DOI: 10.1002/celc.
201402353 Articles
Probing Structure Modification of Palladium
Nanomaterials during Chemical Synthesis by using In Situ
X-ray Diffraction: Electrochemical Properties
Yaovi Holade, Teko W. Napporn,* Claudia Morais, Karine Servat, and K. Boniface Kokoh[a]
Experimental evidence for Pd-based structure modification of
electrocatalysts with hydrogen during their chemical synthesis
is still missing. Therefore, in situ X-ray diffraction (XRD) tech-
niques were as used to investigate hydrogen insertion into the
lattice of Pd nanomaterials during their preparation. It was
shown that the use of NaBH4 as reducing agent led to PdHx
whereas l-ascorbic acid gave Pd nanoparticles. The subsequent
influence of hydrogen insertion on the catalytic properties of
Pd nanostructures was demonstrated by using carbon monox-
1. Introduction
Materials synthesis for energy conversion and storage has
emerged as a crucial target for the development of new appli-
cations. The control of different parameters during the synthe-
sis is essential for obtaining very active and efficient materials.
Pd-based nanomaterials have received tremendous interest
from all areas of science and technology.[1] In electrocatalysis,
Pd-based catalysts are very active toward alcohol electrooxida-
tion[2] and the well-known oxygen reduction reaction (ORR).[3]
Among them, PdAg,[3a] PdNi,[3a] PdCu,[4] and PdAu[3c, 5] exhibit
good kinetics towards ORR. Simes et al.[6] have shown that
PdAu electrodes are good catalysts for sodium borohydride
(NaBH4) mediated electroreduction in fuel cells (FCs). In 2011,
Shim et al.,[5] showed that Pd-Au bimetallic catalysts exhibit en-
hanced kinetics toward ORR. Several FCs with Pd-based nano-
materials have been tested. Recent advances in bioelectro-
chemistry have highlighted the advantage of using abiotic
nanomaterials as suitable substitutes for enzymes for electro-
chemical reaction in biofuel cells, due to their long-term stabili-
ty.[7] In particular, nanosized metal particles can be suitable for
catalyzing electrochemical reactions in membrane-free,
enzyme-free biofuel cells under physiological conditions for ac-
tivating an implantable device as a pacemaker.[8] To this end,
several methods have been proposed to prepare Pd nanoma-
terials.[1a, 2b, 3a, 6, 9] Most of these methods used NaBH4 as a reduc-
ing agent and only a few investigations used a non-hydrogen
[a] Y. Holade, Dr. T. W. Napporn, Dr. C. Morais, Dr. K. Servat,
Prof. Dr. K. B. Kokoh
Department of Chemistry, Universit de Poitiers
IC2MP CNRS UMR 7285, 4 rue Michel Brunet - B27
TSA 51106, 86073 Cedex 9 (France)
E-mail: teko.napporn@univ-poitiers.fr
Supporting Information for this article is available on the WWW under
http://dx.doi.org/10.1002/celc.201402353.
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ide and glucose as probing molecules. High active surface
areas and catalytic activities were found for the unmodified Pd
nanostructures through electrochemical studies. Notably, the
reducing agent has a significant effect on the size distribution
of the nanoparticles. Its use can precisely and effectively tune
their catalytic properties. Consequently, the remarkable behav-
ior uncovered herein provides new strategic routes that can be
used for the preparation of Pd-based nanomaterials.
source reducing agent such as l-ascorbic acid.[10] Unfortunately,
none of these preparative methods took into account the in-
stability of Pd in a hydrogen environment.[7b, 11] As reported by
Zoubov and Pourbaix in the early 60s,[11f] hydrogen absorption
by Pd is accompanied by a change in the crystalline structure
of the metal, probably due to the formation of not only a,
b and solid solutions, but also of hydrides Pd2H (or Pd4H2) or
PdH0.5.[11c, f, 12] The affinity of Pd with hydrogen and the subse-
quent effect on the physical structure of the metal is well-
documented.[13] Another aspect is the effect of the size of the
Pd particles on hydrogen absorption.[11c, 13f, 14] In the early of
2000s, Suleiman et al.[13f] found that lattice parameter expan-
sion occurs during the hydrogen loading of nanometer-sized
palladium combined with the phase transition. Indeed, clusters
of 3.8 nm predominantly have an icosahedral structure, where-
as those of 6.0 nm have a cubic structure.[13f] Based on these
experimental results, more attention must be paid to the ex-
perimental conditions during the preparation of Pd-based
nanomaterials. For their electrochemical applications, control
of the structure of Pd-based nanomaterials is of considerable
interest. It allows an assessment of the fundamental properties
of the electrode as well as aids in the design of advanced
electrodes.
