Electrochemistry Communications 8 (2006) 16251627

www.elsevier.com/locate/elecom

Preparation method of an ultrane carbon supported Pd catalyst as

an anodic catalyst in a direct formic acid fuel cell
Lingling Zhang a, Tianhong Lu
b

a,b

, Jianchun Bao a, Yawen Tang

a,*

, Cun Li

a,*

a
Department of Chemistry, Nanjing Normal University, Nanjing 210097, PR China
Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China

Received 3 July 2006; received in revised form 18 July 2006; accepted 24 July 2006
Available online 30 August 2006

Abstract
It was reported for the rst time that the carbon supported Pd (Pd/C) catalyst was prepared in the aqueous solution with NH4F and
H3BO3. The average size and the relative crystallinity of the Pd particles in the Pd/C catalyst prepared with this method are much lower
than that of the Pd/C catalyst prepared with general reduction method because PdCl2 can form the complex with NH4F. Therefore, the
electrocatalytic activity and stability of the Pd/C catalyst prepared with this method for the formic acid oxidation in the direct formic
acid fuel cell (DFAFC) are better than that of the Pd/C catalyst prepared with the general reduction method. This preparation method is
very simple. Therefore, it is hopeful to have a practical application in the catalyst preparation.
 2006 Elsevier B.V. All rights reserved.
Keywords: Carbon supported Pd catalyst; Formic acid; Direct formic acid fuel cell

Recently, the advantages of DFAFC has being progressively recognized comparing with direct methanol fuel cell
(DMFC) [1]. For example, as a strong electrolyte, formic
acid can facilitate the proton transport within the anode
compartment [2]. It has two orders of magnitude smaller
crossover ux through a Naon membrane than methanol
and then as high as 20 M concentrated formic acid can be
used in the operation of DFAFC [3]. Thus, the power density of DFAFC can be higher than that of DMFC although
the energy density of methanol is higher than that of formic
acid.
In recent years, Ha et al. [13] investigated the Pd/C catalyst as the anodic catalyst for DFAFC and found that the
electrocatalytic activity of Pd for the formic acid oxidation
is better than that of Pt [4,5]. It was reported that when the
average size of the Pd particles is small, the electrocatalytic
activity of Pd catalyst for the formic acid oxidation is high
[6]. However, the average size of the Pd particles in the Pd/
*

Corresponding authors. Tel.: +86 25 83598031.

E-mail address: tianhonglu@263.net (T. Lu).

1388-2481/$ - see front matter  2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.elecom.2006.07.033

C catalyst prepared with the general reduction method is

large.
In this paper, it was reported for the rst time that when
the Pd/C catalyst is prepared in the aqueous solution with
NH4F and H3BO3, the average size of the Pd particles in
the Pd/C catalyst prepared is as small as about 3.2 nm.
Thus, the Pd/C catalyst showed a high electrocatalytic
performance for the formic acid oxidation.
The 20 wt% Pd/C catalyst was prepared as follows.
25.0 mg NH4F, 125 mg H3BO3, and 3.13 mL 0.045 mol/
L PdCl2 were added to 10 mL water. Then, 60 mg Vulcan
XC-72 carbon was added into the above solution. The
suspension obtained was sonicated for 30 min at room
temperature. After the pH was adjusted to 89 using concentrated ammonia, the suspension was slowly added into
10 mL NaBH4 solution with sonicating. The resulting suspension was further sonicated for 30 min. Finally, it was
ltered, washed with triply distilled water and dried in a
vacuum oven at 60 C. The Pd/C catalyst obtained was
noted as the Pd/C-1 catalyst. For comparison, the Pd/
C-2 catalyst was prepared in an aqueous solution without

L. Zhang et al. / Electrochemistry Communications 8 (2006) 16251627

NH4F and H3BO3. Other procedures is as same as that

for the preparation of the Pd/C-1 catalyst. The measurements of the energy dispersive spectra of two Pd/C catalysts indicated that both the Pd/C catalysts contain about
20.0 wt% Pd, illustrating that almost all PdCl2 has been
reduced.
The electrochemical measurements were performed
using CHI 600 electrochemical analyzer and a conventional
three-electrode electrochemical cell at 30 1 C. A Pt plate
and the saturated calomel electrode (SCE) were used as the
auxiliary electrode and the reference electrode, respectively.
All potentials were quoted with respect to SCE. The working electrode was prepared as follows. 8 mg catalyst and
4 mL C2H5OH solution were mixed and 8.9 lL slurry
obtained was spread on the surface of the glassy carbon
(GC) electrode (4 mm in diameter). After drying, 4.5 lL
Naon (5 wt%) solution was covered on the surface of
the catalyst electrode. After drying, the working electrode
was obtained. In the electrochemical measurements, the
current densities are normalized to apparent surface area
of the GC electrode.
The composition of the catalyst was determined using
energy dispersive spectrometer with Vantage Digital
Acquisition Engine (Thermo Noran, USA). The UVvis
absorption spectrum was measured with a PerkinElmer
Model Lambda 17 recording spectrophotometer. The Xray diraction (XRD) measurements of catalysts were performed on Model D/max-rC diractometer using CuKa
radition (k = 0.1540 6 nm) and operating at 45 kV and
100 mA. The image of transmission electron microspectroscopy (TEM) was obtained with a JEOL 2010 microscope operating at 200 kV with nominal resolution.
The UVvis absorption spectroscopic measurements
indicated that the absorption peaks of the PdCl2 solution
appear at 413 and 209 nm. However, they disappear after
NH4F + H3BO3 is added into the PdCl2 solution (Fig. 1),
illustrating the formation of the complex of PdCl2 with
NH4F.

