i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 6 9 2 0 e6 9 2 6

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PdeMnO2eFe2O3/C as electrocatalyst for the formic

acid electrooxidation
€
T. S‚ener a,*, U.B. Demirci b, O.F. Gül c, A. Ata a
a
Gebze Technical University, Material Science and Engineering Department, Gebze, Kocaeli TR-41400, Turkey
b
IEM (Institut Europeen des Membranes), UMR 5635 (CNRS-ENSCM-UM2), Universite Montpellier 2,
Place E. Bataillon, F-34095 Montpellier, France
c
Nis‚antas‚ı University, Sadabad Kampüsü, Mechanical Engineering Department, Hasbahçe Caddesi No: 88,
TR-34030, Kag ıthane, Istanbul, Turkey

article info abstract

Article history: PdeMnO2eFe2O3/C and Pd/C (for comparison to the former) were synthesized by NaBH4
Received 31 December 2014 reduction method and then annealed at 500
C. The catalysts were characterized physically
Received in revised form by various techniques including XRD, TEM, EDX, XPS and ICP. The results showed that both
22 March 2015 MnO2 and Fe2O3 are in the amorphous form while Pd is crystalline for both catalysts. The
Accepted 27 March 2015 particle size of Pd nanoparticles in PdeMnO2eFe2O3/C and Pd/C catalysts were found to be
Available online 17 April 2015 11.6 nm and 10.9 nm, respectively. The total metal weight percent in PdeMnO2eFe2O3/C
was determined as 18% and the metal molar ratios of Pd:Mn:Fe was calculated as 49:20:31.
Keywords: By cyclic voltammetry (CV) and chronoamperometry (CA), the ternary catalyst showed a
Formic acid oxidation superior electrocatalytic activity, namely of z3.4 times higher than Pd/C. The results also
Palladium indicated that amorphous third parties may play a crucial role to improve the catalyst
Manganese oxide activity towards formic acid oxidation. All of these results are reported and discussed in
Iron oxide details herein.
Copyright © 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

Introduction
In the current context of R&D dedicated to novel energy
technologies, low-temperature fuel cells are regarded as
attractive portable power solutions due to high power den-
sities [1,2]. This is important as portable consumer electronics,
with rising power consumption demands due to new 3G ser-
vices, are a widespread market for fuel cells [3].
Methanol (CH3OH) has been widely studied as a fuel of
choice for low-temperature direct liquid-feed fuel cell (i.e.
direct methanol fuel cell), especially by manufacturers of
portable electronics for some years [3e5]. However, methanol
is toxic and burnable, and has a low boiling point [6]. Instead,
naturally occurring formic acid (HCOOH) has been proposed
as an attractive and much promising alternative, namely the
anodic fuel of direct formic acid fuel cell (DFAFC). Advanta-
geously, it is non-flammable and easily stored [7].
Electrooxidation of formic acid, after adsorption on the
electrocatalyst surface (i.e. HCOOH*), takes place via two
parallel pathways. The first is direct, involving the stepwise
liberation of two protons and two electrons (Eqs. (1) and (2)).
The second is indirect (Eq. (3)), with the formation of H2O and
CO in a first step. In both cases, the stepwise electrooxidation
leads to the formation of CO2 as by-product:

