Journal of Alloys and Compounds 718 (2017) 204e214

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Bimetallic PdM (M ¼ Fe, Ag, Au) alloy nanoparticles assembled on

reduced graphene oxide as catalysts for direct borohydride fuel cells


Marta Martins a, Biljana Sljuki €
c a, Onder Metin b, **, Melike Sevim b, Ce
sar A.C. Sequeira a,
Tansel Şener c, Diogo M.F. Santos a, *
a
CeFEMA, Instituto Superior T
ecnico, Universidade de Lisboa, 1049e001 Lisbon, Portugal
b
Department of Chemistry, Faculty of Science, Atatürk University, 25240 Erzurum, Turkey
c
KetenciZade Energy, Istanbul, Turkey

a r t i c l e i n f o a b s t r a c t

Article history: The development of highly active and inexpensive electrode materials is crucial to improve the perfor-
Received 29 March 2017 mance of fuel cells and to boost their commercialisation. In this work, a series of bimetallic palladium
Received in revised form alloy nanoparticles assembled on reduced graphene oxide, namely PdFe/rGO, PdAg/rGO and PdAu/rGO,
4 May 2017
was prepared and tested for oxygen reduction reaction (ORR) and borohydride oxidation reaction (BOR)
Accepted 6 May 2017
Available online 10 May 2017
in alkaline media. The morphology and structure of the as-prepared PdM alloy NPs and PdM/rGO
electrocatalysts were characterised by XRD, TEM, XPS and ICP-MS and their electrochemical activity was
investigated by cyclic and linear scan voltammetry, chronoamperometry, and rotating disc electrode
Keywords:
Palladium alloys
measurements. Among the tested electrocatalysts, PdAu/rGO demonstrated the best performance by
Reduced graphene oxide providing high current densities for both ORR and BOR. The number of electrons exchanged during ORR
Oxygen reduction reaction at PdAu/rGO, PdAg/rGO and PdFe/rGO electrocatalysts was calculated to be 4.0, 2.8 and 2.0, whereas Tafel
Borohydride oxidation reaction slopes were evaluated to be 0.202, 0.182 and 0.173 V dec1, respectively. BOR at PdAu/rGO and PdFe/rGO
Direct borohydride fuel cell proceeds with 5.5 and 2 electrons exchanged, respectively, and the reaction order ranged from 0.4 for
PdAg/rGO to 1 for PdAu/rGO. Furthermore, effect of temperature was studied and BOR activation energy
determined to be 23 kJ mol1.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction temperatures (32.8e250 mW cm2; DMFC: 30e100 mW cm2;

The direct borohydride fuel cell (DBFC) is a type of alkaline fuel
cell that uses a sodium borohydride (NaBH4) solution as the fuel
and oxygen (O2) as the oxidant. They are seen as alternative power
sources for stationary applications and, especially, for portable
applications and transportation [1e5].
DBFCs present attractive features, such as easy handling of the
liquid borohydride fuel, relatively low corrosion due to use of
alkaline electrolyte, high theoretical open circuit voltage (1.64 V;
CH3OH/O2: 1.19 V; H2/O2: 1.23 V; HCOOH/O2: 1.45 V; N2H4/O2:
1.56 V), high energy density (9.3 Wh g1; lithium battery: 0.25 Wh
g1; lead acid battery: 0.02e0.05 Wh g1; nickel-metal hydride
battery: 0.06e0.10 Wh g1) and high power density at ambient
* Corresponding author.
** Corresponding author.
€ Metin), diogosantos@tecnico.
E-mail addresses: ometin@atauni.edu.tr (O.
ulisboa.pt (D.M.F. Santos).
PEMFC: 300e1000 mW cm2) [1e5]. Borohydride oxidation reac-
tion (BOR) in alkaline media is ideally an 8electron process (Eq.
(1)) [6]. However, at many materials used for DBFC anodes, BOR is
an incomplete process due to a concurrent borohydride, BH 4 , hy-
drolysis reaction, so that the number of electrons exchanged is
lower than 8 and BOR becomes represented by Eq. (2), where x is
the actual number of exchanged electrons.
BH    0
4 þ 8 OH / B(OH)4 þ 4 H2O þ 8 e E ¼ 1.24 V vs. SHE (1)
BH  
4 þ x OH / B(OH)4 þ (x  4) H2O þ (4  x/2) H2 þ x e

(2)
Oxygen reduction reaction (ORR) in alkaline conditions can
occur mainly by two mechanisms: one involving the direct transfer
of 4e to produce OH as the end product (full discharge) (Eq. (3)),
and other involving 2e transfer to form hydroperoxide ion, HO2 , as
intermediate species (Eq. (4)) [7,8].

http://dx.doi.org/10.1016/j.jallcom.2017.05.058
0925-8388/© 2017 Elsevier B.V. All rights reserved.
 M. Martins et al. / Journal of Alloys and Compounds 718 (2017) 204e214
O2 þ 2 H2O þ 4 e / 4 OH E0 ¼ 0.401 V vs. SHE (3)
O2 þ H2O þ 2 ee / HO  0
2 þ OH E ¼ 0.065 V vs. SHE (4)
Subsequently, HO 2 can undergo further reduction (Eq. (5)) or
catalytic decomposition (Eq. (6)).
HO e  0
2 þ H2O þ 2e / 3OH E ¼ 0.867 V vs. SHE (5)
2HO
2 / O2 þ 2OH

