Available online at www.sciencedirect.
com
Review Article
Recent advances in bimetallic electrocatalysts for
oxygen reduction: design principles, structure-function
relations and active phase elucidation
María Escudero-Escribano∗ , Kim D. Jensen and
Anders W. Jensen
The electrocatalytic oxygen reduction reaction (ORR) is of
fundamental importance for sustainable energy conversion.
Model studies are essential to elucidate the design principles
as well as the structure-activity-stability relations. Knowledge
from extended surfaces combined with fine control of the
nanoscale structure has enabled the development of highly
efficient nanoparticulate catalysts. This review discusses recent
advances in bimetallic electrocatalysts for enhanced ORR, from
model surfaces to nanoparticles. A special focus has been
placed on novel strategies involving morphology-controlled
Pt-based nanomaterials with enhanced mass activity and high
electrochemically active surface area. We conclude by
highlighting the importance of in situ characterisation methods
in order to both elucidate the active phase and understand the
catalyst degradation mechanisms.
Address
Nano-Science Centre, Department of Chemistry, University of
Copenhagen, Universitetsparken 5, DK-2100 Copenhagen Ø, Denmark
∗
Corresponding author.: Escudero-Escribano, María
(maria.escudero@chem.ku.dk)
Current Opinion in Electrochemistry 2018, XX:XX–XX
This review comes from a themed issue on Surface Electrochemistry
Edited by Marc Koper
For a complete overview see the Issue and the Editorial
Available online XX XXXX 2018
https://doi.org/10.1016/j.coelec.2018.04.013
2451-9103/© 2018 Elsevier B.V. All rights reserved.
Introduction
The oxygen reduction reaction (ORR) is one of the
most intensively investigated electrocatalytic reactions.
Its slow kinetics limits the performance of sustainable
energy conversion devices such as low-temperature fuel
cells [1,2]. Under acidic conditions, at which polymer
electrolyte membrane fuel cells operate, only Pt-based
catalysts are both active and stable for this reaction
[3• ,4,5]. The ORR activity depends strongly on the struc-
www.sciencedirect.com
Please cite this article as: Escudero-Escribano, Jensen, Jensen, Recent advances in bimetallic electrocatalysts for oxy-
gen reduction: design principles, structure-function relations and active phase elucidation, Current Opinion in Elec-
ture of the electrode-electrolyte interface [1,6–9]. There-
fore, detailed knowledge of the interface structure is es-
sential to develop efficient catalysts [10–13].
In order to reduce the Pt loading while increasing the
ORR activity, we can modify the geometric arrangement
[12,14] and/or the electronic structure [15,16] of the Pt
surface atoms. The latter can be achieved by alloying Pt
with other metals [5,17]; this has been widely studied
on Pt-late transition metal alloys [17–20,21•• ]. Most re-
cently, a new set of alloys of Pt and rare- and alkaline-earth
metals have shown unprecedented activity enhancement
over pure Pt [22,23,24•• ,25]. Moreover, some Pt-rare earth
alloys have very negative enthalpy of formation [26],
which may stabilise them kinetically against degradation
through dealloying [27].
Inspired by the work on extended surfaces, espe-
cially by the outstanding activity of Pt3 Ni(111) [11,28• ],
tremendous progress has been made on tailored Pt-
based nanocatalysts with enhanced ORR activity in acid
[18,21,29,30,31•• ,32–35]. The development of electrocat-
alysts for alkaline-based fuel cells [36] has recently re-
ceived increasing attention. Beyond Pt-based materials,
catalysts based on non-precious metals such as Ag can be
stable under alkaline conditions [37–39].
Figure 1 shows a comparison of the specific and mass
activities (normalised by mass of precious group
metal, [PGM]) from rotating disk electrode (RDE)
measurements [35,40] for a selection of some of
the most active ORR electrocatalysts in both acidic
[11,15,22,24•• ,30,31•• ,41–46,47•• ,48• ,49–53] (Figure
1a–c) and alkaline [28• ,37–39,54,55•• ,56• ] (Figure 1d–e)
electrolytes. Most of these catalysts have been reported
between 2014 and 2018, indicating how fast the field is
moving. We note that, in alkaline media, a wide array of
benchmarking potentials, electrolytes and scan rates have
been reported in the literature. To further develop this
field, standardised procedures should be implemented.
Although the work on ORR bimetallic catalysts in alka-
line is an emerging field, it is not within the scope of this
review.
Herein, we review the most recent advances in the devel-
opment of efficient Pt-based ORR electrocatalysts. First,
Current Opinion in Electrochemistry 2018, 000:1–12
JID: COELEC
ARTICLE IN PRESS [mNS;June 16, 2018;4:6]

2 Surface Electrochemistry

Figure 1

Specific and mass activity of a selection of the most active state-of-the-art ORR electrocatalysts in 0.1 M HClO4 acidic (a–c) and various alkaline (d
and e) electrolytes at 0.90 V versus the reversible hydrogen electrode (RHE) unless otherwise stated. (a) Specific activity of ORR nanocatalysts in
0.1 M HClO4 ; the electrochemically active surface area (ECSA) was obtained from CO stripping measurements unless otherwise specified below:
commercial Pt/C TKK 46% [41], PtNi3 @HGS [42], Pd@PtNi octahedral nanoparticles (ECSA from Cu underpotential deposition) [43], dealloyed PtNi
nanoparticles (ECSA from H adsorption) [44], PtCu@PtCuNi/C nanoparticles [46], Pt-Co nanowires (ECSA from H adsorption) [45], Pt-Pb nanoplates
(ECSA from H adsorption) [47•• ], Ptx Gd nanoparticles [48• ], Mo-doped PtNi octahedral nanoparticles [49], Pt-Ni nanowires (ECSA from H
adsorption) [50], Pt3 Ni nanoframes [30], Pt2.5 Ni octahedral nanoparticles [51], Pt nanowires [31•• ], and Ptx Y nanoparticles [52]. (b) Specific activity of
extended electrode surfaces in 0.1 M HClO4 : polycrystalline Pt [24•• ,35], polycrystalline Pt3 Ni and Pt3 Co [15], polycrystalline Pt5 La, Pt5 Ce, Pt5 Tm,
Pt5 Dy, Pt5 Ca, Pt5 Sm, Pt5 Gd and Pt5 Tb [24•• ], polycrystalline Pt3 Y [22], Cu/Pt(111) near-surface alloy [53] and Pt3 Ni(111) [11]. (c) Mass activity of the
nanocatalysts in (a) normalised to the total mass of precious group metal (PGM) [35]. (d) Specific activity of ORR catalysts in alkaline electrolyte: Ag
and AgCo nanoparticles [38], Ag nanoplates [37], AgCu nanoparticles [39], Pt/C and PtCo3 nanoparticles [54], Cu/Pt(111) [55•• ] and Pt3 Ni(111) [28• ].
(e) Mass activity in alkaline electrolyte of the nanocatalysts in (d) together with Pd3 Pb nanoplates [56• ]. The mass activity for Ag-based catalysts
normalised by total mass of catalyst (PGM∗ ). In alkaline, the activity values are given at 0.80, 0.85 or 0.90 V vs. RHE. In particular, the activity on
Ag-based catalysts is typically given at 0.80, due to their low activity at 0.90 V vs. RHE.

we introduce key model studies on the elucidation of the
design principles for the ORR. We then highlight a se-
lection of strategies aiming at improving the mass activ-
ity of nanocatalysts. Finally, we summarise relevant in situ
methods to characterise the active phase and the degra-
dation mechanisms of the catalysts.
Design principles for enhanced oxygen
reduction electrocatalysis on model Pt-alloys
Elucidating the factors governing oxygen reduction is
essential to design more efficient and stable catalysts
[5,24,57–60]. A Sabatier volcano relationship between the
ORR activity and the binding energy of the oxygen-
containing reaction intermediates was established from
density functional theory calculations [59,61,62]: the opti-
mum electrocatalyst should bind OH 0.1 eV weaker than
Pt [61]. The OH binding energy, and thus the ORR
activity, can be tuned by controlling other parameters
such as the Pt-Pt interatomic distance [24•• ,63–65], the
d-band centre [15,19,61,66] and the generalised coordina-
tion number [12]. On Pt-alloys, the OH binding energy
can be weakened by means of ligand [16] and strain ef-
fects [18,67]. Ligand effects occur when the electronic struc-
ture of the surface atoms is modified due to subsurface
alloying [53], and strain effects originate from the forma-
tion of a laterally compressed Pt overlayer [18,24•• ,68].
Model studies on well-defined surfaces have enabled
to separate these electronic effects [24•• ,53,55,69–71].

Current Opinion in Electrochemistry 2018, 000:1–12 www.sciencedirect.com

Please cite this article as: Escudero-Escribano, Jensen, Jensen, Recent advances in bimetallic electrocatalysts for oxy-
gen reduction: design principles, structure-function relations and active phase elucidation, Current Opinion in Elec-
JID: COELEC
ARTICLE IN PRESS [mNS;June 16, 2018;4:6]

Bimetallic electrocatalysts for oxygen reduction Escudero-Escribano, Jensen and Jensen 3

Figure 2

Relationships on Pt-based ORR electrocatalysts: (a) Activity as a function of the potential shift in OH adsorption on Cu/Pt(111) near-surface alloys
(NSAs) by Jensen et al. [55•• ] and Stephens et al. [53]; Activity as a function of (b) the nearest neighbour Pt-Pt distance and (c) the potential shift in H
adsorption on polycrystalline Pt-lanthanide and Pt-alkaline earth alloys by Escudero-Escribano et al. [24•• ] and Vej-Hansen et al. [25]; (d) Specific
activity as a function of the strain on mass-selected Ptx Gd, Ptx Y and Pt nanoparticles by Velázquez-Palenzuela et al. [48• ] and Hernández-Fernández
et al. [52]. The strain (%) was determined through EXAFS after initial ORR activity measurement (filled squares) and after stability test (empty square)
[48• ]. The specific activity in (a–d) corresponds to the kinetic current density evaluated at 0.9 V vs. RHE.