Herein, by using in situ X-ray diffraction (XRD) techniques,
we provide some new insights on hydrogen insertion into the
structure of Pd nanoparticles during their synthesis when
using NaBH4 as reducing agent. Although dilatation of the Pd
lattice parameter due to the insertion of hydrogen (during the
chemical synthesis) into Pd nanoparticle structures has been
suggested before,[2b, 3a, 6] no in situ physical method was used
to elucidate the details. These studies aim to determine the
structure modification caused by hydrogen absorption that
occurs during the chemical synthesis when using NaBH4 as a re-
1  0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim &

ducing agent and to establish the effect of the change on the
electrochemical properties of the resulting material. Pd nano-
particles were prepared according to “Bromide Anion Ex-
change: BAE” method.[2] Herein, the method has been slightly
modified to synthesize two kinds of Pd nanomaterials support-
ed on Vulcan XC 72R carbon (20 wt. %). The material obtained
by using l-ascorbic acid as reducing agent was named Pd/C-
AA and that obtained by using NaBH4 is referred as Pd/C-
NaBH4. After characterization through thermogravimetric analy-
sis (TGA) to determine the real metal loading, transmission
electron microscopy (TEM) was used to analyze the subse-
quent effect of the reducing agent on the size and distribution
of the nanoparticles.
2. Results and Discussion
2.1. TGA and TEM Characterization of the Nanomaterials
Firstly, the expected metal loading was confirmed by using
thermogravimetric analyses: 16 wt. % (Pd/C-NaBH4) and
18 wt. % (Pd/C-AA), which are close to the target value of
20 wt. % (Figure 1). In this figure, Vulcan XC 72R carbon, which
Figure 1. TGA curves at 100 mL min1 air flow and 5 8C min1 linear tempera-
ture variation. Vulcan XC 72R carbon (Curve a); Pd/C-AA (Curve b) and Pd/C-
NaBH4 (Curve c) materials.
was used as support for Pd nanoparticles, was considered as
reference. It was reported that platinum-based nanomaterials
catalyze carbon combustion reaction, which typically takes
place at approximately 600 8C.[8, 15] Based on the results pre-
sented in Figure 1, this character can be extended to Pd nano-
particles. It is worth emphasizing that both Pd/C-AA and Pd/C-
NaBH4 were prepared in high chemical synthesis yield;[2a] that
is, 97 and 99 %, respectively. Compared with other meth-
ods,[7a, 16] this confirms that the BAE approach minimizes metal
loss during the synthesis as recently shown for the preparation
of Pt or gold-based catalysts.[2a, 17] This expected higher value
(> 90 %) for the BAE method has been attributed to its simplic-
ity of implementation.[2a]
Figures 2 a (for Pd/C-AA) and 2 b (for Pd/C-NaBH4) display
TEM micrographs of the as-synthesized nanomaterials. Their
typical high-resolution images (HRTEM) are presented in the
inset. The images show a homogeneous dispersion of the
nanoparticles on the support, and this is demonstrated by the
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Figure 2. TEM micrographs of a) Pd/C-AA and b) Pd/C-NaBH4, and (insets)
their corresponding HRTEM images. Histograms of metal particle size distri-
bution with log-normal fit: more than 400 isolated particles were counted:
c) Pd/C-AA and d) Pd/C-NaBH4 materials.
histograms of particles size distribution depicted in Figure 2 c
(for Pd/C-AA) and 2 d (for Pd/C-NaBH4). The mean particle size
determined from LogNormal function fit (Dm,p) was found to
be 8 and 3 nm for Pd/C-AA and Pd/C-NaBH4, respectively.