(6)
In order to get the maximum energy capacity, it is desirable to
reduce O2 via the 4e pathway. In the case of O2 reduction via the
2e mechanism, not only the efficiency is lower, but generated HO 2 or BOR study using rGO as a support material for PdFe and PdAg
can also lead to electrocatalyst corrosion and chemical degradation
of the membrane separator in fuel cells [9]. It is well known that the
activity of electrocatalysts strongly depends on the electronic and
structural properties of the participating metal. Platinum (Pt)-
based materials are widely used as electrocatalysts for both the
cathode (ORR) and the anode (BOR) processes of the DBFC
[1,10e12]. However, Pt presents limitations related to scarceness
and high price, which hampers the commercialisation of most fuel
cells, particularly of the DBFC.
In this context, recent efforts have been made in the search for
new electrocatalysts with lower cost and higher electrocatalytic
activity for the fuel cell reactions. Specifically, palladium (Pd) is one
of the leading candidates in this respect [2]. Pd is often alloyed with
transition metals to improve its electrocatalytic properties and
activity, in particular for the ORR and BOR [13]. Pd alloys with nickel
(Ni), copper (Co) or iron (Fe) have proven alloying to be an effective
way to reduce the electrocatalysts cost and simultaneously to
enhance their performance for the ORR [13]. On the other hand, the
performance of an electrocatalyst is also affected by the support
material. A desirable support material should have large mesopore
volume to obtain a homogeneous distribution of the metal nano-
particles on the surface, high specific surface area, high electrical
conductivity and sufficient mechanical stability [14]. Additionally,
the surface functional groups and the graphitisation degree of the
supports proved to have effect on the activity and stability of the
electrocatalysts [15]. For these reasons, different carbon materials,
such as carbon black, activated carbon or carbon nanotubes, are
commonly used as support in electrocatalysts [16]. However, low
stability in corrosive fuel cell environments has led to the search for
better electrocatalyst supports. Recent studies involve graphene
oxide (GO) as the metal support, since it contains abundant oxygen
functional groups that act as the binding sites for metal nano-
particles (M NPs) [17,18]. Nonetheless, an excess of these functional
groups on GO surface is not desirable because it decreases the
conductivity and stability of the electrocatalysts. Reduced graphene
oxide (rGO) has been demonstrated to be an optimal candidate to
overcome this issue owing to its advantageous properties such as
high surface area, high conductivity and potentially low-cost
manufacturing [19]. rGO has been pointed out as a support mate-
rial that enhances the activity and stability of metal electrocatalyst
for methanol oxidation and oxygen reduction reactions [20,21]. For
example, Carrera-Cerritos et al. reported better performance for
ORR of Pd nanoparticles (NPs) supported on rGO than that of Pt NPs
supported on carbon black, demonstrating the dependence of the
electrocatalyst activity for the ORR on the interaction of metal NPs
and support material [22]. Bikkaroll et al. [23] also reported
enhanced catalytic activity of rGO towards ORR in alkaline solutions
compared to the starting GO. In recent studies, we also successfully
demonstrated that PdM and PtM (M: Co, Ni, Cu) alloy NPs sup-
ported on rGO show enhanced performances compared to those of
supported on commercial carbon materials at the cathode of Li-air
205
batteries [24,25].
In the present study, rGO was employed as the support material
to decrease the cost and improve the catalytic properties of three
bimetallic PdM alloy NPs, namely PdAu, PdAg and PdFe. Established
protocols reported elsewhere [26e28] were used to synthesise the
monodisperse PdM NPs. In our previous studies, PdAg [27] and
PdAu [28] alloy NPs supported on Ketjenblack carbon were tested
for the formic acid dehydrogenation while PdFe alloy NPs sup-
ported on rGO [26] were used as catalysts in the transfer hydro-
genation of aromatic nitro compounds to aromatic amines. Herein,
PdAu, PdAg and PdFe alloy NPs supported on rGO were tested for
ORR and BOR for potential application in alkaline fuel cells. To the
best of the authors' knowledge, there is no previously reported ORR
alloys, as well as the resulting comparative performance exami-
nation of three PdM alloy NPs synthesised by similar recipes and
deposited on the same support under identical conditions.
2. Experimental
2.1. Synthesis of monodisperse PdM (M: Fe, Ag, Au) alloy
nanoparticles
2.1.1. PdFe alloy NPs
PdFe alloy NPs were prepared as described in authors' previous
report [26]. In a typical recipe, 0.2 g of morpholine borane (MB,
Sigma-Aldrich, 95%), 3 mL of oleylamine (OAm, Sigma-Aldrich, 70%)
and 7 mL of 1-octadecene (ODE, 90%) were mixed in a four-necked
round bottom glass reactor (100 mL) that allows studies under
temperature control and argon gas. Next, the resulting solution was
heated to 100  C. In a separate glass vial, 0.25 mmol of iron(III)
acetylacetonate (Fe(acac)3, Sigma-Aldrich, 97%) and 0.25 mmol of
palladium(II) acetylacetonate (Pd(acac)2, Sigma-Aldrich, 99%) were
dissolved in 3 mL of OAm at room temperature and the resultant
mixture was then injected into the reactor. The reaction mixture
was kept at 110  C for 1 h before cooled down. The NPs were
separated from the mixture solution by adding acetone and
centrifugation at 9000 rpm for 12 min. The separated NPs were
dispersed in hexane and precipitated by ethanol addition, followed
by centrifugation. Subsequently, the solvent was thrown away and
PdFe NPs were re-dispersed in hexane and kept for further use.
2.1.2. PdAg alloy NPs
PdAg alloy NPs were prepared by a modified procedure
described in authors' previous work [27]. Thus, 0.5 mmol of silver(I)
acetate (Ag(Ac), Sigma-Aldrich, 99%) and 0.5 mmol of Pd(acac)2
(Sigma-Aldrich, 99%) were dissolved in a mixture of 4.5 mL of oleic
acid (OAc, Fluka, 95%), 0.5 mL of OAm and 10 mL of ODE in a four-
necked glass reactor under a gentle argon gas flow. The mixture
was first heated to 60  C and kept at this temperature for 5 min, and
then heated to 180  C and kept at this temperature for 20 min. The
NPs were separated by adding isopropanol (40 mL) and centrifu-
gation (9500 rpm, 8 min) after the reaction solution was cooled
down. This purification step was repeated twice to remove the
organic impurities and precursor residues.
2.1.3. PdAu alloy NPs
PdAu alloy NPs were prepared following the author's well-
established method [28]. In a typical recipe, 0.2 g of MB was
mixed with 10.0 mL of OAm in a four-necked glass reactor under a
gentle argon flow. The formed solution was heated to 75  C under
magnetic stirring. Subsequently, 0.07 g of Pd(acac)2 and 0.06 g of
hydrogen tetrachloroaurate(III) hydrate (HAuCl4$H2O, Alfa Aesar,
99.9%) was mixed in 4.0 mL of OAm in a separate glass vial and
injected quickly into the reactor. The resulting solution was heated
206 M. Martins et al. / Journal of Alloys and Compounds 718 (2017) 204e214