Recent works on Cu/Pt(111) near-surface alloys (NSAs)
and Pt-lanthanide alloys provide a strong experimental
proof of the volcano model [24•• ,53,55•• ].
Ligand effects induced by subsurface alloying were stud-
ied in the absence of strain on Cu/Pt(111) NSAs (see
Figure 2a) [53,55•• ]. Cyclic voltammograms (CVs)
showed a positive shift in the OH adsorption region
as the amount of subsurface Cu increased, indicating
destabilisation of adsorbed OH with higher amounts of
Cu [53,55•• ]. As a consequence, the ORR activity as a
function of the OH adsorption follows a Sabatier volcano
relation (Figure 2a), the optimal catalyst exhibiting an
OH binding energy ∼0.1 eV weaker than that of Pt(111)
[53,55•• ]. This volcano-type relation exists both in acid
and alkaline, suggesting that the ORR shares the same
reaction intermediates in both media. The results on
Cu/Pt(111) NSAs provide the key design principle for
the ORR in both electrolytes [55•• ,72].
The ORR activity and stability trends were systemati-
cally studied by controlling strain effects on polycrystalline
Pt-lanthanide alloys [24•• ]. These catalysts present up
to a 6-fold activity enhancement over Pt [23,24•• ,25].
The active phase consists of a thick Pt overlayer un-
der compressive strain formed by acid leaching [24•• ,73].
This overlayer is key for the enhanced kinetic stabil-
ity presented by some Pt-lanthanide alloys [23,24•• ].
The activity versus the bulk nearest-neighbour Pt-Pt dis-
tance follows a volcano relation (Figure 2b). Interestingly,

www.sciencedirect.com Current Opinion in Electrochemistry 2018, 000:1–12

Please cite this article as: Escudero-Escribano, Jensen, Jensen, Recent advances in bimetallic electrocatalysts for oxy-
gen reduction: design principles, structure-function relations and active phase elucidation, Current Opinion in Elec-
JID: COELEC
ARTICLE IN PRESS [mNS;June 16, 2018;4:6]

4 Surface Electrochemistry

Figure 3

(a) Mass activity at 0.9 V vs. RHE as a function of the electrochemically active surface area (ECSA) from RDE measurements for recently developed
nanoparticulate catalysts (values from [18,30,31•• ,34,41,43,44,47•• ,48• ,49,51,52,77,78,79• ]). The ECSA was determined from: CO-stripping
measurements where available (references [30,31•• ,48• ,49,51,52,79• ]), Cu underpotential deposition for Pd@PtNi octahedral nanoparticles [43] and
H adsorption for references [18,34,41,44,47•• ,77,78]. The figure shows both activity and ECSA before (filled blue) and after stability test (hollow blue)
if provided (see original references for details). The blue arrow illustrates the importance of increasing the ECS in order to obtain enhanced mass
activities. We note that the number of cycles and conditions of the stability test (e.g. potential range, temperature, wave nature of the voltammetry)
vary considerably for the different nanoparticulate catalysts, impeding any direct comparison. (b) Elemental mapping of 9 nm Ptx Y mass selected
NPs by Hernandez-Fernandez et al. [52]; (c) Transmission electron microscopy (TEM) image of 9 nm Pt2.5 Ni octahedral NPs by Choi et al. [51]; (d)
TEM image of biaxially strained Pt-Pb nanoplates by Bu et al. [47•• ]; (e) TEM image of Pt3 Ni nanoframes by Chen et al. [30]; and (f) illustration and
TEM image of jagged Pt nanowires by Li et al. [31•• ].

compressed overlayers present a negative shift in the H
adsorption from the CVs, the ORR activity increasing lin-
early with the potential shift (Figure 2c). This shift in-
dicates destabilisation of adsorbed H, Pt5 Tb exhibiting
the maximum destabilisation. Our trends strongly suggest
that Pt5 Tb presents the highest compressive strain; be-
yond larger levels of bulk strain, the Pt overlayer likely
become unstable and relaxes toward lower surface strain
[24•• ]. The relaxation of the most strained overlayers sug-
gests that there is a limit to how far we can tune the ac-
tivity by controlling the compressive strain without strain
relaxation.
Knowledge from extended Pt-rare earth electrodes en-
abled the development of nanoparticulate catalysts
[48• ,52,74]. Mass selected Ptx Gd and Ptx Y nanoparticles
synthesised in a magnetron nanoparticle source showed
very high ORR activity [48• ,52]. The ORR activity in-
creased exponentially with the compressive strain from
extended X-ray absorption fine structure measurements
(Figure 2d) [48• ], in agreement with the formation of a
Pt shell under compressive strain. Moreover, the loss in
specific activity after accelerated stability tests could be
explained by strain relaxation.
Recent strategies for the development of
efficient nanoparticulate electrocatalysts
The past years have witnessed tremendous progress on
the development of bimetallic nanoparticles for ORR
[29,75,76]. It is technologically relevant to compare the
catalyst mass activity, that is the product of the spe-
cific activity and the electrochemically active surface
area (ECSA). Figure 3a shows the mass activity as a
function of the ECSA for a selection of state-of-the-art

Current Opinion in Electrochemistry 2018, 000:1–12 www.sciencedirect.com

Please cite this article as: Escudero-Escribano, Jensen, Jensen, Recent advances in bimetallic electrocatalysts for oxy-
gen reduction: design principles, structure-function relations and active phase elucidation, Current Opinion in Elec-
JID: COELEC
ARTICLE IN PRESS
Bimetallic electrocatalysts for oxygen reduction Escudero-Escribano, Jensen and Jensen
nanocatalysts before and after stability test (if provided)
[18,30,31•• ,34,41,43,44,47•• ,48• ,49,51,52,77,78,79• ]. In-
creasing the ECSA is key for enhanced activities
[3,80]; the catalysts presenting the highest mass ac-
tivity in Figure 3a [30,31,47•• ,49] achieve this by in-
creasing the ECSA. We have used ECSA data deter-
mined from CO-stripping measurements where available
[30,31,48• ,49,51,52,79• ]. However, many works in the lit-
erature evaluate the ECSA from other methods such
as H adsorption [18,34,41,44,47•• ,77,78]. Since the lat-
ter is typically affected by electronic effects on Pt-alloys
[24•• ,69,74], we recommend using CO-stripping instead.
Core-shell nanoparticles, where a Pt shell surrounds a core
of a foreign metal/alloy [81,82], enable high ECSAs and
can achieve increased activity and stability [65,77,83,84].
Notably, core-shell nanoparticles typically present a high
stability; Pd9 Au cores showed an impressive mass activity
loss of only 6% after 100 000 potential cycles (0.6–1.0 V
vs. RHE at 80 °C) [77]. However, most core-shell cata-
lysts incorporate expensive core-metals, resulting in mass
activities normalised by PGM comparable to Pt/C both in
RDE [85,86] and membrane electrode assembly (MEA)
measurements [87]. Recent works employ non-precious
metals [88,89] or porous/hollow cores [90–94]. Similar to
core-shell nanoparticles, dealloyed nanoparticles consist
of a Pt-rich shell around a Pt-alloy core, because of deal-
loying of the less noble metal [18,34,44,95]. Nanoconfined
dealloyed nanoparticles have recently been synthesised
[42,79,96], this method enabling higher ECSA and im-
proved stability by reducing metal leaching, particle ag-
glomeration and carbon corrosion [42,97,98].
Strain-controlled nanoparticles provide an attractive route
to enhance the ORR activity [99]. Mass-selected Ptx Y
[52] (see Figure 3b) and Ptx Gd [48• ] nanoparticles exhibit
very high mass activity thanks to the formation of a com-
pressed Pt-shell. Their ECSA is limited by the thick Pt-
shell required for optimum strain (Figure 2d), resulting
in optimal nanoparticle sizes of around 8–9 nm. The high
oxygen affinity of rare earths hinders the chemical synthe-
sis of these alloys [100]. Recently, alloyed Pt-Y nanopar-
ticles were synthesised on a gram scale for the first time
[101]; further optimisation of this method could enable
to control the composition and size and the nanoparticles,
thus allowing improved activity.
In the search of more active catalysts, shape-controlled
nanoparticles have emerged [102–104]. Their intrinsic ac-
tivity can be enhanced by exposing highly active facets. In
particular, octahedral PtNi catalysts [43,51,105• ] can facil-
itate highly active Pt3 Ni(111) facets [11]. Octahedral Mo-
doped Pt3 Ni [49] achieved a mass activity of 7.0 A/mgPt
[106,107]. This could be in part related to the high ECSA
achieved by the small particle size (4.2 nm), as compared
to octahedral Pi2.5 Ni (9 nm). Although stable below 1.1 V
vs. RHE, Mo-doped Pt3 Ni shows a specific activity loss
www.sciencedirect.com
Please cite this article as: Escudero-Escribano, Jensen, Jensen, Recent advances in bimetallic electrocatalysts for oxy-
gen reduction: design principles, structure-function relations and active phase elucidation, Current Opinion in Elec-
[mNS;June 16, 2018;4:6]
5
of 78% after only 1000 cycles between 0.6 and 1.26 V
vs. RHE, suggesting a metastable configuration. Recent
works have shown that doping Pt-Ni nanoparticles with
Rh [108] and Au [109] also enhance the stability. How-
ever, stabilising shape-controlled nanoparticles without
activity loss still remains a key challenge [110].
Morphology-controlled catalysts including 1D nanowires
[31,45,50,111], 2D nanoplates [47•• ,112] and 3D
nanoframes [30,113–115] provide a highly attractive
approach to enhance catalytic activity while maintaining
high Pt-surface utilisation. Strained Pt-Pb nanoplates
[47•• ] (see Figure 3d) achieved an activity of 4.3 A/mgPt
by combining strain effects with an increase in the
surface-to-volume ratio. Notably, Pt3 Ni nanoframes
(Figure 3e) present both an outstanding mass activity of
5.7 A/mgPt and high stability [30]. Pt-based nanowires
are of special interest due to their high ECSA. Jagged
Pt nanowires (see Figure 3f) yielded a record-breaking
activity of 13.6 A/mgPt [31]. The cause of the activity
enhancement is still uncertain; simulations suggest that
it is related to the formation of a highly uncoordinated
surface configuration. Furthermore, the unique 1D na-
ture of nanowires with multiple support anchor points
are believed to inhibit Ostwald ripening and particle
agglomeration [31,116], a major cause for degradation
[41]. In addition, because of their highly crystalline sur-
faces, nanoframes [30] and nanowires [31,45] have few
lattice boundaries and less defective sites vulnerable to
Pt dissolution [117•• ].
Addressing the stability of nanoparticulate catalysts is of
fundamental importance to develop technologically rel-
evant catalysts [21•• ]. Hence, understanding the mecha-
nisms governing degradation of Pt-based catalysts is crit-
ical. Several key mechanisms have been identified; these
include Oswald ripening, particle detachment, Pt disso-
lution and leaching alloying elements [41,116]. More-
over, carbon supported catalysts suffer from carbon cor-
rosion. Some concepts such as nanostructured thin films
circumvent this problem [4]; however, these are signifi-
cantly limited by low ECSAs. Some recent strategies in-
clude the development of more stable support materials
[118] and unsupported catalysts such as aerogels [65,119].
For a more detailed discussion on both degradation mech-
anisms and mitigation strategies we refer to other recent
reviews [94,120].
Finally, the impressive activity enhancement from RDE
experiments has not been translated to MEA measure-
ments in fuel cells yet [29,121]. Furthermore, many ORR
electrocatalysts achieve high mass activities by increasing
their intrinsic activities at a cost of lower ECSA as com-
pared to Pt/C. At low overpotentials (0.9 V vs. RHE), this
strategy leads to impressive values [121]. However, when
increasing the overpotential to typical fuel cell voltages
(0.6–0.7 V vs. RHE), the improvement factors gradually
Current Opinion in Electrochemistry 2018, 000:1–12
JID: COELEC
ARTICLE IN PRESS [mNS;June 16, 2018;4:6]