Clearly, at this experimental level, in contrast to NaBH4, l-ascor-
bic acid promotes the formation of large nanoparticles. The
difference in size is explained by the fact that l-ascorbic acid is
a weak reducing agent, whereas NaBH4 has strong reduction
abilities.[18] Actually, the molar ratio between the reducing
agent and Pd is 15 for 0.1 m NaBH4 and 7 for 0.1 m l-ascorbic
acid. Increasing the l-ascorbic acid concentration up to 1 m (or
ratio up to 15) could probably have an effect on the particle
size reduction.
The decrease in the mean particle size, which was evaluated
from TEM analysis, might be in the range of the results from
XRD (denoted here as Lv). However, with XRD, we can only
measure the crystallite size, which is the coherent diffracting
crystalline domain, which is very different from particle size. It
should be noticed that one particle can be composed of sever-
al crystallites. Prior to the comparison of crystallite sizes by
XRD, the average particle size determined by TEM analyses
must be normalized with the total volume of the counted par-
ticles (Dv, 3D representation). The procedure is explained in
detail in our recent paper.[17] Indeed, XRD measurements con-
cern the 3D structure; so the result from TEM must be in the
same range before any comparison. When these fundamentals
are understood, particle size from TEM (Dv) must always be
bigger than crystallite (domain) size from XRD (Lv) or, in case of
small nanoparticles, both of them can be the same. The
domain size (evaluated from XRD) should never be larger than
the particle size determined by TEM, when the latter value is
normalized with volume.
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2.2. Structural Characterization by using In Situ XRD
Pd/C-AA and Pd/C-NaBH4 were first characterized by XRD at
30 8C. We report in Figure S 1a the XRD pattern for Pd/C-AA
sample. Except for the peak at approximately 258, assigned to
Vulcan XC 72R carbon[17] and those marked by an asterisk (red)
due to the sample support [the ribbon in kanthal (Iron-
Chrome-Aluminum alloy)], the others belong to Pd, which ex-
hibit face-centered cubic (fcc) symmetry. For Pd/C-AA, peaks
are situated at 39.9, 46.5, 68.0, 81.6, 86.6, 104.5, 119.7, and
125.48 and correspond, respectively, to the crystallographic
planes (111), (200), (220), (311), (222), (400), (331), and (420);
see Table S1. Parameters for Pd/C-NaBH4 can be found in
Table S2. Surprisingly, peaks shift towards lower diffraction
angles compared with the Pd/C-AA sample. This can be attrib-
uted to changes in the Pd nanoparticles derived from the two
opposite reducing agents: hydrogen content (NaBH4) and free-
hydrogen compound (l-ascorbic acid). To gain further details,
quantitative analyses were performed through analysis of the
lattice parameter. This parameter was determined by two
methods: interplanar spacing of the crystallographic plane
(hkl) method [Eq. (2)] and Bragg’s law,[19] [Eq. (3)], which is the
combination of Equations (1) and (2). The results are summar-
ized in Tables S1 and S2 for different crystallographic planes.
l ¼ 2dsinq
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
aðhklÞ ¼ dðhklÞ h2 þ k2 þ l2
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
h2 þ k 2 þ l 2
aðBraggÞ ¼ l
2 sin q
In these equations, l is the wavelength of X-ray (1.54060 );
a is the lattice parameter; q is the Bragg’s angle and d(hkl) is the
interplanar spacing of crystallographic plane (hkl).