to 220  C at a rate of 5e7  C min1 and kept at this temperature for ORR studies were carried out in O2-saturated 1 M NaOH solution
30 min before cooling it to room temperature. The NPs were by bubbling in the gas for 15 min prior the measurements and
separated from the mixture solution by adding 2-propanol and keeping the O2-atmosphere during the measurements. BOR studies
centrifugation at 9000 rpm for 12 min. The NPs were dispersed in were carried out in 2 M NaOH supporting electrolyte containing
hexane and precipitated by ethanol addition and subsequent NaBH4 concentrations ranging from 0.01 to 0.12 M. Temperature
centrifugation. The solvent was then thrown away and PdAu NPs influence on BOR at the studied electrocatalysts was explored by
were re-dispersed in hexane and kept for further use. controlling the solution temperature (25e65  C) with water cir-
culation using a Haaeke F3 thermostatic bath. The studies were
2.2. Preparation, characterisation, and electrochemical evaluation performed using cyclic voltammetry (CV), linear scan voltammetry
of the electrocatalysts and chronoamperometry (CA) with rotating disc electrode (RDE).
CVs for BOR studies were recorded using a scan rate of 0.01e1 V s1
2.2.1. Assembly of PdM alloy NPs on rGO range. All RDE LSVs were recorded using scan rate of 0.01 V s1 and
Details of the rGO synthesis procedure and its structural char- a rotation rate in the 400e2800 rpm range. The current densities
acterisation can be found in authors' previous reports [29]. PdM were normalised using the geometric surface area of the GC disc
alloy NPs were assembled on rGO nanosheets by well-established electrode (0.1963 cm2).
liquid phase self-assembly method, which the authors previously
used for the assembly of other metal NPs [30]. In a typical assemble
3. Results and discussion
protocol, 100 mg of rGO was dispersed in the 75 mL of ethanol/
hexane mixture (v/v ¼ 2/1) and then 50 mg of hexane dispersions
3.1. Characterisation of PdM (M ¼ Fe, Ag, Au) alloy NPs and PdM/
of PdM alloy NPs were added into the mixture. Next, the resulting
rGO electrocatalysts
mixture was sonicated for 2 h. To separate the PdM/rGO electro-
catalysts from the solution, the mixtures were centrifuged at
The structure of the prepared PdM NPs was examined by XRD
7500 rpm for 10 min after washing in ethanol several times and
(Fig. 1). All the PdM NPs have face centred cubic (fcc) crystal phase
then dried in vacuum.
with highly observable (111) facets. It is clear that the (111) facets of
the PdM NPs are shifted to higher 2q degrees compared to the
2.2.2. Characterisation of the electrocatalysts
metallic Pd (JCPDS card no: 01-071-3757), indicating the solid-
The crystal structure and PdM alloy formation was examined by
solution (alloy) formation between Pd and Fe, Ag, or Au.
X-ray diffraction (XRD) analysis of PdFe, PdAg, and PdAu alloy NPs
Fig. 2AeC shows the representative TEM images of colloidal
using a PANalytical Empyrean diffractometer with Cu Ka radiation
PdM alloy NPs while Fig. 2GeH are the TEM-image associated
(40 kV, 15 mA, 1.54051 Å). Transmission electron microscopy (TEM)
particle size histograms. All PdM alloy NPs were found to have
images of the colloidal PdFe, PdAg, and PdAu alloy NPs and of the
uniform particle size distribution with the average particle size of
rGO-supported electrocatalysts were obtained with FEI Technai G2
5.2 nm for PdFe (Fig. 2A and G), 2.2 nm for PdAg (Fig. 2B and H) and
Spirit BiO(TWIN) instrument working at 120 kV. The surface
4.8 nm for PdAu NPs (Fig. 2C and I), calculated by counting at least
structure of the PdM/rGO catalysts was analysed by X-ray photo-
100 untouched particles manually. Among the as-prepared PdM
electron spectroscopy (XPS) using a SPECS XP Flexmod (Germany)
alloy NPs, only PdFe alloy NPs show variety in their shapes, most
equipped with a PHOIBOS hemispherical energy analyser. A
probably due to the distinct nucleation and small radius of Fe atoms
monochromatic Al Ka X-ray excitation (hn ¼ 15 kV, 400 W) source
compared to those of Ag and Au atoms, which have properties and
was employed in the XPS data acquisition. The metal content in the
radius more similar to Pd. Next, a series of inductively coupled
electrocatalysts was determined by inductively coupled plasma -
plasma-mass spectrometry (ICP-MS) analysis was performed to
mass spectrometry (ICP-MS) using an Agilent Technologies 7800
determine the composition of the as-synthesised PdM alloy NPs.
instrument.