6 Surface Electrochemistry

Figure 4

Selection of in situ characterisation of the electrochemical interface of relevance for oxygen reduction: (a) Schematic representation of a selection of
techniques that provide an in situ insight into ORR electrocatalysts: in situ optical spectroscopy, electrochemical methods combined with mass
spectrometry, electrochemical scanning probe microscopy and in situ X-ray characterisation techniques. (b) Correlation of CO stretching from in situ
FTIR with the ORR activity of Pt-Ni nanoparticles, adapted from Beermann et al. [105• ]. (c) Pt(111) oxidation and catalyst roughening probed by in
situ GI-XRD, adapted from Ruge et al. [132]. (d) Electrochemical flow cell combined with ICP-MS monitoring the Pt/Ni dissolution during dealloying of
Pt-Ni nanoparticles, adapted from Baldizzone et al. [138]. (e) In situ STM images and CVs of a Pt(111) electrode surface during oxidation-reduction
cycles, adapted from Jacobse et al. [141•• ].

decrease. Since the ECSA is unaffected by such poten-
tial relationship, it is desirable to develop nanocatalysts
with optimised mass activity and ECSA [3• ]. Finally, it
would be beneficial to combine RDE methods with com-
plementary tools with reaction environments and current
density ranges resembling those of fuel cells [122,123]. It
was recently demonstrated that gas diffusion electrodes
provide similar catalytic performances to those measured
in MEAs [124• ], thus allowing catalyst benchmarking un-
der realistic conditions.
In situ elucidation of the active surface phase
and degradation mechanisms
In order to develop more efficient and stable electrocat-
alysts, it is key to identify the active phase. Traditionally,
characterising the active surface phase has relied on ex
situ surface science studies before and/or after the electro-
chemical tests. However, during the electrocatalytic reac-
tions, the active sites evolve and their dynamics depend
on the interface structure. Thus, we need to understand
this structure under reaction conditions. Recent develop-
ments in advanced in situ characterisation techniques en-
able probing the interface at the atomic and molecular
level (see Figure 4a) [125,126]. Electrochemical methods
combined with in situ spectroscopy, synchrotron-based X-
ray studies, mass spectrometry and scanning probe mi-
croscopy can provide key in situ insight on the structure-
reactivity relations as well as degradation mechanisms.
Below, we briefly summarise some recent examples.