The evaluation of the lattice parameter by using Equation (3)
for different crystallographic planes (hkl) gave 3.89–3.90  for
Pd/C-AA and 3.93–3.95  for the Pd/C-NaBH4, whereas Pd bulk
has 3.89  as lattice parameter.[11c, 12b] Values obtained for Pd/C-
AA are equal to or slightly greater than that of the bulk. This
can be explained by a dilatation of the lattice parameter due
to the small size of Pd particles, as already reported.[13f] Howev-
er, this slight dilatation is not sufficient to explain the more sig-
nificant variation observed for Pd/C-NaBH4 material. In our pre-
vious work as well as in other reports,[3a, 6] we assumed that
there is hydrogen insertion in the Pd crystal lattice.[2b] This in-
sertion occurs into the network of Pd nanoparticles during the
chemical synthesis, using NaBH4 as reducing agent. To further
explore this hypothesis, in situ XRD experiments under
a helium atmosphere were performed at different tempera-
tures to insure the removal of absorbed hydrogen (see Experi-
mental Section for full details). Indeed, if the presence of hy-
drogen in the Pd crystal is effective, the relaxation of the crys-
tal lattice should occur at higher temperature; in this case,
above 60 8C. The maximum temperature was set at 150 8C to
avoid Vulcan carbon combustion; nevertheless, hydrogen re-
lease from the network of Pd nanoparticles must be effective
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above this temperature. A final diffractogram was recorded at
the initial temperature (30 8C) for comparison. The complete
XRD patterns are reported in Figure S1b and S1c. The lattice
parameters were calculated by using the Bragg law (aBragg) and
also by interplanar spacing (a(hkl)). The obtained values are re-
ported in Tables S1 and S2. Figure 3 a–d present the (111) and
ð1Þ
Figure 3. In situ XRD patterns for (111) and (220) crystallographic planes of
ð2Þ the catalysts a,b) Pd/C-AA and c,d) Pd-NaBH4 at different temperatures.
ð3Þ
(220) diffraction peaks of Pd obtained at different temperatures
for the two synthesized materials. As shown, no shift of the
peak position is observed when AA is used as reducing agent
(Pd/C-AA). Moreover, the determined lattice parameter did not
vary for different temperatures. In contrast to the behavior de-
scribed for Pd/C-AA material, the Pd/C-NaBH4 materials pre-
pared by using NaBH4 as reducing agent showed a shift of the
peak position and a variation of the interplanar spacing of
crystallographic plane (hkl), d(hkl). In fact, the peak positions
shift toward higher 2q values when the temperature increased
(see Figure 3 c,d, and Table S2). As shown in Figure 2 c and 2d,
the shift is 0.38 and 0.78 for (111) and (200) planes, respectively.
The complete set of results is summarized in Table S2. This dif-
ference in the XRD patterns recorded for the two kinds of ma-
terials results from a potential modification of Pd nanomateri-
als by the reducing agent. From this in situ XRD study, it was
found that the peak positions increased toward those of Pd/C-
AA when the temperature was increased. As seen in Table S2
(Pd/C-NaBH4 material), results at 150 8C and at 30 8C show that
Pd regains its initial peak positions beyond 150 8C.
Figure 4 shows aBragg values obtained for the well-defined
peak (220) at different temperatures. The aBragg value remains
constant for the Pd/C-AA material, whereas for Pd/C-NaBH4
material, the lattice parameter decreases at increasing temper-
atures (see Table S2). For the final temperature (150 8C), the ob-
tained aBragg value is the same for both materials, indicating
that the hydrogen absorbed during the synthesis was totally
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Figure 4. Evolution of Bragg’s lattice parameter for (220) crystallographic
plane during in situ XRD analysis: (&) Pd/C-AA; (*) Pd-NaBH4 at different
temperatures. At 30 8C after heat-treatment at 150 8C: (~) Pd/C-AA; (N) Pd-
NaBH4.
desorbed at 150 8C. The average crystallite size evaluated by
the Debye–Scherrer relation (not shown) demonstrated that
there is no increase of the particles size during this thermal
treatment. This treatment can affect the structure and the
properties of the palladium nanoparticles. Indeed, it is well-
known that the lattice distance usually has a notable effect on
the catalytic properties of the nanomaterials by tuning the d-
band center of the metal nanoparticles. Corollary, the dilatation
of the Pd lattice parameter will induce a significant change in
the catalytic performance of the particles because the latter
are conditioned by the valence electrons of the metal. To this
end, electrochemical tests were undertaken to identify any
change in the catalytic properties of the material.
2.3. Electrochemical Characterization of the Nanomaterials
by CO Stripping
The catalytic activities of the two as-prepared Pd nanomateri-
als were then investigated. For an initial characterization of cat-
alytic performance, experiments on carbon monoxide electro-
oxidation by CO stripping were undertaken in alkaline medium
to probe the surface of the nanoparticles. To conduct the CO
stripping experiment, three steps were involved: 1) adsorption
of CO on the electrode at a fixed potential (herein 0.3 V vs.