The compositions were found to be Pd52Fe48, Pd58Ag42 and
Pd51Au49. In addition, the metallic loading ratio of the alloy NPs on
2.2.3. Electrochemical measurements
rGO was found to be 15e16 wt.% approximately. As-prepared PdM
Electrochemical measurements were performed on Gamry
alloy NPs were subsequently assembled on rGO via sonication in
PCI4/300 potentiostat/galvanostat with Pine AFCPRB rotator using
the hexane dispersion for 1 h. Fig. 2DeF shows the representative
a three-electrode cell of 50 mL volume. The counter electrode was a
TEM images of Pd52Fe48/rGO (Fig. 2D), Pd58Ag42/rGO (Fig. 2E) and
Pt coil and the reference was a saturated calomel electrode (SCE,
Pd51Au49/rGO (Fig. 2F) electrocatalysts where NPs were well-
KCl std.). The potentials measured with the SCE reference were then
dispersed over rGO nanosheets with no observable morphology
converted to the reversible hydrogen electrode (RHE) scale. All
potentials shown throughout the manuscript are referred to the
RHE scale. The working electrode was based on the PdAu/rGO,
PdAg/rGO or PdFe/rGO electrocatalysts. The electrocatalysts were
studied as a thin layer deposited on a smooth glassy carbon (GC)
disc electrode. Catalytic inks were prepared by dispersing each
electrocatalyst in 2 wt.% solution of polyvinylidene fluoride (PVDF,
Aldrich) in N methyl-2-pyrrolidone (NMP, Johnson Matthey) and
then ultrasonically mixed for 30 min. Suspension was pipetted onto
GC surface, yielding an electrocatalyst loading of 2 mg cm2, i.e.,
PdM loading of ca. 0.3 mg cm2, and then heated at 100  C over-
night for the solvent to evaporate.
Electrochemical characterisation of the prepared PdM/rGO alloy
electrodes was carried out in 0.5 M H2SO4 at a scan rate of
0.05 V s1 to determine their electrochemical surface area (ECSA).
The roughness factors (RF) of the electrodes were determined as
ratios of the ECSA (in cm2) and geometric area. Fig. 1. XRD patterns of the PdM alloy NPs.
 M. Martins et al. / Journal of Alloys and Compounds 718 (2017) 204e214
Fig. 2. Representative TEM images and the associated particle size histograms of (A,G) PdFe NPs, (B,H) PdAg NPs and (C,I) PdAu NPs, and TEM images of (D) PdFe/rGO, (E) PdAg/rGO
and (F) PdAu/rGO electrocatalysts.
and particle size change. The PdM/rGO were directly used as elec-
trocatalysts without any purification step.
X-ray photoelectron spectroscopy (XPS) analysis was then car-
ried out to get additional information on the surface structure of
the PdM/rGO catalysts. Fig. 3 shows the survey and the high-
resolution XPS spectra of PdAu/rGO, PdFe/rGO and PdAg/rGO
catalysts.
XPS survey spectrum of PdAu/rGO catalyst indicates the pres-
ence of C, O, Pd and Au atoms as expected (Fig. 3A). Upon the ex-
amination of high-resolution XPS spectra of PdAu/rGO catalysts for
Pd3d and Au4f core-levels (Fig. 3B and C), two main peaks are
observed for both levels at binding energies of 335.4 eV and
340.7 eV for Pd3d (Fig. 3B) and 83.6 eV and 87.3 eV for Au4f
(Fig. 3C), which reveal that both metals are in the metallic state
[31]. However, there is a shift to higher binding energies for Pd3d,
while the contrary is observed for Au4f indicating a charge transfer
from Au to Pd and thus indicating alloy formation. In the case of
PdFe/rGO catalyst, the presence of C, O, Fe, and Pd atoms was
207
determined by XPS survey spectrum (Fig. 3D). There are two main
peaks observable at the high-resolution XPS spectrum for the Pd3d
region at 334.7 and 340.0 eV (Fig. 3E) and for Fe2p region at 709.7
and 722.8 eV (Fig. 3F), which is indicative of metallic Pd and oxi-
dised Fe species. This is not surprising for the XPS analysis of Fe
samples because the catalyst sample is exposed to air for a certain
time during the sample preparation and it is well-known that Fe is
highly sensitive to air, being easily oxidised. The XPS survey scan
demonstrates the existence of C, O, Ag, and Pd atoms on the surface
of rGO/PdAg catalysts (Fig. 3G). Two main peaks were observable
for Pd3d region at binding energies of 346.5 and 341.0 eV and for
Ag3d region at 380.6 and 374.3 (Fig. 3H and I), which indicates that
both metals are in the metallic state [32]. A shift observed on the
Ag3d5/2 core-level indicates the alloy formation between Ag and
Pd. From the XPS analyses of the PdM/rGO catalysts, it is concluded
that Pd is found both in the metallic state and alloyed with the Au,
Fe or Ag metals.
The electrochemical characterisation of the PdM/rGO
208 M. Martins et al. / Journal of Alloys and Compounds 718 (2017) 204e214