Current Opinion in Electrochemistry 2018, 000:1–12 www.sciencedirect.com

Please cite this article as: Escudero-Escribano, Jensen, Jensen, Recent advances in bimetallic electrocatalysts for oxy-
gen reduction: design principles, structure-function relations and active phase elucidation, Current Opinion in Elec-
JID: COELEC
ARTICLE IN PRESS
Bimetallic electrocatalysts for oxygen reduction Escudero-Escribano, Jensen and Jensen
In situ infrared spectroscopy is very powerful to ex-
amine the electrochemical interface at the molecular
level. Fourier transform infrared spectroscopy (FTIR) in
the attenuated total reflectance (ATR) mode has been
recently used on Pt/C under ORR conditions in or-
der to study the adsorption of anions from different
electrolytes under mass controlled conditions [127]. On
Pt-Ni/C bimetallic octahedral nanoparticles, the ORR ac-
tivity could be correlated to the CO binding energies from
FTIR–ATR (Figure 4b) [105• ].
Synchrotron-based spectroscopic techniques such as X-
ray absorption spectroscopy or ambient-pressure X-ray
photoelectron spectroscopy are essential to directly probe
the electrocatalyst surface as well as the reaction inter-
mediates of the ORR [52,128–131]. Recently, the oxida-
tion potentials and surface roughening were elucidated
on Pt(111) by means of in situ gracing incidence X-ray
diffraction (GI-XRD) and small-angle X-ray scattering
(see Figure 4c) [132,133]. Similar investigations on Pt-
alloys may result in further insights on the formation
and degradation mechanisms on strained Pt overlayers
[73,134].
Understanding corrosion on bimetallic alloys remains a
crucial challenge [135,136]. Combining inductively-
coupled plasma mass spectrometry with on-line
electrochemical flow cells or RDE has recently pro-
vided important insights into degradation mechanisms
[137,116,117•• ]. Figure 4d shows the degradation during
dealloying of Pt-Ni nanoparticles [138].
Lastly, electrochemical scanning tunnelling microscopy
can play an essential role in the visualisation of the active
phase and the surface dissolution [139,140] down to the
atomic level. Figure 4e shows potential-induced surface
roughening on Pt(111) under repeated oxidation and re-
duction cycles [141•• ]. Combining electrochemistry with
high-resolution EC-STM can enable structural informa-
tion at the atomic level. Both EC-STM [141•• ] and in situ
GI-XRD/SAXS [132,133] studies on Pt(111) oxidation-
driven restructuring offer important insight for the devel-
opment of technologically relevant Pt-alloy nanocatalysts,
as Pt-alloys form Pt(111)-like surfaces after acid leaching
[139]. These studies, together with new approaches on
elucidating and monitoring the active site during reaction
conditions [142• ] are expected to play a crucial role in the
development of more efficient active sites on bimetallic
ORR electrocatalysts.
Concluding remarks and outlook
In the recent years, remarkable progress has been made
on improving and understanding the activity enhance-
ment of bimetallic ORR catalysts. Model studies on Pt-
based electrodes have provided key insights on the de-
sign principles for the ORR. This knowledge, combined
with precise control of size, shape and morphology has
www.sciencedirect.com
Please cite this article as: Escudero-Escribano, Jensen, Jensen, Recent advances in bimetallic electrocatalysts for oxy-
gen reduction: design principles, structure-function relations and active phase elucidation, Current Opinion in Elec-
[mNS;June 16, 2018;4:6]
7
led to the development of nanoparticulate catalysts with
intrinsic activities close to those observed for extended
model surfaces. Further investigations on novel catalysts
under more realistic operating conditions might provide
insights that enable a reduction in the current gap be-
tween RDE and MEA measurements. Thus far, only a
few novel concepts have been tested in real devices; how-
ever, the results suggest that mass activity at low over-
potential as an exclusive performance indicator is insuffi-
cient. Nevertheless, significant advances have been made
on the efficiency of ORR nanocatalysts; in particular, the
combination of high ECSA and mass activity presented
by morphology-controlled nanocatalysts is highly encour-
aging. Yet, to further develop more active and stable elec-
trocatalysts, a better understanding of the active phase is
critical. In situ studies are essential in order to fully unlock
the complex structural and chemical changes taking place
during the electrocatalytic reaction.
Acknowledgments
We gratefully acknowledge the Villum Foundation V-SUSTAIN grant 9455
to the Villum Center for the Science of Sustainable Fuels and Chemicals.
M.E.-E. gratefully acknowledges support from the Villum Foundation
under the VILLUM Young Investigator Programme (project no. 19412).
The authors also acknowledge support from the Innovation Fund Denmark.
References and recommended reading
Papers of particular interest, published within the period of review, have
been highlighted as:
•
••
Paper of special interest
Paper of outstanding interest.
1. Stamenkovic VR, Strmcnik D, Lopes PP, Markovic NM: Energy
and fuels from electrochemical interfaces. Nat Mater 2017,
16:57–69. https://doi.org/10.1038/nmat4738.
2. Hong WT, Risch M, Stoerzinger KA, Grimaud A, Suntivich J,
Shao-Horn Y: Toward the rational design of non-precious
transition metal oxides for oxygen electrocatalysis. Energy
Environ Sci 2015, 8:1404–1427.
https://doi.org/10.1039/C4EE03869J.
3. Kongkanand A, Mathias MF: The priority and challenge of
• high-power performance of low-platinum proton-exchange
membrane fuel cells. J Phys Chem Lett 2016, 7:1127–1137.
https://doi.org/10.1021/acs.jpclett.6b00216.
This perspective addresses the technical importance of ECSA for
high-power performance and describes the loading limitations imposed
on PEMFCs at operational current-densities.
4. Debe MK: Electrocatalyst approaches and challenges for
automotive fuel cells. Nature 2012, 486:43–51.
https://doi.org/10.1038/nature11115.
5. Stephens IEL, Bondarenko AS, Grønbjerg U, Rossmeisl J,
Chorkendorff I: Understanding the electrocatalysis of oxygen
reduction on platinum and its alloys. Energy Environ Sci 2012,
5:6744. https://doi.org/10.1039/c2ee03590a.
6. Koper MTM: Structure sensitivity and nanoscale effects in
electrocatalysis. Nanoscale 2011, 3:2054.
https://doi.org/10.1039/c0nr00857e.
7. Markovic NM, Ross PN: Surface science studies of model fuel
cell electrocatalysts. Surf Sci Rep 2002, 45:121–229.
8. Sheng T, Tian N, Zhou ZY, Lin WF, Sun SG: Designing Pt-based
electrocatalysts with high surface energy. ACS Energy Lett
2017, 2:1892–1900.
https://doi.org/10.1021/acsenergylett.7b00385.
Current Opinion in Electrochemistry 2018, 000:1–12
JID: COELEC
ARTICLE IN PRESS
8 Surface Electrochemistry
9. Kobayashi S, Wakisaka M, Tryk DA, Iiyama A, Uchida H: Effect of
alloy composition and crystal face of Pt-Skin/Pt 100– x Co x
[(111), (100), and (110)] single crystal electrodes on the
oxygen reduction reaction activity. J Phys Chem C 2017,
121:11234–11240. https://doi.org/10.1021/acs.jpcc.6b12567.
10. Strmcnik D, Kodama K, van der Vliet D, Greeley J,
Stamenkovic VR, Marković NM: The role of non-covalent
interactions in electrocatalytic fuel-cell reactions on platinum.
Nat Chem 2009, 1:466–472. https://doi.org/10.1038/nchem.330.
11. Stamenkovic VR, Fowler B, Mun BS, Wang G, Ross PN,
Lucas Ca, Marković NM: Improved oxygen reduction activity
on Pt3Ni(111) via increased surface site availability. Science
2007, 315:493–497. https://doi.org/10.1126/science.1135941.
12. Calle-Vallejo F, Tymoczko J, Colic V, Huy Vu Q, Pohl MD,
Morgenstern K, Loffreda D, Sautet P, Schuhmann W,
Bandarenka AS: Finding optimal surface sites on
heterogeneous catalysis by counting nearest neighbors.
Science 2015, 350:185–190.
13. Da He Z, Hanselman S, Chen YX, Koper MTM, Calle-Vallejo F:
Importance of solvation for the accurate prediction of oxygen
reduction activities of Pt-based electrocatalysts. J Phys Chem
Lett 2017, 8:2243–2246.
https://doi.org/10.1021/acs.jpclett.7b01018.
14. Strmcnik D, Escudero-Escribano M, Kodama K, Stamenkovic VR,
Cuesta Á, Markovic NM: Enhanced electrocatalysis of the
oxygen reduction reaction based on patterning of platinum
surfaces with cyanide. Nat Chem 2010, 2:880–885.
https://doi.org/10.1038/NCHEM.771.
15. Stamenkovic V, Mun BS, Mayrhofer KJJ, Ross PN, Markovic NM,
Rossmeisl J, Greeley J, Nørskov JK: Changing the activity of
electrocatalysts for oxygen reduction by tuning the surface
electronic structure. Angew Chem Int Ed 2006, 45:2897–
2901.
16. Kitchin JR, Nørskov JK, Barteau MA, Chen JG: Modification of
the surface electronic and chemical properties of Pt(111) by
subsurface 3d transition metals. J Chem Phys 2004,
120:10240–10246.
17. a Gasteiger H, Kocha SS, Sompalli B, Wagner FT: Activity
benchmarks and requirements for Pt, Pt-alloy, and non-Pt
oxygen reduction catalysts for PEMFCs. Appl Catal B Environ
2005, 56:9–35. https://doi.org/10.1016/j.apcatb.2004.06.021.
18. Strasser P, Koh S, Anniyev T, Greeley J, More K, Yu C, Liu Z,
