the University of Grenoble-Alpes
through the AGIR program (Grant No. LL1492017G) and
from the French National Research Agency through the
HOLLOW project (Grant No. ANR-14-CE05-0003-01).
■
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DOI: 10.1021/acscatal.6b01106
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4684 DOI: 10.1021/acscatal.6b01106

ACS Catal. 2016, 6, 4673−4684