Fig. 3. XPS survey spectra of (A) PdAu/rGO, (D) PdFe/rGO, and (G) PdAg/rGO catalysts and the corresponding high-resolution core-level spectra of (B) Pd3d and (C) Au4f (in PdAu/
rGO), (E) Pd3d and (F) Fe2p (in PdFe/rGO), and (H) Pd3d and (I) Ag3d (in PdAg/rGO).

electrocatalysts was initially carried out by cyclic voltammetry in
typical conditions, i.e., deaerated 0.5 M H2SO4 solution at a scan rate
of 0.05 V s1 [33,34]. Fig. 4 illustrates the representative CV of PdAu/
rGO where an anodic and a cathodic peak appear in the potential
window from 0.15 to 1.65 V. A broad anodic peak observed at ca.
0.95 V on the forward scan can be attributed to the formation of Pd
surface oxides. Subsequently, a better defined cathodic peak at ca.
0.62 V observed on the reverse scan could be readily assigned to the
reduction of those oxides. Consequently, the electrochemical sur-
face area (ECSA) of PdM/rGO electrodes was calculated from the
 M. Martins et al. / Journal of Alloys and Compounds 718 (2017) 204e214
Fig. 4. CV of PdAu/rGO in deaerated 0.5 M H2SO4 solution recorded at scan rate of
0.05 V s1 and calculated ECSA and RF values for the PdM/rGO electrodes (inset).
reduction of PdO, assuming that the charge necessary to reduce the
oxide monolayer is 424 mC cm2 [33]. The obtained ECSA and
roughness factor (RF) values are shown in the inset of Fig. 4.
Namely, ECSA of PdAu/rGO, PdFe/rGO and PdAg/rGO were deter-
mined to be 2.81, 3.59 and 5.78 m2 g1, respectively, with the
highest ECSA of PdAg/rGO reflecting the smaller size of its M NPs.
These values are comparable or lower than those reported for Pt/C
(2.52 m2 g1), Pd/C (7.48 m2 g1), AuxPdy NPs (2.22e17.28 m2 g1)
or Au-Pd NPs/rGO (32.81 m2 g1) [35,36].
3.2. Oxygen reduction studies
Initial study of the oxygen reduction at PdM/rGO electro-
catalysts was done by recording CVs in deaerated (N2-saturated)
and then in O2-saturated 1 M NaOH. Fig. S1 in electronic supple-
mentary information (ESI) shows direct comparison of these CV
curves for PdAu/rGO revealing its good ORR activity. Namely, a peak
corresponding to metal oxides reduction is observed at ca. 0.65 V at
CV recorded in deaerated (O2-free) 1 M NaOH solution. This peak
increases noticeably in O2-saturated solution, indicating that the O2
reduction takes place along with the oxides electrochemical
reduction. Subsequently, the RDE experiments were conducted in
O2-saturated 1 M NaOH and ORR onset potentials were found to be
ca. 0.82, 0.75 and 0.72 V for PdAu/rGO, PdAg/rGO and PdFe/rGO,
respectively. The recorded values are comparable or somewhat
shifted negatively in respect to those previously reported for ORR at
Pd-based electrocatalysts (for instance, 0.82 V for Pd-Ag, 0.85 V for
Pd/Vulcan, 0.86 V for Pd/KB, 0.90 for Pd/rGO, 0.91 V for Au@Pd core-
shell nanothorns, 0.93 V for Au/rGO and 1.10 V for Au-Pd NPs/rGO)
[35,37e39]. The onset potential for PdAu/rGO is comparable to that
for ORR at Pt/C (0.83 V) as benchmark electrocatalyst [40]. The
highest current densities were obtained at PdAu/rGO, while the
current densities at PdFe/rGO and PdAg/rGO were similar and
notably lower than those at PdAu/rGO (Fig. 5A and B). Furthermore,
the current density recorded at PdAu/rGO (2.76 mA cm2) at 0.4 V
using rotation of 1600 rpm was higher than those recorded at 10%
Pt/C (0.24 mA cm2) and 10% Pd/C (0.24 mA cm2) [41] and com-
parable to those reported at Pt/rGO (3.31 mA cm2) [41], Pd/rGO
(3.00 mA cm2) [41,42], Au/rGO (2.55 mA cm2) [43], PtPd/rGO
electrocatalysts of different morphologies (2.64e3.99 mA cm2)
[41] and previously reported PdAu/rGO (2.94 mA cm2) [35]. Spe-
cific current densities at 0.4 V using rotation of 1600 rpm were
found to be 1.13, 1.46 and 9.2 A g1 for PdAg/rGO, PdFe/rGO and
PdAu/rGO, respectively. Again, the value obtained for PdAu/rGO
was higher than values reported for 10% Pt/C (7.75 A g1) and 10%
Pd/C (7.33 A g1), and lower than those reported for Pt/rGO
209
(17.17 A g1), Pd/rGO (15.56 A g1) and different PtPd/rGO elec-
trocatalysts (13.88e22.72 A g1) [41].
PdAu/rGO ORR activity derives from synergistic effects between
Pd, Au and rGO. In fact, rGO was reported to exhibit a low elec-
trocatalytic activity for the ORR, indicating that rGO not only acts as
a support but also has synergistic effects on the catalytic perfor-
mance of PdAu NPs by facilitating the electron transfer [40]. High
dispersion of the M NPs onto high specific surface rGO support
provides more active sites for ORR. The strong interactions between
M NPs and rGO prevents the M NPs agglomeration, as well as their
detachment from the support. Presence of Au atoms modifies
electronic structures of Pd atoms, with Au atoms acting as elec-
tronic promoters [44,45]. Namely, ORR includes both the breaking
of the OeO bond and the formation of the OH bond [46,47]. The
surface reactivity of a metal is governed by its d-band centre energy
(εd), so that the changes of εd result in different ORR activities [48].
It was shown that higher εd facilitates the OeO bond breaking,
while hampering the OH bond formation, leading to strongly bound
adsorbates. On the other hand, lower εd promotes the OH bond
formation, while weakening the adsorbates binding. The presence
of more electronegative Au favours the electron-withdraw from Au
to adjacent Pd, weakens the Pd-O adsorption and facilitates the
removal of poisoning intermediate species, thus enhancing the
catalytic performance and stability of PdAu/rGO electrocatalysts
[49].
As expected, ORR current densities recorded at PdM/rGO elec-
trocatalysts increased with increasing the electrode rotation rates
owing to the higher amounts of O2 reaching the electrode surface
under the convective flow. Fig. 5C, shows the ORR polarisation
curves for PdAu/rGO ranging from 0 to 2400 rpm. The LSV data
recorded for each electrocatalyst at different rotation rates were
used to determine the ORR kinetic parameters. Koutecky-Levich (K-
L) equation (Eq. (7)) decomposes the measured ORR current den-
sity, j, into the diffusion-limited current density, jd, and the kinetic
current density, jk, components,
1 1 1 1 1
¼ þ ¼ þ (7)
j jd jk 0:62nFD2=3 n1=6 Cbulk u1=2 jk
where F is Faraday's constant (96485 C mol1), u is the electrode
rotation rate (rad s1), Cbulk is the O2 concentration in O2-saturated
1 M NaOH solution (8.4  107 mol cm3), D is the O2 diffusion
coefficient (1.56  105 cm2 s1) and n is the kinematic viscosity of
the solution (1.19  102 cm2 s1) [50].
The pure Faradaic currents in O2-saturated 1 M NaOH solution
were obtained by subtracting the background current obtained in
deaerated solution under the same conditions. The number of
exchanged electrons, n, can be determined from the slope of the K-L
plots (Fig. 5D), j1 vs. u1/2. The n values calculated in the 0.2e0.3 V
potential region were found to be 4.0, 2.8 and 2.0 for PdAu/rGO,
PdAg/rGO and PdFe/rGO electrocatalyst, respectively. These n
values suggest that PdAu/rGO reduces O2 to OH via direct mech-
anism, while PdAg/rGO and PdFe/rGO reduce it to HO 2 ion. The
synergistic effect between metallic components of an alloy on their
ORR activity has been previously reported. Lv et al. demonstrated
enhanced catalytic activity of PdAu/rGO for ORR and improved
stability in alkaline media compared to Pd/C [35]. Furthermore, Ji
et al. suggested that synergistic effect between graphene and Au
weakens the adsorption of anions that normally poison the elec-
trocatalyst surface [51]. As mentioned, ORR activity is determined
by the ability of a metal to break OeO bond and the stability of the
adsorbed oxygen atom (generated by O2 splitting) predicted by the
thermodynamic data, as well as by the metals ability for the OH
adsorption and oxide formation, as OH adsorption tends to inhibit
ORR [38,52].
210 M. Martins et al. / Journal of Alloys and Compounds 718 (2017) 204e214