Kaya S, Nordlund D, Ogasawara H, Toney MF, Nilsson A:
Lattice-strain control of the activity in dealloyed core-shell
fuel cell catalysts. Nat Chem 2010, 2:454–460.
https://doi.org/10.1038/nchem.623.
19. Stamenkovic VR, Mun BS, Arenz M, Mayrhofer KJJ, Lucas CA,
Wang GF, Ross PN, Markovic NM: Trends in electrocatalysis on
extended and nanoscale Pt-bimetallic alloy surfaces. Nat
Mater 2007, 6:241–247.
20. Toda T, Igarashi H, Uchida H, Watanabe M: Enhancement of the
electroreduction of oxygen on Pt alloys with Fe, Ni, and Co. J
Electrochem Soc 1999, 146:3750–3756.
21. Han B, Carlton CE, Kongkanand A, Kukreja RS, Theobald BRC,
•• Gan L, O’Malley R, Strasser P, Wagner FT, Shao-Horn Y: Record
activity and stability of dealloyed bimetallic catalysts for
proton exchange membrane fuel cells. Energy Environ. Sci.
2015, 8:258–266. https://doi.org/10.1039/C4EE02144D.
This paper reports a record breaking MEA activity of dealloyed Pt-Ni/C,
exceeding the 2020 target from the Department of Energy of the United
States.
22. Greeley J, Stephens IEL, Bondarenko AS, Johansson TP,
Hansen HA, Jaramillo TF, Rossmeisl J, Chorkendorff I,
Nørskov JK: Alloys of platinum and early transition metals as
oxygen reduction electrocatalysts. Nat. Chem 2009,
1:552–556. https://doi.org/10.1038/nchem.367.
23. Escudero-Escribano M, Verdaguer-Casadevall A, Malacrida P,
Grønbjerg U, Knudsen BP, Jepsen AK, Rossmeisl J,
Stephens IEL, Chorkendorff I: Pt5Gd as a highly active and
stable catalyst for oxygen electroreduction. J Am Chem Soc
2012, 134:16476–16479. https://doi.org/10.1021/ja306348d.
Current Opinion in Electrochemistry 2018, 000:1–12
Please cite this article as: Escudero-Escribano, Jensen, Jensen, Recent advances in bimetallic electrocatalysts for oxy-
gen reduction: design principles, structure-function relations and active phase elucidation, Current Opinion in Elec-
[mNS;June 16, 2018;4:6]
24. Escudero-Escribano M, Malacrida P, Hansen MH,
•• Vej-Hansen UG, Velázquez-Palenzuela A, Tripkovic V, Schiøtz J,
Rossmeisl J, Stephens IEL, Chorkendorff I: Tuning the activity of
Pt alloy electrocatalysts by means of the lanthanide
contraction. Science 2016, 352:73–76.
https://doi.org/10.1126/science.aad8892.
This report presents a new set of highly active Pt-alloy electrocatalysts;
the lattice parameter of the bulk alloys controls their electrocatalytic
properties.
25. Vej-Hansen UG, Escudero-Escribano M, Velázquez-Palenzuela A,
Malacrida P, Rossmeisl J, Stephens IEL, Chorkendorff I, Schiøtz J:
New platinum alloy catalysts for oxygen electroreduction
based on alkaline earth metals. Electrocatalysis 2017,
8:594–604. https://doi.org/10.1007/s12678- 017- 0375- 9.
26. Malacrida P, Escudero-Escribano M, Verdaguer-Casadevall A,
Stephens IEL, Chorkendorff I: Enhanced activity and stability of
Pt–La and Pt–Ce alloys for oxygen electroreduction: the
elucidation of the active surface phase. J Mater Chem A 2014,
2:4234. https://doi.org/10.1039/c3ta14574c.
27. Dubau L, Lopez-Haro M, Castanheira L, Durst J, Chatenet M,
Bayle-Guillemaud P, Guétaz L, Caqué N, Rossinot E, Maillard F:
Probing the structure, the composition and the ORR activity
of Pt3Co/C nanocrystallites during a 3422h PEMFC ageing
test. Appl Catal B Environ 2013, 142–143:801–808.
https://doi.org/10.1016/j.apcatb.2013.06.011.
28. Staszak-Jirkovský J, Subbaraman R, Strmcnik D, Harrison KL,
• Diesendruck CE, Assary R, Frank O, Kobr L, Wiberg GKH,
Genorio B, Connell JG, Lopes PP, Stamenkovic VR, Curtiss L,
Moore JS, Zavadil KR, Markovic NM: Water as a promoter and
catalyst for dioxygen electrochemistry in aqueous and
organic media. ACS Catal 2015, 5:6600–6607.
https://doi.org/10.1021/acscatal.5b01779.
This work presents interesting results for the ORR in alkaline aqueous
and organic media; Pt3Ni(111) shows a record in activity of
∼170mA/cm2 in 0.1M KOH alkaline media.
29. Banham D, Ye S: Current status and future development of
catalyst materials and catalyst layers for proton exchange
membrane fuel cells: an industrial perspective. ACS Energy
Lett 2017, 2:629–638.
https://doi.org/10.1021/acsenergylett.6b00644.
30. Chen C, Kang Y, Huo Z, Zhu Z, Huang W, Xin HL, Snyder JD, Li D,
Herron Ja, Mavrikakis M, Chi M, More KL, Li Y, Markovic NM,
Somorjai Ga, Yang P, Stamenkovic VR: Highly crystalline
multimetallic nanoframes with three-dimensional
electrocatalytic surfaces. Science 2014, 343:1339–1343.
https://doi.org/10.1126/science.1249061.
31. Li M, Li M, Zhao Z, Cheng T, Fortunelli A, Chen C, Yu R, Gu L,
•• Merinov B, Lin Z, Zhu E, Yu T, Jia Q, Guo J, Zhang L, Iii WAG,
Huang Y, Duan X: Ultrafine jagged platinum nanowires enable
ultrahigh mass activity for the oxygen reduction reaction.
Science 2016, 259:1414–1419.
https://doi.org/10.1126/science.aaf9050.
In this report, jagged Pt-nanowires demonstrate an unprecedented
mass activity of 13.6 A/mgPt, by combining high specific activity with
high ECSA.
32. Lv H, Li D, Strmcnik D, Paulikas AP, Markovic NM,
Stamenkovic VR: Recent advances in the design of tailored
nanomaterials for efficient oxygen reduction reaction. Nano
Energy 2016, 29:149–165.
https://doi.org/10.1016/j.nanoen.2016.04.008.
33. Liu W, Rodriguez P, Borchardt L, Foelske A, Yuan J,
Herrmann AK, Geiger D, Zheng Z, Kaskel S, Gaponik N, Kötz R,
Schmidt TJ, Eychmüller A: Bimetallic aerogels:
high-performance electrocatalysts for the oxygen reduction
reaction. Angew Chemie Int Ed 2013, 52:9849–9852.
https://doi.org/10.1002/anie.201303109.
34. Wang D, Xin HL, Hovden R, Wang H, Yu Y, Muller Da, DiSalvo FJ,
Abruña HD: Structurally ordered intermetallic platinum-cobalt
core-shell nanoparticles with enhanced activity and stability
as oxygen reduction electrocatalysts. Nat Mater 2013,
12:81–87. https://doi.org/10.1038/nmat3458.
35. Pedersen CM, Escudero-Escribano M, Velázquez-Palenzuela A,
Christensen LH, Chorkendorff I, Stephens IEL: Benchmarking
www.sciencedirect.com
JID: COELEC
ARTICLE IN PRESS
Bimetallic electrocatalysts for oxygen reduction Escudero-Escribano, Jensen and Jensen
Pt-based electrocatalysts for low temperature fuel cell
reactions with the rotating disk electrode: oxygen reduction
and hydrogen oxidation in the presence of CO (review article).
Electrochim Acta 2015, 179:647–657.
https://doi.org/10.1016/j.electacta.2015.03.176.
36. Varcoe JR, Atanassov P, Dekel DR, Herring AM, Hickner MA,
Kohl PA, Kucernak AR, Mustain WE, Nijmeijer K, Scott K, Xu T,
Zhuang L: Anion-exchange membranes in electrochemical
energy systems. Energy Environ Sci 2014, 7:3135–3191.
https://doi.org/10.1039/C4EE01303D.
37. Garlyyev B, Liang Y, Butt FK, Bandarenka AS: Engineering of
highly active silver nanoparticles for oxygen electroreduction
via simultaneous control over their shape and size. Adv
Sustain Syst, vol 1 2017 1700117.
https://doi.org/10.1002/adsu.201700117.
38. Holewinski A, Idrobo JC, Linic S: High-performance Ag-Co
alloy catalysts for electrochemical oxygen reduction. Nat
Chem 2014, 6:828–834. https://doi.org/10.1038/nchem.
2032.
39. Wu X, Chen F, Zhang N, Qaseem A, Johnston RL: Engineering
bimetallic Ag–Cu nanoalloys for highly efficient oxygen
reduction catalysts: a guideline for designing Ag-based
electrocatalysts with activity comparable to Pt/C-20%. Small
2017, 13:1–13. https://doi.org/10.1002/smll.201603876.
40. Mayrhofer KJJ, Strmcnik D, Blizanac BB, Stamenkovic V,
Arenz M, Markovic NM: Measurement of oxygen reduction
activities via the rotating disc electrode method: from Pt
model surfaces to carbon-supported high surface area
catalysts. Electrochim Acta 2008, 53:3181–3188.
https://doi.org/10.1016/j.electacta.2007.11.057.
41. Meier JC, Galeano C, Katsounaros I, Witte J, Bongard HJ,
Topalov AA, Baldizzone C, Mezzavilla S, Schüth F, Mayrhofer KJJ:
Design criteria for stable Pt/C fuel cell catalysts. Beilstein J
Nanotechnol 2014, 5:44–67. https://doi.org/10.3762/bjnano.5.5.
42. Pizzutilo E, Knossalla J, Geiger S, Grote JP, Polymeros G,
Baldizzone C, Mezzavilla S, Ledendecker M, Mingers A,
Cherevko S, Schüth F, Mayrhofer KJJ: The space confinement
approach using hollow graphitic spheres to unveil activity and
stability of Pt-Co nanocatalysts for PEMFC. Adv Energy Mater,
vol 7 2017 1700835. https://doi.org/10.1002/aenm.201700835.
43. Choi S, Shao M, Lu N, Ruditskiy A, Peng H, Park J, Guerrero S,
Wang J, Kim MJ, Xia Y: Synthesis and characterization of Pd @
Pt-Ni core-shell octahedra with high activity toward oxygen
reduction. ACS Nano 2014, 10:10363–10371.
https://doi.org/10.1021/nn5036894.
44. Cui C, Gan L, Heggen M, Rudi S, Strasser P: Compositional
segregation in shaped Pt alloy nanoparticles and their
structural behaviour during electrocatalysis. Nat Mater 2013,
12:765–771. https://doi.org/10.1038/nmat3668.
45. Bu L, Guo S, Zhang X, Shen X, Su D, Lu G, Zhu X, Yao J, Guo J,
Huang X: Surface engineering of hierarchical platinum-cobalt
nanowires for efficient electrocatalysis. Nat Commun, vol 7
2016. https://doi.org/10.1038/ncomms11850.
46. Park J, Kanti Kabiraz M, Kwon H, Park S, Baik H, Il Choi S, Lee K:
Radially phase segregated PtCu@PtCuNi Dendrite@Frame
nanocatalyst for the oxygen reduction reaction. ACS Nano
2017, 11:10844–10851.