RHE) for approximately 5 min; 2) nitrogen or argon was then
bubbled for more than 15 min to completely remove nonad-
sorbed CO in the bulk solution; 3) Finally, cyclic voltammetry
measurements were performed. In this case, only the remain-
ing CO that was adsorbed at the electrode surface was electro-
oxidized during the forward potential scan. In the reverse scan,
there were no reactive species that would be oxidized again. It
should be noted that, the adsorption step starts after record-
ing a steady-state cyclic voltammogram (CV). CVs before CO
stripping experiments at 20 mV s1 in a supporting electrolyte
(0.1 m NaOH) are depicted in Figure 5 a (Pd/C-AA) and 5 d (Pd/
C-NaBH4) as solid black curves, scaled versus RHE. Rigorously,
the CV for the third step must be superimposed on the normal
steady-state CV. This occurs only when CO adsorption does not
induce any irreversible modification on the catalytic surface, as
observed on Pt-based electrode materials. All typical specific
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Figure 5. CO stripping experiments at 20 mV s1 in 0.1 mol L1 NaOH at
25 8C; CO was adsorbed at 0.3 V vs. RHE for 5 min. Full CVs of a) Pd/C-AA
and b) Pd/C-NaBH4 : CV before oxidation (black solid line), CO oxidation (red
dotted line), and first cycle after CO stripping (blue dashed line). c) Compari-
son of polarization curves.
domains of Pd are present on the CVs that were recorded with
a lower potential limit set at 0.3 V vs. RHE to avoid any irrever-
sible hydrogen insertion (absorption) in the Pd nanocrys-
tal.[2b, 20] During the forward potential scan, hydroxyl adsorption
occurs before 0.6 V vs. RHE, followed by Pd surface oxidation,
which takes place at high potentials. When the upper potential
limit is fixed at 1.45 V vs. RHE, the formed PdII oxide (PdO) is
then reduced during the backward potential scan at approxi-
mately 0.63 V vs. RHE.[2b, 6] The red dotted curves in Figure 5 a
and 5 b illustrate the adsorbed CO electrooxidation. This reac-
tion is concurrent with the hydroxyl formation at the Pd sur-
face, indicating a Langmuir–Hinshelwood mechanism,[21] which
involves two adsorbed species. The most important aspect
concerns the comparison of the performance of the two kinds
of catalytic electrodes. For this purpose, we compared the two
polarization curves recorded during the first cycle of the CO
stripping experiment (Figure 5 c ). The current was normalized
with the electrochemical active surface area (SA, see the Exper-
imental Section for the method) and also by the Pd weight. By
taking account the active sites (via SA) and the metal content,
we can obtain real activity values for comparison. For the
same Pd nanoparticle structures, because particles from NaBH4
are very small compared with those from AA, a very large dif-
ference in terms of activity was expected. Otherwise, Pd/C-
NaBH4 must be more active than Pd/C-AA. Against all expecta-
tions, Pd/C-AA exhibited the best catalytic activity by present-
ing good kinetics at lower potentials than Pd/C-NaBH4. More
importantly, Pd/C-AA shows a specific current density of
18.2 A cm2 g1 at 820 mV vs. RHE; an 18.2 % increase com-
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pared with Pd/C-NaBH4 (15.4 A cm2 g1 at 830 mV vs. RHE).
This improvement in catalytic activity could be supported by
the formation of PdHx when NaBH4 is used as reducing agent.
Indeed, the presence of the absorbed hydrogen as PdHx can
significantly reduce the chemisorption of CO on Pd and, subse-
quently, the activity of the nanoparticles. These electrochemi-
cal results constitute experimental evidence for modification
by hydrogen insertion of the catalytic properties of palladium
nanoparticles. The specific electrochemical active surface area
obtained by the PdO peak reduction method (see Experimen-
tal Section) is 60 m2 g1 for Pd/C-AA and 81 m2 g1 for Pd/C-
NaBH4, whereas the utilization of the CO stripping charge
gives values of 51 m2 g1 (Pd/C-AA) and 74 m2 g1 (Pd/C-
NaBH4). In both cases, the obtained values are high when com-
pared with reported values of 28 m2 g1 obtained under the
same experimental conditions.[6] Furthermore, it should be
stated that the differences obtained by using the two methods
were expected and they were attributed to the incomplete CO
monolayer.[22] The differences between the studied materials
are not unexpected and are consistent with the obtained parti-
cle size distributions, with the particles being smaller for Pd/C-
NaBH4.