Fig. 5. Results of ORR study at PdAg/rGO, PdAu/rGO and PdFe/rGO alloy electrocatalysts, including (A) the LSVs in O2-saturated 1 M NaOH solution at 0.01 V s1 and 1600 rpm, (B)
the Tafel slopes and current densities at 0.4 V at 1600 rpm, (C) RDE LSVs of PdAu/rGO at rotation rates up to 2400 rpm and (D) the corresponding Koutecky-Levich plots.

Well defined diffusion-limited current densities were not the amount of Ag in the alloy) [38].
reached at the three electrocatalysts, similarly to previously re-
ported behaviour of PdAg [38]. Thus, diffusion-limited current
3.3. Borohydride oxidation studies
densities deviate from the expected values of ca. 1.5 mA cm2 for 2-
electron and 3 mA cm2 for 4-electron pathway. Deviations from
Initial study of BOR at PdM/rGO electrocatalysts was performed
the expected ORR diffusion-limited current density values have
by recording CVs in 0.03 M NaBH4 in 2 M NaOH solution from the
been previously reported due to the pseudo-capacitance of the
materials' OCP (in the 0.13 to 0.22 V range) up to 1.57 V. All three
carbon support in the double layer region [53]. Moreover, diffusion-
studied electrocatalysts showed activity for BOR with higher cur-
limited current density is also influenced by the electrocatalyst
rent densities and additional oxidation peaks observed compared
loading so that it remains constant until the loading is decreased
to CVs recorded in the supporting electrolyte with no BH 4 present.
below a limit at which the amount of electrocatalyst cannot spread
Fig. 6A shows typical CVs obtained for PdAg/rGO electrocatalyst in
over the whole surface of the GC support and uncovered areas
2 M NaOH solution in the presence and in the absence of 0.03 M
remain. This limit depends on the specific surface area of the
NaBH4. In the borohydride-containing solution a distinctive
electrocatalysts e the higher the area, the lower the amount of
oxidation peak a1 is seen at ca. 0.92 V on the anodic scan, as well as
electrocatalyst required to maintain the constant value of diffusion-
an oxidation peak c1 at ca. 0.62 V on the back scan. No CVs of PdAu/
limited current density [53].
rGO and PdFe/rGO were qualitatively similar to that of PdAg/rGO
Additionally, Tafel analysis of ORR at PdAg/rGO, PdAu/rGO and
with somewhat broader peaks. The a1 peak is attributed to oxida-
PdFe/rGO was carried out. Tafel slope is related with the rate at
tion of both BH 4 and its hydrolysis products, mainly BH3OH .

which the current density increases with the increase of the 
Namely, BH3OH ions can be fully oxidised according to Eq. (8) with
applied potential and can reveal changes in the apparent ORR
release of 6 electrons [56e58].
mechanism. Thus, Tafel plots (Fig. S2 in ESI) were constructed by
fitting the LSV data in the low overpotential region, obtained at
BH3OH þ 6 OH / B(OH)
4 þ 3 H2O þ 6 e