https://doi.org/10.1021/acsnano.7b04097.
47. Bu L, Zhang N, Guo S, Zhang X, Li J, Yao J, Wu T, Lu G, Ma J-Y,
•• Su D, Huang X: Biaxially strained PtPb/Pt core/shell nanoplate
boosts oxygen reduction catalysis. Science 2016,
354:1410–1414. https://doi.org/10.1126/science.aah6133.
This work shows that the ORR activity on exposed Pt(110) facets can
be enhanced by tensile strain using biaxial Pt-Pb nanoplates with a high
surface-to-volume ratio.
48. Velázquez-Palenzuela A, Masini F, Pedersen AF,
• Escudero-Escribano M, Deiana D, Malacrida P, Hansen TW,
Friebel D, Nilsson A, Stephens IEL, Chorkendorff I: The
enhanced activity of mass-selected PtxGd nanoparticles for
oxygen electroreduction. J Catal 2015, 328:297–307.
This paper shows that strain can be maintained on PtxGd
www.sciencedirect.com
Please cite this article as: Escudero-Escribano, Jensen, Jensen, Recent advances in bimetallic electrocatalysts for oxy-
gen reduction: design principles, structure-function relations and active phase elucidation, Current Opinion in Elec-
[mNS;June 16, 2018;4:6]
9
nanoparticles, the activity increasing for larger nanoparticles presenting
higher compressive strain.
49. Huang X, Cao L, Chen Y, Zhu E, Lin Z, Li M, Yan A, Zettl A,
Wang YM, Duan X, Mueller T: High-performance transition
metal – doped Pt 3 Ni octahedra for oxygen reduction
reaction. Science 2015, 348:1230–1234.
50. Jiang K, Shao Q, Zhao D, Bu L, Guo J, Huang X: Phase and
composition tuning of 1D platinum-nickel nanostructures for
highly efficient electrocatalysis. Adv Funct Mater, vol 27 2017.
https://doi.org/10.1002/adfm.201700830.
51. Choi S-I, Xie S, Shao M, Odell JH, Lu N, Peng H-C, Protsailo L,
Guerrero S, Park J, Xia X, Wang J, Kim MJ, Xia Y: Synthesis and
characterization of 9nm Pt-Ni octahedra with a record high
activity of 3.3 A/mg(Pt) for the oxygen reduction reaction.
Nano Lett 2013, 13:3420–3425.
https://doi.org/10.1021/nl401881z.
52. Hernandez-Fernandez P, Masini F, McCarthy DN, Strebel CE,
Friebel D, Deiana D, Malacrida P, Nierhoff A, Bodin A, Wise AM,
Nielsen JH, Hansen TW, Nilsson A, Stephens IEL, Chorkendorff I:
Mass-selected nanoparticles of PtxY as model catalysts for
oxygen electroreduction. Nat Chem 2014, 6:732–738.
https://doi.org/10.1038/nchem.2001.
53. Stephens IEL, Bondarenko AS, Perez-Alonso FJ, Calle-Vallejo F,
Bech L, Johansson TP, Jepsen AK, Frydendal R, Knudsen BP,
Rossmeisl J, Chorkendorff I: Tuning the activity of Pt(111) for
oxygen electroreduction by subsurface alloying. J Am Chem
Soc 2011, 133:5485–5491. https://doi.org/10.1021/ja111690g.
54. Oezaslan M, Hasche´ F, Strasser P: Oxygen electroreduction on
PtCo3, PtCo and Pt3Co alloy nanoparticles for alkaline and
acidic PEM fuel cells. J Electrochem Soc 2012, 159:B394–B405.
https://doi.org/10.1149/2.075204jes.
55. Jensen KD, Tymoczko J, Rossmeisl J, Bandarenka A,
•• Chorkendorff I, Escudero-Escribano M, Stephens IEL:
Elucidation of the oxygen reduction volcano in alkaline media
using a copper-platinum(111) alloy. Angew Chemie Int Ed 2018,
57:2800–2805. https://doi.org/10.1002/anie.201711858.
This work on Cu/Pt(111) alloys shows that the key descriptor controlling
the oxygen reduction in alkaline media is, as in acid, the binding to the
reaction intermediates.
56. Wang K, Qin Y, Lv F, Li M, Liu Q, Lin F, Feng J: Intermetallic
• Pd3Pb nanoplates enhance oxygen reduction catalysis with
excellent methanol tolerance. Small 2018, 1700331:1–8.
https://doi.org/10.1002/smtd.201700331.
This paper presents Pd3Pb nanoplates as highly active ORR catalysts
in alkaline media with excellent MeOH tolerance for direct methanol fuel
cells.
57. Calle-Vallejo F, Pohl MD, Reinisch D, Loffreda D, Sautet P,
Bandarenka AS: Why conclusions from platinum model
surfaces do not necessarily lead to enhanced nanoparticle
catalysts for the oxygen reduction reaction. Chem Sci 2017,
8:2283–2289. https://doi.org/10.1039/C6SC04788B.
58. Suntivich J, May KJ, Gasteiger HA, Goodenough JB,
Shao-Horn Y: A perovskite oxide optimized for oxygen
evolution catalysis from molecular orbital principles. Science
2011, 334:1383–1385. https://doi.org/10.1126/science.1212858.
59. Busch M, Halck NB, Kramm UI, Siahrostami S, Krtil P,
Rossmeisl J: Beyond the top of the volcano? A unified
approach to electrocatalytic oxygen reduction and oxygen
evolution. Nano Energy 2016, 29:126–135.
60. Kodama K, Jinnouchi R, Takahashi N, Murata H, Morimoto Y:
Activities and stabilities of Au-modified stepped-Pt
single-crystal electrodes as model cathode catalysts in
polymer electrolyte fuel Cells. J Am Chem Soc 2016,
138:4194–4200. https://doi.org/10.1021/jacs.6b00359.
61. Nørskov JK, Rossmeisl J, Logadottir A, Lindqvist L, Kitchin JR,
Bligaard T, Jonsson H: Origin of the overpotential for oxygen
reduction at a fuel-cell cathode. J Phys Chem B 2004,
108:17886–17892.
62. Kulkarni A, Siahrostami S, Patel A, Nørskov JK: Understanding
catalytic activity trends in the oxygen reduction reaction.
Chem Rev 2017. https://doi.org/10.1021/acs.chemrev.7b00488.
Current Opinion in Electrochemistry 2018, 000:1–12
JID: COELEC
ARTICLE IN PRESS
10 Surface Electrochemistry
63. Mukerjee S, Srinivasan S, Soriaga MP, McBreen J: Role of
structural and electronic-properties of Pt and Pt alloys on
electrocatalysis of oxygen reduction - an in-situ Xanes and
Exafs investigation. J Electrochem Soc 1995, 142:1409–1422.
64. Jia Q, Liang W, Bates MK, Mani P, Lee W, Mukerjee S: Activity
descriptor identification for oxygen reduction on
platinum-based bimetallic nanoparticles : in situ observation
of the linear relationship. ACS Nano 2015, 9:387–400.
65. Cai B, Hübner R, Sasaki K, Rellinghaus B, Adzic RR,
Eychmüller A: Core-shell structuring of pure metallic aerogels
towards highly efficient Pt utilization for the oxygen reduction
reaction. Angew Chemie Int Ed 2018.
https://doi.org/10.1002/anie.201710997.
66. Zhang JL, Vukmirovic MB, Xu Y, Mavrikakis M, Adzic RR:
Controlling the catalytic activity of platinum-monolayer
electrocatalysts for oxygen reduction with different
substrates. Angew Chem Int Ed 2005, 44:2132–2135.
67. Mavrikakis M, Hammer B, Nørskov JK: Effect of strain on the
reactivity of metal surfaces. Phys Rev Lett 1998, 81:2819–2822.
68. Asano M, Kawamura R, Sasakawa R, Todoroki N, Wadayama T:
Oxygen reduction reaction activity for strain-controlled
Pt-based model alloy catalysts: surface strains and direct
electronic effects induced by alloying elements. ACS Catal
2016, 6:5285–5289. https://doi.org/10.1021/acscatal.6b01466.
69. Hoster HE, Alves OB, Koper MTM: Tuning adsorption via strain
and vertical ligand effects. Chemphyschem. 2010,
11:1518–1524.
70. Heider EA, Jacob T, Kibler LA: Platinum overlayers on
PtxRu1-x(111) electrodes: tailoring the ORR activity by lateral
strain and ligand effects. J Electroanal Chem 2018.
https://doi.org/10.1016/j.jelechem.2017.10.063.
71. Deng YJ, Tripkovic V, Rossmeisl J, Arenz M: Oxygen reduction
reaction on Pt overlayers deposited onto a gold film: ligand,
strain, and ensemble effect. ACS Catal 2016, 6:671–676.
https://doi.org/10.1021/acscatal.5b02409.
72. Schilter D: Electrocatalysis: volcano spews out hot new
catalyst. Nat Rev Chem 2018, 2:116.
https://doi.org/10.1038/s41570- 018- 0116.
73. Pedersen AF, Ulrikkeholm ET, Escudero-Escribano M,
Johansson TP, Malacrida P, Pedersen CM, Hansen MH,
Jensen KD, Rossmeisl J, Friebel D, Nilsson A, Chorkendorff I,
Stephens IEL: Probing the nanoscale structure of the
catalytically active overlayer on Pt alloys with rare earths.
Nano Energy 2016, 29:249–260.
https://doi.org/10.1016/j.nanoen.2016.05.026.
74. Zamburlini E, Jensen KD, Stephens IEL, Chorkendorff I,
Escudero-Escribano M: Benchmarking Pt and Pt-lanthanide
sputtered thin films for oxygen electroreduction: fabrication
and rotating disk electrode measurements. Electrochim Acta
2017, 247:708–721.
https://doi.org/10.1016/j.electacta.2017.06.146.
75. Strasser P, Gliech M, Kuehl S, Moeller T: Electrochemical
processes on solid shaped nanoparticles with defined facets.
Chem Soc Rev 2018. https://doi.org/10.1039/c7cs00759k.
76. Tian XL, Xu YY, Zhang W, Wu T, Xia BY, Wang X: Unsupported
platinum-based electrocatalysts for oxygen reduction
reaction. ACS Energy Lett 2017, 2:2035–2043.
https://doi.org/10.1021/acsenergylett.7b00593.
77. Sasaki K, Naohara H, Choi Y, Cai Y, Chen W-F, Liu P, Adzic RR:
Highly stable Pt monolayer on PdAu nanoparticle
electrocatalysts for the oxygen reduction reaction. Nat
Commun 2012, 3:1115. https://doi.org/10.1038/ncomms2124.
78. Wang JX, Ma C, Choi Y, Su D, Zhu Y, Liu P, Si R, Vukmirovic MB,
Zhang Y, Adzic RR: Kirkendall effect and lattice contraction in
nanocatalysts : a new strategy to enhance sustainable
activity. J Am Chem Soc 2011, 133:13551–13557.
https://doi.org/10.1021/ja204518x.
79. Mezzavilla S, Baldizzone C, Swertz AC, Hodnik N, Pizzutilo E,
•
Polymeros G, Keeley GP, Knossalla J, Heggen M, Mayrhofer KJJ,
Current Opinion in Electrochemistry 2018, 000:1–12
Please cite this article as: Escudero-Escribano, Jensen, Jensen, Recent advances in bimetallic electrocatalysts for oxy-
gen reduction: design principles, structure-function relations and active phase elucidation, Current Opinion in Elec-