* Corresponding author. Tel.: þ90 262 677 2715; fax: þ90 262 677 2309.
E-mail address: tansel.sener@gmail.com (T. S‚ener).
http://dx.doi.org/10.1016/j.ijhydene.2015.03.145
0360-3199/Copyright © 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 6 9 2 0 e6 9 2 6
HCOOH* / COOH* þ Hþ þ e / CO2 þ 2Hþ þ 2e
HCOOH* / HCOO* þ Hþ þ e / CO2 þ 2Hþ þ 2e
HCOOH* / CO* þ H2O / CO2 þ 2Hþ þ 2e
This is called as the “dual path mechanism” [8]. The stan-
dard potential for formic acid electrooxidation E
(HCOOH/
CO2, Hþ) is 0.25 V at 25
C. Though lower than that of
methanol (E
(CH3OH/CO2, Hþ) ¼ 0.02 V), the electrooxidation
of formic acid benefits from it, the electrode not behaving in a
reversible manner.
Among the metals tested so far, Pd has shown to be the
most efficient. It does not only exhibit high electrocatalytic
activity, but it is also resistant to CO poisoning [9,10]. However,
as a noble metals it has a cost barrier. With the objectives to
improve its electrocatalytic performance while decreasing its
content, different strategies have been developed: (i) disper-
sion onto different sole carbonaceous supports or their hybrid
form with metal oxides; (ii) nanostructuration; (iii) alloying
with a secondary electroactive metal; (iv) combining with a
secondary inactive phase (third-body effect) [11e15]. For
instance, for the strategy (iv), Huang et al. showed that the
presence of manganese oxide MnO2 nanolamella allows
improving the electrocatalytic activity of Pd/graphene by 300%
[16]. Such improvement is explained in terms of large elec-
trochemically active surface area. The beneficial presence of a
metal oxide was also demonstrated by Ji et al. for Pd nano-
particles dispersed onto carbon nitrideeFe3O4 [17]. It is worth
noting that similar findings were achieved with the hybrid
electrocatalyst PdeFe2O3 in ethanol electrooxidation and the
coreeshell amorphous-Fe2O3@Pt nanoparticles in methanol
electrooxidation [18,19]. The secondary phase Fe2O3 has a
promoting (third-body) effect for removing the adsorbed CO-
like intermediate species and enhancing the selectivity in CO2.
Herein, we report, for the first time, the promotional effect
of MnO2 and Fe2O3 for improving the electrocatalytic activity
of Pd towards formic acid electrooxidation. Via a simple
NaBH4 reduction method, Pd, MnO2 and Fe2O3 were co-
precipitated onto the carbon support Vulcan XC-72. The
electrocatalytic activity of PdeMnO2eFe2O3/C was character-
ized by cyclic voltammetry and chronoamperometry, and
compared to the performance of Pd/C. The elemental
composition, morphology, crystal structure and surface elec-
tronic state of PdeMnO2eFe2O3/C were analyzed by induc-
tively coupled plasma mass spectrometry (ICP), energy
dispersive X-ray (EDX), transmission electron microscopy
(TEM), X-ray diffraction (XRD), and X-ray photoelectron spec-
troscopy (XPS).
Experimental procedure
The chemical reagents were palladium nitrate dihydrate
Pd(NO3)2$2H2O (Purity: 99.9%) (Aldrich), manganese chloride
tetrahydrate MnCl2$4H2O (99.99%) (SigmaeAldrich), iron
chloride FeCl2 (99.99%) (SigmaeAldrich), sodium hydroxide
NaOH (97.00%) (SigmaeAldrich), sodium borohydride NaBH4
6921
(1) (99%) (SigmaeAldrich), sodium citrate C6H5Na3O7 (99.0%)