(8)
scan rate of 0.01 V s1 in the absence of rotation, to the Tafel
equation [54]. ORR Tafel slopes at PdFe/rGO, PdAg/rGO and Pd Au/
Alternatively, BH3OH ions can be oxidised in a stepwise process
rGO were evaluated to be 0.173, 0.182 and 0.202 V dec1, respec-
with release of 3 electrons (Eqs. (9)e(11)),
tively. These values are comparable or higher than those reported
for ORR at Pt/Vulcan (0.057 and 0.231 V dec1), bulk Pd (0.055 and
BH3OH þ OH / BH2(OH)
2 þ ½ H2 þ e

(9)
0.080 V dec1) and carbon-supported Pd NPs (0.046 and 0.140 V
dec1 at Pd/Vulcan, 0.061 and 0.159 V dec1 at Pd/KB and
BH2(OH)  
2 þ OH / BH(OH)3 þ ½ H2 þ e

(10)
0.063e0.101 V dec1 at Pd/MWCNTs) in alkaline media [38,55].
They are also comparable to Tafel slopes previously reported for
BH(OH)  
3 þ OH / B(OH)4 þ ½ H2 þ e

(11)
PdAg alloys (0.044e0.059 V dec1 for low overpotential region and
0.163e0.223 V dec1 for high overpotential region, depending on
with overall reaction given by Eq. (12) [56,59,60].
 M. Martins et al. / Journal of Alloys and Compounds 718 (2017) 204e214 211

Fig. 6. (A) CVs of PdAg/rGO electrocatalyst at scan rate of 0.1 V s1 in 2 M NaOH solution in the presence and in the absence of 0.03 M NaBH4. (B) Comparison of peak current
densities recorded at the PdM/rGO electrocatalysts. (C) RDE LSV measurements of PdAg/rGO at 0.01 V s1 and different rotation rates. (D) K-L plots of PdFe/rGO and PdAu/rGO. (E)
CAs of PdAu/rGO at 0.9 V and 1000 rpm for four different NaBH4 concentrations. (F) CAs of PdAg/rGO at 0.9 V and 1200 rpm at temperatures ranging from 25 to 65  C. All ex-
periments carried out in 0.03 M NaBH4 þ 2 M NaOH solution at 25  C unless otherwise stated.

BH3OH þ 3 OH / B(OH)