[mNS;June 16, 2018;4:6]
Schüth F: Structure-activity-stability relationships for
space-confined PtxNiy nanoparticles in the oxygen reduction
reaction. ACS Catal 2016, 6:8058–8068.
https://doi.org/10.1021/acscatal.6b02221.
This paper shows the synthesis and structure-activity-stability relations
for spaced-confined Pt-Ni nanoparticles with enhanced durability
towards metal leaching and particle agglomeration.
80. Nonoyama N, Okazaki S, Weber AZ, Ikogi Y, Yoshida T: Analysis
of oxygen-transport diffusion resistance in
proton-exchange-membrane fuel cells. J Electrochem Soc
2011, 158:B416. https://doi.org/10.1149/1.3546038.
81. Adzic RR, Zhang J, Sasaki K, Vukmirovic MB, Shao M, Wang JX,
Nilekar aU, Mavrikakis M, Valerio Ja, Uribe F: Platinum
monolayer fuel cell electrocatalysts. Top Catal 2007,
46:249–262. https://doi.org/10.1007/s11244- 007- 9003- x.
82. Strasser P: Free electrons to molecular bonds and back:
closing the energetic oxygen reduction (ORR)-oxygen
evolution (OER) cycle using core-shell nanoelectrocatalysts.
Acc Chem Res 2016, 49:2658–2668.
https://doi.org/10.1021/acs.accounts.6b00346.
83. Strickler AL, Jackson A, Jaramillo TF: Active and stable Ir@Pt
core–shell catalysts for electrochemical oxygen reduction.
ACS Energy Lett 2016:244–249.
https://doi.org/10.1021/acsenergylett.6b00585.
84. Kuttiyiel KA, Choi YM, Sasaki K, Su D, Hwang SM, Yim SD,
Yang TH, Park GG, Adzic RR: Tuning electrocatalytic activity of
Pt monolayer shell by bimetallic Ir-M (M=Fe, Co, Ni or Cu)
cores for the oxygen reduction reaction. Nano Energy 2016,
29:261–267. https://doi.org/10.1016/j.nanoen.2016.05.024.
85. Wang X, Il Choi S, Roling LT, Luo M, Ma C, Zhang L, Chi M, Liu J,
Xie Z, Herron JA, Mavrikakis M, Xia Y: Palladium-platinum
core-shell icosahedra with substantially enhanced activity
and durability towards oxygen reduction. Nat Commun, vol 6
2015. https://doi.org/10.1038/ncomms8594.
86. Kuttiyiel KA, Sasaki K, Choi Y, Su D, Liu P, Adzic RR: Bimetallic
IrNi core platinum monolayer shell electrocatalysts for the
oxygen reduction reaction. Energy Environ Sci 2012, 5:5297.
https://doi.org/10.1039/c1ee02067f.
87. Kongkanand A, Subramanian NP, Yu Y, Liu Z, Igarashi H,
Muller DA: Achieving high-power PEM fuel cell performance
with an ultralow-Pt-content core-shell catalyst. ACS Catal
2016, 6:1578–1583. https://doi.org/10.1021/acscatal.5b02819.
88. Tian X, Luo J, Nan H, Zou H, Chen R, Shu T, Li X, Li Y, Song H,
Liao S, Adzic RR: Transition metal nitride coated with atomic
layers of Pt as a low-cost, highly stable electrocatalyst for the
oxygen reduction reaction. J Am Chem Soc 2016,
138:1575–1583. https://doi.org/10.1021/jacs.5b11364.
89. Kuttiyiel KA, Choi YM, Hwang SM, Park GG, Yang TH, Su D,
Sasaki K, Liu P, Adzic RR: Enhancement of the oxygen
reduction on nitride stabilized pt-M (M=Fe, Co, and Ni)
core-shell nanoparticle electrocatalysts. Nano Energy 2015,
13:442–449. https://doi.org/10.1016/j.nanoen.2015.03.007.
90. Chattot R, Asset T, Drnec J, Bordet P, Nelayah J, Dubau L,
Maillard F: Atomic-scale snapshots of the formation and
growth of hollow PtNi/C nanocatalysts. Nano Lett 2017,
17:2447–2453. https://doi.org/10.1021/acs.nanolett.7b00119.
91. Zhang L, Roling LT, Wang X, Vara M, Chi M, Liu J, Il Choi S,
Park J, Herron JA, Xie Z, Mavrikakis M, Xia Y: Platinum-based
nanocages with subnanometer-thick walls and well-defined,
controllable facets. Science 2015, 349:412–416.
https://doi.org/10.1126/science.aab0801.
92. Zhang Y, Ma C, Zhu Y, Si R, Cai Y, Wang JX, Adzic RR: Hollow
core supported Pt monolayer catalysts for oxygen reduction.
Catal Today 2013, 202:50–54.
https://doi.org/10.1016/j.cattod.2012.03.040.
93. Wang X, Figueroa-Cosme L, Yang X, Luo M, Liu J, Xie Z, Xia Y:
Pt-based icosahedral nanocages: using a combination of
{111} facets, twin defects, and ultrathin walls to greatly
enhance their activity toward oxygen reduction. Nano Lett
2016, 16:1467–1471.
https://doi.org/10.1021/acs.nanolett.5b05140.
www.sciencedirect.com
JID: COELEC
ARTICLE IN PRESS
Bimetallic electrocatalysts for oxygen reduction Escudero-Escribano, Jensen and Jensen
94. Asset T, Chattot R, Fontana M, Mercier-Guyon B, Job N, Dubau L,
Maillard F: A review on recent developments and prospects for
oxygen reduction reaction on hollow Pt-alloy nanoparticles.
ChemPhysChem 2018. https://doi.org/10.1002/cphc.201800153.
95. Wang C, Chi M, Li D, Strmcnik D, Van Der Vliet D, Wang G,
Komanicky V, Chang K, Paulikas AP, Tripkovic D, Pearson J,
More KL, Markovic NM, Stamenkovic VR: Design and synthesis
of bimetallic electrocatalyst with multilayered Pt-skin
surfaces. J Am Chem Soc 2011, 133:14396–14403.
https://doi.org/10.1021/ja2047655.
96. Baldizzone C, Mezzavilla S, Carvalho HWP, Meier JC,
Schuppert AK, Heggen M, Galeano C, Grunwaldt J-D, Schueth F,
Mayrhofer KJJ: Confined-space alloying of nanoparticles for
the synthesis of efficient PtNi fuel-cell catalysts. Angew Chem
Int Ed 2014, 53:14250–14254.
https://doi.org/10.1002/anie.201406812.
97. Galeano C, Meier JC, Soorholtz M, Bongard H, Baldizzone C,
Mayrhofer KJJ, Schüth F: Nitrogen-doped hollow carbon
spheres as a support for platinum-based electrocatalysts.
ACS Catal 2014, 4:3856–3868.
https://doi.org/10.1021/cs5003492.
98. Polymeros G, Baldizzone C, Geiger S, Grote JP, Knossalla J,
Mezzavilla S, Keeley GP, Cherevko S, Zeradjanin AR, Schüth F,
Mayrhofer KJJ: High temperature stability study of carbon
supported high surface area catalysts—expanding the
boundaries of ex-situ diagnostics. Electrochim Acta 2016,
211:744–753. https://doi.org/10.1016/j.electacta.2016.06.105.
99. Luo M, Guo S: Strain-controlled electrocatalysis on
multimetallic nanomaterials. Nat Rev Mater, vol 2 2017.
https://doi.org/10.1038/natrevmats.2017.59.
100. Brandiele R, Durante C, Gradzka E, Rizzi GA, Zheng J,
Badocco D, Centomo P, Pastore P, Granozzi G, Gennaro A: One
step forward to a scalable synthesis of platinum-yttrium
alloyed nanoparticles on mesoporous carbon for oxygen
reduction reaction. J Mater Chem A 2016, 4:12232–12240.
https://doi.org/10.1039/C6TA04498K.
101. Roy C, Knudsen BP, Pedersen CM, Velázquez Palenzuela AA,
Christensen LH, Damsgaard CD, Stephens IEL, Chorkendorff I:
Scalable synthesis of carbon supported platinum - lanthanide
and rare earth alloys for oxygen reduction. ACS Catal 2018.
https://doi.org/10.1021/acscatal.7b03972.
102. Vidal-iglesias FJ, Arań-Ais RM, Solla-Gulloń J, Herrero E,
Feliu JM: Electrochemical characterization of
shape-controlled Pt nanoparticles in different supporting
electrolytes. ACS Catal 2012, 2:901–910
dx.doi.org/10.1021/cs200681x.
103. Arán-Ais RM, Solla-Gullón J, Gocyla M, Heggen M,
Dunin-Borkowski RE, Strasser P, Herrero E, Feliu JM: The effect
of interfacial pH on the surface atomic elemental distribution
and on the catalytic reactivity of shape-selected bimetallic
nanoparticles towards oxygen reduction. Nano Energy 2016,
27:390–401. https://doi.org/10.1016/j.nanoen.2016.07.024.
104. Wang Y-J, Long W, Wang L, Yuan R, Ignaszak A, Fang B,
Wilkinson DP: Unlocking the door to highly active ORR
catalysts for PEMFC applications: polyhedron-engineered
Pt-based nanocrystals. Energy Environ Sci 2018.
https://doi.org/10.1039/C7EE02444D.
105. Beermann V, Gocyla M, Kühl S, Padgett E, Schmies H, Goerlin M,
• Erini N, Shviro M, Heggen M, Dunin-Borkowski RE, Muller DA,
Strasser P: Tuning the electrocatalytic oxygen reduction
reaction activity and stability of shape-controlled Pt-Ni
nanoparticles by thermal annealing -elucidating the surface
atomic structural and compositional changes. J Am Chem Soc
2017, 139:16536–16547. https://doi.org/10.1021/jacs.7b06846.
In this work, in situ FTIR spectroscopy shows a correlation between CO
stretching frequency and activity for shape-controlled Pt-Ni
nanoparticles.
106. Cao L, Mueller T: Theoretical insights into the effects of
oxidation and mo-Doping on the structure and stability of
Pt-Ni nanoparticles. Nano Lett 2016, 16:7748–7754.
https://doi.org/10.1021/acs.nanolett.6b03867.
www.sciencedirect.com
Please cite this article as: Escudero-Escribano, Jensen, Jensen, Recent advances in bimetallic electrocatalysts for oxy-
gen reduction: design principles, structure-function relations and active phase elucidation, Current Opinion in Elec-
[mNS;June 16, 2018;4:6]
11
107. Jia Q, Zhao Z, Cao L, Li J, Ghoshal S, Davies V, Stavitski E,
Attenkofer K, Liu Z, Li M, Duan X, Mukerjee S, Mueller T,
Huang Y: Roles of Mo surface dopants in enhancing the ORR
performance of octahedral PtNi nanoparticles. Nano Lett 2018
acs.nanolett.7b04007.
https://doi.org/10.1021/acs.nanolett.7b04007.
108. Beermann V, Gocyla M, Willinger E, Rudi S, Heggen M,
Dunin-Borkowski RE, Willinger MG, Strasser P: Rh-doped Pt-Ni
octahedral nanoparticles: understanding the correlation
between elemental distribution, oxygen reduction reaction,
and shape stability. Nano Lett 2016, 16:1719–1725.
https://doi.org/10.1021/acs.nanolett.5b04636.
109. Lu BA, Sheng T, Tian N, Zhang ZC, Xiao C, Cao ZM, Bin Ma H,
Zhou ZY, Sun SG: Octahedral PtCu alloy nanocrystals with
