electro-oxidation of ethanol [8]. Moreover, Shao et al. and Yin et al.
demonstrated that the {100}-facet-enclosed Pd nanocrystals also
showed a higher activity than the other types of Pd nanocrystals
towards the methanol electro-oxidation [9,10].
In order to further maximize the catalytic activity of Pd nano-
crystals and minimize the use of precious Pd metal, a combination
of Pd nanocrystals with carbon materials, such as carbon black,
carbon nanotubes and carbon nanofibers, has been considered an
effective way [11,12]. These carbon materials supports can enhance
the dispersity of Pd nanocrystals and increase the utilization and
efficiency of Pd-based electrocatalysts [11]. Among the carbon
materials, graphene, with distinctive 2-dimensional sheet structure
consisting of a few layers of sp
2
-hybridized carbon lattice [13,14],
has received great attention due to its outstanding physicochemical
properties, such as large specific surface area, superior electrical
conductivity and good mechanical strength [12,15e18]. Thus, it is
expected to be the best candidate for the combination with Pd
nanocrystals to design novel catalyst for direct alcohols fuel cells
(DAFCs) [19e22]. So far, Pd nanostructures supported on graphene
are mostly nanospheres [20,21,23], nanoclusters [24], and nano-
dendrites [11,25]. The study about the preparation of cube-shaped
Pd nanocrystals attached graphene composites and their applica-
tion in the electro-oxidation of alcohols is rarely reported. A com-
plete understanding about the details of the formation mechanism
of PdNCs on the surface of RGO is also lacking, including the
influencing of substrate and experimental factors, and the rela-
tionship between structure and properties. In anticipation of
fascinating electrochemical properties of Pd nanocubes attached
graphene, it is desirable to develop a facile chemical method for the
synthesis of Pd nanocubes anchoring on graphene and further
investigate their electrocatalytical performance towards ethanol
oxidation.
In the present work, we attempt to synthesize the cube-shaped
Pd nanocrystals/reduced graphene oxide composites via a facile
one-step method, in which the reduction of graphite oxide and
metal precursor was carried out simultaneously by employing
ascorbic acid (AA) and potassium bromide (KBr) as the soft
reducing and capping agents, respectively [23,26,27]. Herein, the
experimental factors affecting the morphology and structure of Pd
nanoparticles on the graphene, such as the role of reduced gra-
phene oxide, concentrations of KBr and AA, the reduction time and
reaction temperature, have been systematically investigated to
explore the formation mechanism of Pd nanocubes. The
morphology and structure of Pd nanocubes/reduced graphene ox-
ide (PdNCs/G) composites were characterized by transmission
electron microscopy (TEM), field-emission scanning electron mi-
croscopy (FE-SEM), X-ray diffraction (XRD) and X-ray photoelec-
tron spectroscopy (XPS). Further electrochemical experiments
including cyclic voltammograms and chronoamperometry were
performed toward the electro-oxidation of ethanol. The results
revealed superior electrocatalytic activity and stability of the
PdNCs/G as compared with both reduced graphene oxide sup-
ported Pd nanoparticles (PdNPs/G) and free-standing PdNCs,
showing a great potential as new anode catalysts in DAFCs.
2. Experimental section
2.1. Chemicals and materials
Potassium tetrachloropalladite (II) (K
2
PdCl
4
) was purchased
from Aldrich Chem Co. Graphite was obtained from Alfa Aesar and
5wt% nafion was purchased from DuPont. Ascorbic acid (AA), Po-
tassium Bromide (KBr), sulfuric Acid, KMnO4, K
2
S
2
O
8
and P
2
O
5
were purchased from Sinopharm Chemical Reagent Co and used
without further purification. All chemicals were analytically pure
and used as received without further purification. The deionized
water for solution preparation was from a Kertone Ultrapure Water
System P60-CY (Kertone Water Treatment Co. Ltd, resistivity
>18 M
U
cm).
2.2. Synthesis of PdNCs/G, PdNPs/G composites and PdNCs
The graphite oxide (GO) powder were prepared from graphite
powder via a modified Hummers' method [28]. 12.5 mg GO was
first dissolved in 40 mL pure water and exfoliated using ultrasonic
treatment for 1 h to achieve well dispersion. Then, 1 mL of 0.035 M
K
2
PdCl
4
and 1 mL of 0.03 mM KBr were mixed with 48 mL pure
water. Next, the resulting solution was mixed with the above GO
dispersed solution, following the addition of 200 mg AA as the
reductant. The mixture was kept stirring for 1 h at a temperature of
85
C under reflux conditions. Finally, solid powders were collected
via centrifugation, sequentially washed with double-distilled water
and ethanol for several cycles, and dried at 60
C in a vacuum oven
for 12 h. The PdNCs/G composite was then obtained. Similarly, Pd
nanoparticles attached reduced graphene oxide (PdNPs/G) and free
standing Pd nanocubes (PdNCs) were prepared by the same pro-
cedure in the above description without the capping agent and
supporting materials, respectively.
2.3. Electrochemical characterizations of PdNCs/G
The working electrodes were independently fabricated as fol-
lows. First, a glassy carbon (GC) disk (diameter ¼ 3 mm) electrode
was polished with slurry of 1, 0.3 and 0.05
m
m alumina to mirror
finish, rinsed with pure water and dried at room temperature in a
vacuum oven for hours. Then, 2 mg of PdNCs/G composite was
dispersed in the mixture of 0.9 mL H
2
O and 0.1 mL 5 wt% Nafion
using ultrasonic treatment to form a homogeneous black suspen-
sion. Finally, 5
m
L of the catalyst suspension was carefully pipetted
onto the surface of the GC disc and dried at room temperature to
form a layer that prevented the catalyst particles from detaching.
The as-prepared PdNCs/G working electrodes were for electro-
chemical evaluations. PdNPs/G and PdNCs working electrodes were
prepared using the same procedure described above.
All electrochemical measurements including cyclic voltammo-
grams (CV) and chronoamperometry (CA) were conducted using a
550 electrochemical workstation (Gaoss Union Instrument Com-
pany, China) at room temperature in a conventional three-
electrode cell, with PdNCs/G, PdNPs/G or PdNCs modified glassy
carbon electrode as the working electrode, a Pt wire as the counter
electrode and a Ag/AgCl electrode saturated with KCl as the refer-
ence electrode. Before each experiment, N
2
gas (99.999%) was used
to remove the dissolved oxygen in the solution to preserve an inert
atmosphere.
2.4. Physicochemical characterizations of PdNCs/G
Pd nanocubes/reduced graphene oxide composites were char-
acterized by XRD using a D8-Advance diffractometer (Bruker, Ger-
many) with Cu K
a
radiation source (
l
¼ 0.15418 nm) and glass
plates as a substrate. The morphology and structure of the samples
were characterized using TEM (FEI TECNAI 20, USA, and JEOL 2100F
with an image-corrector, Japan) and FE-SEM (JSM-7100F, Japan).
EDS analysis of chemical composition was taken by the analyzer
coupled to the FE-SEM. XPS were recorded by a SPeCS system
(PHOIBOS 150, Germany) with Al K
a
radiation (h
n
¼ 1486.6 eV), and
the vacuum in the analysis chamber was maintained at about
10
9
mbar. By EDS, the Pd loading amounts were calculated to be
43.2% in PdNCs/G and 48.2% in PdNPs/G.
Y. Zhang et al. / Journal of Power Sources 280 (2015) 422e429 423