4 þ 3/2 H2 þ 3 e

(12)
Peak c1 is attributed to the oxidation of BH3OH, generated
during BH 4 hydrolysis during anodic scan and subsequently
adsorbed on the electrocatalysts surface.
The highest a1 peak current density was recorded at PdAu/rGO,
followed by PdAg/rGO (ca. 8 times lower than in the case of PdAu/
rGO), while the lowest one was recorded at PdFe/rGO (ca. 25 times
lower than in the case of PdAu/rGO) (Fig. 6B). Similar behaviour has
been recently reported for ultrathin Au nanowires supported on
rGO [61] as well as for Au nano-cages and Ag nano-cubes supported
on graphene [62]. Oxidation peak potentials at electrocatalysts
prepared herein were less positive or close to those at these
literature-reported electrocatalysts.
BOR onset potential value at PdAu/rGO (0.13 V) was the most
negative, followed by PdFe/rGO (0.07 V) and then PdAg/rGO
(0.22 V). Still, the values for all three studied electrocatalysts were
less negative than calculated value of standard electrode potential
of direct BH 4 oxidation reaction (Eq. (1)), due to mixed potentials
originating from the oxidation of both BH 4 and its hydrolysis
products, specifically H2 (Eq. (13)).
½ H2 þ OH / H2O þ e E0 ¼ 0.83 V vs. SHE (13)
BOR onset potential of ca. 0.20 V at Pd/C, 0.25 V at Au/C, and in
the 0.20 to 0.10 V range at PdxAu1-x/C were previously reported
[63]. Although CV data are not sufficient to conclude on the BOR
mechanism at the studied electrocatalysts, it is evident that BH 4
oxidation and hydrolysis proceed in parallel at the three PdM/rGO
(M ¼ Au, Ag, Fe).
In order to get better insight into the reaction mechanism, CVs
were subsequently recorded using scan rates up to 1 V s1. Peak
212 M. Martins et al. / Journal of Alloys and Compounds 718 (2017) 204e214
potential was observed to shift to more positive values along with
the increase of the peak current. Assuming that BOR proceeds as a
one-step irreversible process, Eq. (14) was used for calculation of
the anodic charge transfer coefficient, a,
" !   #
RT D1=2 ð1  aÞna Fn 1=2
0
Ep ¼ E þ 0:78 þ ln þ ln
ð1  aÞna F ks RT
(14)
where E0 is the formal potential (V), R is the universal gas constant
(8.314 J K1 mol1), T is the temperature (K), na is the number of
electrons involved in the rate determining step (assumed to be 1), D
is the diffusion coefficient for BH 2 1
4 (cm s ) and ks is the standard
1
heterogeneous rate constant (cm s ). a values of 0.97, 0.95 and
0.78 were calculated for BOR at PdAu/rGO, PdAg/rGO and PdFe/rGO
electrocatalysts, respectively, with these high values evidencing the
irreversibility of the process.
BOR at the three studied electrocatalysts was also examined
using LSV RDE. Measurements were done at scan rate of 0.01 V s1
and temperature of 25  C, varying the electrode rotation rate from
400 to 2800 rpm. Current densities were observed to increase with
the increase of rotation rate, except in the case of PdAg/rGO. For this
electrocatalyst, a weak rotation rate effect was observed for higher
rates (>1200 rpm) (Fig. 6C), indicating kinetic limitations as pre-
viously reported for Ag/C and different Ag alloys including Ag-Pd
[59,64]. At higher potentials, BH 4 is depleted at the anode and it
is not replenished by the convective effect, thus leading to bell-
shaped curves. The number of exchanged electrons, n, was calcu-
lated using the K-L equation (Eq. (7)) [55]. From the slope of the j1
vs. u1/2 plots for potential of 0.85 V (Fig. 6D), n value of 5.5 was
evaluated for BOR at PdAu/rGO, with the n for PdFe/rGO being close
to 2. The n values lower than 8 confirm that BOR proceeds via in-
direct mechanism that includes formation of BH3OH and its
further oxidation. BOR was previously reported to be a 2.4 and
3.6electron reaction at Pd/carbonised polyaniline depending on
the synthesis procedure [65]. 4electron reaction at Pd/MWCNT
[60] and 4- to 8-electron reaction at Pd/VulcanXC72, depending on
the potential [63,66]. n values between 4.6 and 6.6 were reported
for Au/C and for AuFe/VulcanXC72 [67], and of ca. 4 for Ag/Vul-
canXC72 [11].
Fuel composition is one of DBPFC key operational parameters
that need to be optimised for a cell to reach it best performance.
Therefore, CAs of the three studied electrocatalysts were recorded
in 2 M NaOH supporting electrolyte for NaBH4 concentrations
ranging from 0.01 to 0.12 M. Increase of current density could be
observed when increasing the fuel concentration in case of PdAg/
rGO and PdAu/rGO electrocatalysts (Fig. 6E). It should be noted that
NaOH concentration is as important factor, since stability of NaBH4
is improved and hydrolysis is suppressed at solutions of higher pH
values. For instance, NaBH4 decomposition, after 6 h, was 33% at pH
9, but only 5% at pH 11 [68]. The reaction order of BOR at PdAu/rGO
and PdAg/rGO electrocatalysts was evaluated from the CA data
using Eq. (15),
j ¼zCb (15)
where b is the reaction order with respect to BH 4 and z is a con-
stant. b values were found to range from 1 for PdAu/rGO to 0.4 for
PdAg/rGO. BOR was previously reported to be a first order reaction
at Pd/C [63], bulk Au [69], and Pt [70], and at some carbon-
supported alloys, such as Pt0.75Co0.25/C. Reaction orders of 0.4 and
1.85 at Pt0.75Ni0.25/C and Pt/C electrocatalysts, respectively, were
also reported [56].
CA RDE measurements recorded at the PdM/rGO in 0.03 M
NaBH4 þ 2 M NaOH in the temperature region 25e65  C revealed
increase of current density with increase of temperature, with this
increase being more pronounced when increasing the temperature
above 45  C (Fig. 6F). Still, hydrolysis becomes more pronounced at
these temperatures as well, as evidenced by the formation of gas
bubbles that lead to fluctuations in the electrode area.
The increase of current density with temperature observed for
PdAg/rGO was used for the evaluation of apparent activation en-
ergy, Eapp
a , of BOR at this electrocatalysts, by applying the Arrhenius
equation (Eq. (16)).
vlogjjj DEapp
a
¼ (16)
vð1=TÞ 2:3R
Eapp
a value of 23 kJ mol1 was evaluated for PdAg/rGO electro-
catalyst. BOR Eapp
a value of 27 kJ mol1 has been previously reported
for Au [68] and values of 10e26 kJ mol1 for Pd/C, depending on the
carbon support and synthesis procedure [65]. The obtained value is
higher than value reported for some Pd-based electrodes, for
instance Ni/PdNi (12 kJ mol1) [68]. It is worth mentioning that the
BOR Eapp
a value obtained for PdAg/rGO is comparable to those ob-
tained for carbon-supported Pt alloys (20 kJ mol1 for (Pt0.75Ni0.25/C
and 25 kJ mol1 for Pt0.75Co0.25/C) [56] and lower than value re-
ported for Pt/C (34 kJ mol1) [56] and comparable or lower than
values for unsupported Pt alloys (17e70 kJ mol1 for PtAu,
depending on Au at.%) [71] and 30 kJ mol1 for PtDy) [12].
4. Conclusions
Bimetallic PdM (M ¼ Au, Ag, Fe) alloy nanoparticles were pre-
pared and assembled on rGO. TEM analysis revealed that PdM NPs
were uniform in size with diameters in the 2.5e4.0 nm range.
Subsequently, the performance of the three fabricated electro-
catalysts was evaluated for the ORR and BOR in alkaline media by
the RDE method. The highest ORR current densities, the highest
number of electrons exchanged in the ORR and the lowest Tafel
slope were evaluated for PdAu/rGO electrocatalyst, demonstrating
its higher electrocatalytic activity compared to PdAg/rGO and PdFe/
rGO. Similarly, the highest BOR current densities and number of
exchanged electrons were observed at PdAu/rGO. In summary,
obtained results suggest that the studied electrocatalysts are po-
tential candidates for the anode (borohydride oxidation) and
cathode (oxygen reduction) reactions in DBFCs.
Acknowledgements
The authors would like to thank Fundaça ~o para a Cie
^ncia e a
Tecnologia (FCT, Portugal) for grant INCENTIVO/CTM/UI0084/2014
(M. Martins), for postdoctoral research grant no. SFRH/BPD/77768/


2011 (B. Sljuki c), and for contract no. IF/01084/2014/CP1214/
CT0003 under IF2014 Programme (D.M.F. Santos). O. € Metin thanks
to the Turkish Academy of Sciences (TUBA) for the financial support
in the context of Young Scientist Award Program (GEBIP). M. Sevim
thanks to The Scientific and Technological Research Council of
Turkey (TUBITAK) for a fellowship. We also thank to Dr. Emre Gür
for his help getting the XPS spectra.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jallcom.2017.05.058.
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