(SigmaeAldrich), 5 wt% Nafion solution (SigmaeAldrich) and
Vulcan XC-72 carbon (Cabot Corp.; denoted C) with a specific
(2) BET area of 250 m2/g and an average size of 40 nm. All were
used as purchased without further treatment.
The metal precursors were completely dissolved in
(3) 18.2 MU cm ultrapure water. Then, 6 mL of aqueous solution of
0.1 M sodium citrate was added to 500 mL H2O at 90
C and
under N2, and vigorously stirred for 10 min. The metal pre-
cursors were then added to the solution, which was thor-
oughly mixed for 10 min at 90
C. Then, a freshly prepared
0.2 M NaBH4 solution was added till pH z 9. The reaction
lasted 10 min under vigorous mixing. Then, 240 mg of carbon
(ultrasonicated for 20 min in the mixture consisting of 40 mL
2-propanol (Aldrich) and 40 mL H2O) was added and the slurry
was stirred for 24 h in room conditions. The suspension was
finally centrifuged (Eppendorf 5702) to separate the phases,
the solid was washed with deionized water several times. The
as-obtained electrocatalysts were dried in a freeze drier
(Labconco Freezone 2.5, <0.05 bar at 83
C) for 48 h and then
stored in a vial kept in room conditions. The as-obtained
electrocatalyst is denoted PdeMnO2eFe2O3/C. The metal
oxides-free counterpart was prepared in similar conditions
and is denoted Pd/C.
Elemental analysis was performed by using ICP (Thermo
Jarrell Ash Atomscan-25) and EDX (Oxford Instruments X-
Sight 6498). Morphologies were examined by TEM (Jeol JSM
6335-F). XRD was performed on a Philips PW3710 diffractom-
eter using the Cu Ka radiation. XPS measurements were ob-
tained using SPECS GmbH PHOIBOS-150 with monochromatic
Al Ka (1486.6 eV). Thermogravimetric analysis (TGA) was
carried out using the analyzer PerkinElmer Pyris1.
Electrochemical measurements were performed with a
conventional three-electrode cell and a Gamry electro-
chemical workstation, with a working electrode, a carbon road
as counter electrode, and a reference electrode (Ag/AgCl, KCl
std). The working electrode is a Pt one with a surface area of
1 cm2. It was coated with the catalyst slurry prepared by
mixing 5 mg of catalyst, 5 mL of the 5 wt% Nafion solution and
1 mL of ethanol (Sigma Aldrich). The coated electrode was
dried for 10 min at 80
C. Cyclic voltammetry (CVs) measure-
ments were performed in room conditions at a scan rate of
50 mV/s. The electrolytes were as follows: nitrogen-saturated
aqueous solution of 0.5 M H2SO4 and nitrogen-saturated
aqueous solution of 0.5 M H2SO4 with 0.5 M HCOOH. Nitro-
gen saturation was done for 20 min. Chronoamperometry (CA)
measurements were performed in room conditions at 0.3 V vs.
Ag/AgCl in nitrogen-saturated aqueous solution of 0.5 M
H2SO4 with 0.5 M HCOOH.
Results and discussion
EDX analysis of Pd/C (Fig. 1) confirmed the presence of Pd only.
The loading of Pd was found to be 20 wt% (confirmed by TGA
under air). EDX analysis of PdeMnO2eFe2O3/C confirmed the
presence of Pd, Mn and Fe (Fig. 2). The ternary electrocatalyst
was initially prepared with the targeted mole ratio
0.33:0.33:0.33. The EDX data revealed a ratio of 0.25:0.28:0.47.
This is consistent with the ratio of 0.2:0.31:0.49 obtained by
6922 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 6 9 2 0 e6 9 2 6