Intensity (a.u.)

1626

a
0

20

40

60

80

2/( )
Fig. 2. The XRD patterns of: (a) the Pd/C-1 and (b) Pd/C-2 catalysts.

Fig. 2 shows the XRD patterns of two Pd/C catalysts. It

was found from Fig. 2 that except the carbon peak at about
24.7, the 2h values of other four characteristic peaks of the
Pd particles in both catalysts correspond to (1 1 1), (2 0 0),
(2 2 0) and (3 1 1) crystal faces of the face centered cubic
crystalline of Pd (ASTM standard 5-681(Pd)). The average
sizes of the Pd particles can be calculated using Debye
Scherrer formula [7,8]
B2h 0:94k=L cos h
where B(2h) is the width of half peak, k, incident wavelength, L, particle diameter, h, diraction angle.
Then, the ratio of the intensities of Pd(1 1 1) and carbon
peaks is the relative crystallinities of the Pd particles. The
average sizes of the Pd particles in the Pd/C-1 and Pd/C2 catalysts are 3.2 and 15.5 nm, respectively, and the relative crystallinities of the Pd particles the Pd/C-1 and Pd/
C-2 catalysts are 1.55 and 3.97, respectively. The average
size the Pd particles in the Pd/C-1 catalyst obtained from
TEM measurements (Fig. 3) is about 3.0 nm, which is in

2.5

absorbance

2.0

1.5

1.0

0.5

0.0
200

300

400

500

wavelength/nm
Fig. 1. The UVvis absorption spectra of 1.8 104 M PdCl2 solution: (a)
before and (b) after adding NH4F + H3BO3.

Fig. 3. The TEM image of the Pd/C-1 catalyst.

L. Zhang et al. / Electrochemistry Communications 8 (2006) 16251627

a
6

b
I/mA.cm-2

10

I/mA.cm-2

good agreement with that from the above XRD

measurement.
The measurement of the cyclic voltammograms of two
Pd/C catalyst electrodes in the 0.5 M H2SO4 solution indicated that the hydrogen adsorption/desorption peaks at the
Pd/C-1 catalyst electrode are larger than that at the Pd/C-2
catalyst electrode. The coulombic charges of the hydrogen
desorption peaks for the Pd/C-1 and Pd/C-2 catalysts are
2.10 103 and 0.86 103 C/cm2, respectively. Then, the
electrochemically active surface areas of the Pd/C-1 and
Pd/C-2 catalysts were calculated to be 35.2 and 14.4 m2 g,
respectively according to the procedure in the literature
[9]. It is due to this the average size of the Pd particles in
the Pd/C-1 catalyst is smaller than that in the Pd/C-2
catalyst.
Fig. 4 displays the cyclic voltammograms of 0.5 M
HCOOH in the 0.5 M H2SO4 solution at the two catalyst
electrodes. It can be observed from Fig. 4 that in the positive scan direction, the potentials of the two oxidation
peaks of HCOOH at the Pd/C-1 and Pd/C-2 catalyst electrodes are the same, 0.085 and 0.546 V. However, the current densities of the two oxidation peaks at the Pd/C-1
catalyst electrode (Fig. 4, Curve a) are 6.36 103 and
3.25 103 A/cm2, while at the Pd/C-2 catalyst electrode,
they are 4.78 103 and 2.78 103 A/cm2 (Fig. 4, Curve
b). It clearly demonstrated that the electrocatalytic activity
of the Pd/C-1 catalyst for the formic acid oxidation is
higher than that of the Pd/C-2 catalyst.
Fig. 5 shows the chronoamperometric curves of 0.5 M
HCOOH in 0.5 M H2SO4 solution at the Pd/C-1 and Pd/
C-2 catalyst electrodes at 0.10 V. It can be observed from
Fig. 5 that the current densities at the Pd/C-1 and Pd/C2 catalyst electrodes at 1000 s are 1.54 and 0.15 mA/cm2,
respectively. The above results demonstrated that the electrocatalytic stability of the Pd/C-1 catalyst for the formic
acid oxidation is also higher than that of the Pd/C-2
catalyst.

1627

b
0
0

200

400

600

800

1000

t/s
Fig. 5. The chronoamperometric curves of 0.5 M HCOOH in 0.5 M
H2SO4 solution at: (a) the Pd/C-1 and (b) Pd/C-2 catalyst electrodes.
Fixed potential: 0.10 V.

It can be concluded form the above results that the Pd/

C-1 catalyst prepared in the aqueous solution with NH4F
and H3BO3 possesses as small as 3.2 nm average size of
Pd particles because PdCl2 can form the complex with
NH4F. The average size of the Pd particle in the Pd/C2 catalyst prepared with the general reduction method is
as large as 15.5 nm. Thus, the electrocatalytic activity
and stability of the Pd/C-1 catalyst for the formic acid
oxidation are better than that of the Pd/C-2 catalyst
because the average size of the Pd particles in the Pd/C1 catalyst is smaller and the electrochemically active surface area is larger than that of the Pd particles in the
Pd/C-2 catalyst.
Acknowledgements
The authors are grateful for the support of the National
Natural Science Foundation of China (20473038,
20573057), the Natural Science Foundation of Education
Committee of Jiangsu Province (05KJB150061), the Natural Science Foundation of Department of Science and
Technology of Jiangsu Province (BK2006224).
References

2
0
-2
-0.2

0.0

0.2

0.4

0.6

0.8

E/V(vs.SCE)
Fig. 4. The cyclic voltammograms of 0.5 M HCOOH in 0.5 M H2SO4
solution at: (a) the Pd/C-1 and (b) Pd/C-2 catalyst electrodes.

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