high performance for oxygen reduction reaction and their
enhanced stability by trace Au. Nano Energy 2017, 33:65–71.
https://doi.org/10.1016/j.nanoen.2017.01.003.
110. Li D, Wang C, Strmcnik D, Tripković DV, Sun X, Kang Y, Chi M,
Snyder J, van der Vliet D, Tsai Y, Stamenkovic V, Sun S,
Markovic N: Functional links between Pt single crystal
morphology and nanoparticles with different size and shape:
the oxygen reduction reaction case. Energy Environ Sci 2014,
7:4061–4069. https://doi.org/10.1039/C4EE01564A.
111. Huang H, Li K, Chen Z, Luo L, Gu Y, Zhang D, Ma C, Si R, Yang J,
Peng Z, Zeng J: Achieving remarkable activity and durability
toward oxygen reduction reaction based on ultrathin
Rh-doped Pt nanowires. J Am Chem Soc 2017, 139:8152–8159.
https://doi.org/10.1021/jacs.7b01036.
112. Liu H, Zhong P, Liu K, Han L, Zheng H, Yin Y, Gao C: Synthesis of
ultrathin platinum nanoplates for enhanced oxygen reduction
activity. Chem Sci 2018, 0:1–7.
https://doi.org/10.1039/C7SC02997G.
113. Becknell N, Son Y, Kim D, Li D, Yu Y, Niu Z, Lei T, Sneed BT,
More KL, Markovic NM, Stamenkovic VR, Yang P: Control of
architecture in rhombic dodecahedral Pt-Ni nanoframe
electrocatalysts. J Am Chem Soc 2017, 139:11678–11681.
https://doi.org/10.1021/jacs.7b05584.
114. Luo S, Tang M, Shen PK, Ye S: Atomic-scale preparation of
octopod nanoframes with high-index facets as highly active
and stable catalysts. Adv Mater 2017:29.
https://doi.org/10.1002/adma.201601687.
115. Luo S, Shen PK: Concave platinum-copper octopod
nanoframes bounded with multiple high-index facets for
efficient electrooxidation catalysis. ACS Nano 2017,
11:11946–11953. https://doi.org/10.1021/acsnano.6b04458.
116. Cherevko S, Kulyk N, Mayrhofer KJJ: Durability of
platinum-based fuel cell electrocatalysts: dissolution of bulk
and nanoscale platinum. Nano Energy 2016, 29:275–298.
https://doi.org/10.1016/j.nanoen.2016.03.005.
117. Lopes PP, Strmcnik D, Tripkovic D, Connell JG, Stamenkovic V,
•• Markovic NM: Relationships between atomic level surface
structure and stability/activity of platinum surface atoms in
aqueous environments. ACS Catal 2016, 6:2536–2544.
https://doi.org/10.1021/acscatal.5b02920.
This study combines in situ ICP-MS detection with RDE measurements
on single-crystalline Pt surfaces, revealing the atomic-scale
structure-stability relations.
118. Jackson C, Smith GT, Inwood DW, Leach AS, Whalley PS,
Callisti M, Polcar T, Russell AE, Levecque P, Kramer D: Electronic
metal-support interaction enhanced oxygen reduction
activity and stability of boron carbide supported platinum. Nat
Commun, vol 8 2017. https://doi.org/10.1038/ncomms15802.
119. Cai B, Henning S, Herranz J, Schmidt TJ, Eychmüller A:
Nanostructuring noble metals as unsupported
electrocatalysts for polymer electrolyte fuel cells. Adv Energy
Mater, vol 7 2017 1700548.
https://doi.org/10.1002/aenm.201700548.
120. Chung DY, Yoo JM, Sung YE: Highly durable and active
Pt-based nanoscale design for fuel-cell oxygen-reduction
electrocatalysts. Adv Mater 2018, 1704123:1–20.
https://doi.org/10.1002/adma.201704123.
Current Opinion in Electrochemistry 2018, 000:1–12
JID: COELEC
ARTICLE IN PRESS
12 Surface Electrochemistry
121. Stephens IEL, Rossmeisl J, Chorkendorff I: Toward sustainable
fuel cells. Science 2016, 354:1378–1379.
https://doi.org/10.1126/science.aal3303.
122. Zalitis CM, Kramer D, Kucernak AR: Electrocatalytic
performance of fuel cell reactions at low catalyst loading and
high mass transport. Phys Chem Chem Phys 2013, 15:4329.
https://doi.org/10.1039/c3cp44431g.
123. Pinaud BA, Bonakdarpour A, Daniel L, Sharman J, Wilkinson DP:
Key considerations for high current fuel cell catalyst testing
in an electrochemical half-cell. J Electrochem Soc, vol 164
2017. https://doi.org/10.1149/2.0891704jes.
124. Inaba M, Jensen AW, Sievers GW, Escudero-Escribano M,
• Zana A, Arenz M: Benchmarking high surface area
electrocatalysts in a gas diffusion electrode: measurement of
oxygen reduction activities under realistic conditions. Energy
Environ Sci 2018, 11:988–994.
This work shows the design and application of a GDE that enable
measuring the ORR activity of nanocatalysts, showing performance
data comparable to MEAs.
125. Wu CH, Weatherup RS, Salmeron MB: Probing
electrode/electrolyte interfaces in situ by X-ray
spectroscopies: old methods, new tricks. Phys Chem Chem
Phys 2015, 17:30229–30239.
https://doi.org/10.1039/C5CP04058B.
126. Choi Y-W, Mistry H, Roldan Cuenya B: New insights into
working nanostructured electrocatalysts through operando
spectroscopy and microscopy. Curr Opin Electrochem 2017,
1:95–103. https://doi.org/10.1016/j.coelec.2017.01.004.
127. Nesselberger M, Arenz M: In situ FTIR spectroscopy: probing
the electrochemical interface during the oxygen reduction
reaction on a commercial platinum high-surface-area
catalyst. ChemCatChem 2016, 8:1125–1131.
https://doi.org/10.1002/cctc.201501193.
128. Russell AE, Rose A: X-ray absorption spectroscopy of low
temperature fuel cell catalysts. Chem Rev 2004,
104:4613–4636. http://pubs3.acs.org/acs/journals/doilookup?
in_doi=10.1021/cr020708r.
129. Casalongue HS, Kaya S, Viswanathan V, Miller DJ, Friebel D,
Hansen Ha, Nørskov JK, Nilsson A, Ogasawara H: Direct
observation of the oxygenated species during oxygen
reduction on a platinum fuel cell cathode. Nat Commun 2013,
4:2817. https://doi.org/10.1038/ncomms3817.
130. Zhang J, Sasaki K, Sutter E, Adzic RR: Stabilization of platinum
oxygen-reduction electrocatalysts using gold clusters.
Science 2007, 315:220–222.
https://doi.org/10.1126/science.1134569.
131. Ogasawara H, Kaya S, Nilsson A: Operando X-ray
photoelectron spectroscopy studies of aqueous
electrocatalytic systems. Top Catal 2016, 59:439–447.
https://doi.org/10.1007/s11244- 015- 0525- 3.
132. Ruge M, Drnec J, Rahn B, Reikowski F, Harrington DA, Carlà F,
Felici R, Stettner J, Magnussen OM: Structural reorganization
of Pt(111) electrodes by electrochemical oxidation and
reduction. J Am Chem Soc 2017, 139:4532–4539.
https://doi.org/10.1021/jacs.7b01039.
Current Opinion in Electrochemistry 2018, 000:1–12
Please cite this article as: Escudero-Escribano, Jensen, Jensen, Recent advances in bimetallic electrocatalysts for oxy-
gen reduction: design principles, structure-function relations and active phase elucidation, Current Opinion in Elec-
[mNS;June 16, 2018;4:6]
133. Drnec J, Ruge M, Reikowski F, Rahn B, Carlà F, Felici R,
Stettner J, Magnussen OM, Harrington DA: Initial stages of
Pt(111) electrooxidation: dynamic and structural studies by
surface X-ray diffraction. Electrochim Acta 2017, 224:220–227.
https://doi.org/10.1016/j.electacta.2016.12.028.
134. Escudero-Escribano M, Pedersen AF, Ulrikkeholm ET, Jensen KD,
Hansen MH, Rossmeisl J, Stephens IEL, Chorkendorff I: Active
phase formation and stability of Gd/Pt(111) electrocatalysts
for oxygen reduction: an in situ surface X-ray diffraction
study. Under review in Chemistry - A European Journal 2018.
135. Mezzavilla S, Cherevko S, Baldizzone C, Pizzutilo E, Polymeros G,
Mayrhofer KJJ: Experimental methodologies to understand
degradation of nanostructured electrocatalysts for PEM fuel
cells: advances and opportunities. ChemElectroChem 2016,
3:1524–1536. https://doi.org/10.1002/celc.201600170.
136. Dubau L, Maillard F: Unveiling the crucial role of temperature
on the stability of oxygen reduction reaction electrocatalysts.
Electrochem Commun 2016, 63:65–69.
https://doi.org/10.1016/j.elecom.2015.12.011.
137. Mayrhofer KJJ, Hartl K, Juhart V, Arenz M: Degradation of
carbon-supported Pt bimetallic nanoparticles by surface
segregation. J Am Chem Soc 2009, 131:16348–16349.
https://doi.org/10.1021/ja9074216.
138. Baldizzone C, Gan L, Hodnik N, Keeley GP, Kostka A, Heggen M,
Strasser P, Mayrhofer KJJ: Stability of dealloyed porous Pt/Ni
nanoparticles. ACS Catal 2015, 5:5000–5007.
https://doi.org/10.1021/acscatal.5b01151.
139. Wan LJ, Moriyama T, Ito M, Uchida H, Watanabe M: In situ STM
imaging of surface dissolution and rearrangement of a Pt-Fe
alloy electrocatalyst in electrolyte solution. Chem Commun
2002:58–59. https://doi.org/10.1039/b107037a.
140. Kobayashi S, Aoki M, Wakisaka M, Kawamoto T, Shirasaka R,
Suda K, Tryk DA, Inukai J, Kondo T, Uchida H: Atomically flat Pt
skin and striking enrichment of Co in underlying alloy at
Pt3Co(111) single crystal with unprecedented activity for the
oxygen reduction reaction. ACS Omega 2018, 3:154–158.
https://doi.org/10.1021/acsomega.7b01793.
141. Jacobse L, Huang Y-F, Koper MTM, Rost MJ: Correlation of
•• surface site formation to nanoisland growth in the
electrochemical roughening of Pt(111). Nat Mater 2018,
17:277–282. https://doi.org/10.1038/s41563- 017- 0015- z.
Using EC-STM, this paper presents direct evidence of the formation
and growth of nanoislands during cyling up to potential regions relevant
for ORR.
142. Pfisterer JHK, Liang Y, Schneider O, Bandarenka AS: Direct
• instrumental identification of catalytically active surface
sites. Nature 2017, 549:74–77.
This work presents the use of tunneling noise to identify catalytic active
regions in EC-STM with a resolution of only 1–2nm.
www.sciencedirect.com