Fig. 1 e EDX spectrum of Pd/C, revealing the presence of C

and Pd. The signal of Cu is due to the grid.

ICP. The loading of the metal/oxides phases in

PdeMnO2eFe2O3/C was determined as being 18 wt%. Fig. 3 e XRD patterns of PdeMnO2eFe2O3/C and Pd/C.
The XRD patterns of both PdeMnO2eFe2O3/C and Pd/C
(Fig. 3) show sharp peaks at 2q 40.1
, 46.7
, and 68.2
, due to the
reflections of the (111), (200) and (220) planes of face centred
Pd0 (consistently with the XRD observations) while that at
cubic Pd0 (JCPDS No. 65-6174). The peak at 2 q 25
is due to the
higher BE (336.9 and 341.6 eV respectively) is indicative of
(002) plane of the hexagonal structure of the carbon support.
oxidized Pd (i.e. PdO). Only part of Pd, which is the main part,
The characteristic diffraction peaks of crystalline Fe2O3 and
is thus in metallic state. With respect to the Mn element, the
MnO2 are not observed but there is a noticeable upward shift
signals for Mn 2p1/2 (654.1 eV) and Mn 2p3/2 (642.5 eV) can be
from the origin line because of amorphous Fe2O3 (2q range
ascribed to manganese dioxide MnO2. The BEs for Fe 2p3/2
30e40
) and amorphous MnO2 (2q range 15e60
) [20,21].
(711.4 eV) and 2p1/2 (724.7 eV) suggests the occurrence of
Another possible explanation could be that the diffraction
Fe2O3. Accordingly, the ternary electrocatalyst catalyst is
peaks of crystalline metal oxides can be significantly weak-
mainly composed by Pd0, Fe2O3 and MnO2.
ened due to strong interactions with a noble metal like Pd
PdeMnO2eFe2O3/C and Pd/C were scrutinized by TEM
[22e24]. With the help the Scherer's equation (based on the
(Fig. 5). The particle size of the Pd nanoparticles (isolated and
full-width at half-maximum of the (111) plane), the crystallite
dispersed) in Pd/C was found to be 11 nm, in agreement with
sizes of Pd were calculated as being 11.6 nm and 10.9 nm in
the crystallite size determined by XRD (10.9 nm). With respect
PdeMnO2eFe2O3/C and Pd/C, respectively. Actually, the pres-
to PdeMnO2eFe2O3/C, it has been difficult to determine the
ence of the metal oxides has a negligible effect on the crys-
particle size of the Pd nanoparticles because they cannot be
tallite size of Pd.
distinguished from the sponge-like agglomerates of the
Fig. 4 shows the XPS spectra of PdeMnO2eFe2O3/C, and
amorphous MnO2 and Fe2O3 phases. Similar observations
specifically the Pd 3d, Mn 2p and Fe 2p core levels. They were
were reported elsewhere for amorphous Fe2O3 prepared from
analyzed and ascribed with the help of the NIST XPS database
FeCl3$6H2O we also used [26]. The TEM observations indicates
[25]. The signals of Pd 3d5/2 and Pd 3d3/2 were deconvoluted.
that there would be strong interaction between the oxides and
In both cases two peaks fitted. For each signal, the peak with
Pd, which is consistent with the XRD observations.
lower binding energy (BE; 335.6 and 340.8 EV) is attributed to
The electrochemical active surface area (ECSA) of the
electrocatalysts was determined by measuring cyclic vol-
tammograms with nitrogen-saturated aqueous solution of
0.5 M H2SO4 (Fig. 6). The ECSA value can be measured by
integrating the coulombic charge under the hydrogen
desorption peak and by using the following equation:

Fig. 2 e EDX spectrum of PdeMnO2eFe2O3/C, revealing the
presence of C, Mn, Fe and Pd.
QH
ECSA ¼ (4)
0:21  LPd
where QH is the coulombic charge density for hydrogen
desorption, 0.21 mC/cm2 is the charge required for the
adsorption of a hydrogen monolayer, and Lpd (mg) is the
weight of Pd loaded onto the working electrode [27].
Accordingly, the ECSA values were calculated for
PdeMnO2eFe2O3/C and Pd/C and were found to be 67 and
29 m2/g Pd, respectively. The particles size being similar for
both electrocatalysts, the highest ECSA for the ternary
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 6 9 2 0 e6 9 2 6 6923

Fig. 5 e TEM images of (a, b) PdeMnO2eFe2O3/C and (c)

Pd/C.

Fig. 4 e XPS spectra of PdeMnO2eFe2O3/C: (A) Pd 3d core

level; (B) Mn 2p core level; (C) Fe 2p core level.
6924 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 6 9 2 0 e6 9 2 6

Fig. 6 e Cyclic voltammograms of PdeMnO2eFe2O3/C and

Pd/C in 0.5 M H2SO4 aqueous solution (purged 20 min with
N2) at the scan rate of 50 mV/s.

electrocatalysts may be explained by the presence of the

amorphous phases MnO2 and Fe2O3, which in comparison to
crystalline phases should offer more structural distortion and
accordingly more electrochemically accessible sites
[21,28,29]. Hence, better electrocatalytic performance could
be expected for PdeMnO2eFe2O3/C.
The electrocatalysts were tested in electrooxidation of
formic acid. Fig. 7A shows the CV curves for aqueous 0.5 M
H2SO4 solution with 0.5 M HCOOH, at a scan rate of 50 mV/s
and in the potential range [(0.3)e1.3]. V. The CV profiles are
equivalent. There are two electrooxidation peaks during the
positive (forward) potential scan. They are denoted with f1 and Fig. 7 e (A) Cyclic voltammograms and (B)
f2. The former corresponds to formic acid direct electro- chronoamperograms (at 0.3 V vs. Ag/AgCl) of
oxidation via Eq. (1) or Eq. (2) (dehydrogenation), and the po- PdeMnO2eFe2O3/C and Pd/C at a scan rate of 50 mV/s in
tential of PdeMnO2eFe2O3/C is negatively shifted of 50 mV 0.5 M H2SO4 aqueous solution with 0.5 M HCOOH.
compared to Pd/C. The latter peak is due to formic acid elec-
trooxidation by dehydration as described by Eq. (3). The peak
current densities at f1 and f2 for PdeMnO2eFe2O3/C are ca. 3.4
times higher than those for Pd/C (Table 1). This confirms the conditions, the performance (Table 1) is higher in comparison
better electrocatalytic performance, as expected from the to Mo2C/carbon nanotubes supported Pd nanoparticles
ESCA values discussed above. The improvement can be (0.845 A/mg), Ag34Au33Pd33 nanosponge (1.02 A/mg), and
explained by the presence of the amorphous phases MnO2 and nanoporous PdPt alloy (1.29 A/mg) [33e35].
Fe2O3, which would offer more electroactive sites. Further- The performance of Pd/C prepared in this work (0.5 A/mg)
more, the oxide phases would make Pd less sensitive to is less than commercial Pd/C (Etek) (z0.65 A/mg) [36]. This
poisoning by strong adsorption of intermediates like HCOO* may be due to the smaller particles size of commercial Pd/C
(Eq. (2)) of CO* (Eq. (3)). In the negative (reverse) potential scan, (4.1 nm). Indeed, the particles size of our Pd/C sample is
there is one electrooxidation peak. It is denoted b. The elec-
trooxidation of formic acid on newly reduced Pd surfaces
takes place [21,30e32]. The peak current density at b for Table 1 e Summary of the CV results (peak current
PdeMnO2eFe2O3/C is ca. 5.8 times higher than that for Pd/C density and potential) for the PdeMnO2eFe2O3/C (1) and
(Table 1). Last, there is another electrooxidation peak, denoted Pd/C (2) electrocatalysts.
i, at 1.3 V. It is due to further electrooxidation of intermediates Current density (A/mg Pd) Potential (V)
[32].
f1 f2 b i f1 f2 b
The mass current density of PdeMnO2eFe2O3/C at the peak
f1 can be compared to values reported so far for Pd-based (1) 1.72 0.67 2.04 2.15 0.05 0.7 0.32
(2) 0.5 0.2 0.35 0.91 0.1 0.67 0.3
electrocatalysts studied in similar electrolytes. In our
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 6 9 2 0 e6 9 2 6
centred at 10.9 nm. The promotional addition of metal oxides
such as CeOx and MnO2 for Pd/C was reported elsewhere [37].
Wang et al. [38] showed that the performance of PdCeOx/C is
about 5 times higher than that of Pd/C. The particles of CeOx
act as anchoring sites leading to a higher electrochemical
surface area. El-Deab showed that the performance of
PteMnO2/C is about 3,5 higher than that of Pd/C [39]. MnO2
acts as a catalytic mediator facilitating the retrieval of the Pt
active sites through oxidation of the adsorbed CO (poison) to
CO2. Similar improvements were reported by Huang and
Wang [16] with the addition of MnO2 nanolamella to the active
phase Pd.
The durability of PdeMnO2eFe2O3/C and Pd/C was exam-
ined by CA. The curves recorded at 0.30 V are given in Fig. 7B.
At this potential, continuous formic acid electrooxidation
occurs. The polarization currents first drop within several
hundreds of seconds, due to the formation of double layer
capacitance, and then are relatively stable (quasi-equilibrium
steady state) [40]. The current is higher for PdeMnO2eFe2O3/C
over the whole time range, confirming its better electro-
catalytic activity. The limiting current on PdeMnO2eFe2O3/C
is almost 4 times higher than that obtained on Pd/C, with 350
and 90 mA/mg Pd respectively. This is indicative of the better
durability of PdeMnO2eFe2O3/C, due to a more efficient
removal of poisonous intermediates [41]. This is also
confirmed by the upper current decay rate that is higher for
the ternary electrocatalyst (Fig. 7B). Therefore, the results
show that the presence of the amorphous MnO2 and Fe2O3
phases leads to much better tolerance to poisoning.
Conclusion
The combination of metal oxides such as MnO2 and Fe2O3 with
metallic Pd has shown to lead to a carbon-supported ternary
electrocatalyst that is much performing than the Pd/C coun-
terpart in electrooxidation of formic acid. This is a very
promising result because: (i) the synthesis of the electro-
catalyst is facile; and (ii) better performance in terms of elec-
trooxidation and durability can be achieved while reducing
the Pd loading. This opens the way to electrocatalysts with
improved activity.
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