2.4. Electrochemical Activity of the Nanomaterials toward
Glucose Oxidation
Among the carbohydrates that can be used as fuel in biofuel
cells, glucose is an excellent probing molecule for various ap-
plications.[2a, 7a, c, 8, 23] In the case of the hybrid[2a, 7a] or abiotic[7c, 8]
biofuel cells, abiotic anode materials have been utilized to re-
place some enzymes. More importantly, it was recently report-
ed that replacing enzymes in biofuel cells by metal nanoparti-
cles that are well-dispersed onto carbon substrate leads to an
improvement in the long-term stability of the fuel cell.[8] For
the first time, the authors have found that a membrane-free
biofuel cell in which abiotic nanoparticles replaced enzymes[24]
can successfully substitute batteries for the activation of a pace-
maker under physiological conditions. The as-prepared Pd/C
catalysts were characterized electrochemically thorough the
glucose oxidation reaction. As pointed out above, the investi-
gations were performed in alkaline medium to measure the in-
trinsic activity of the catalyst in the absence of some blocking
anions such as chloride and phosphate in physiological buf-
fered solution. Figure 6 a shows the CV in N2-saturated 0.1 m
NaOH (dotted curve a) and in the presence of 10 mm of glu-
cose (solid curve b) on Pd/C-AA electrode. The same graphs
normalized with the glassy carbon geometrical surface area
(0.07 cm2) is provided in Figure S2. Glucose oxidation starts at
approximately 0.4 V vs. RHE followed by a peak current at ap-
proximately 0.82 V vs. RHE associated with the bulk glucose
oxidation to gluconate.[2a, 7a, 21b] This onset potential is much
lower than those reported elsewhere[10b, 25] and reflects good ki-
netics of the Pd/C catalyst synthesized through the BAE syn-
thetic route. The decrease in the current is then attributed to
catalyst deactivation due to PdO formation. During the nega-
tive going scan, the surface becomes active after 0.6 V vs. RHE
because of the reduction of PdO to Pd; a reaction that typically
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Figure 6. a) Cyclic voltammograms recorded at 25 8C and 20 mV s1 in N2-sa-
turated 0.1 mol L1 NaOH (dotted curve a) and in the presence of 10 mm
glucose (solid curve b) on Pd/C-AA electrode. b) Comparison of polarization
curves on (c) Pd/C-AA and (g) Pd/C-NaBH4.
takes place in this potential range. We then examined the two
electrode materials derived from Pd/C-AA and Pd/C-NaBH4 cat-
alysts by comparing their polarization curves (Figure 6 b). As
can be observed in Figure 6 b, no significant difference in the
specific activity was found between the two anode catalysts
toward the glucose oxidation reaction, despite the size distri-
bution of the Pd particles produced by the reducing agents.
This could be due to the fact that glucose is a larger molecule
than CO. The specific activity thus seems to be unaffected by
the particle size difference. Therefore, for the glucose oxidation
reaction, AA could be used to synthesize Pd nanoparticles
without activity loss.
The peak position depends on the electrode material
(shape, size, etc) and on the method of preparation. The
anodic peak potential is situated at 0.84 and 0.82 V vs. RHE on
Pd/C-NaBH4 and Pd/C-AA, respectively. The position was ap-
proximately 1.07 V vs. RHE on Pd/C synthesized from micro-
wave assisted polyol method[26] and 1.15 V vs. RHE on Pd nano-
wires.[25a] These values show clearly that the glucose oxidation
shifts toward lower potentials on the Pd/C catalyst prepared
by using the BAE approach. By using geometrical surface area
normalization (see Figure S2), the peak current density was ap-
proximately 5.5 mA cm2 on Pd/C-AA electrode, which is an en-
hanced activity compared with other reports.[25–27] Additionally,
it is notable that Pd/C-AA showed good catalytic performance
for glucose electrooxidation in buffered solution at pH 7.4.
When it was used as anode material in a hybrid glucose bio-
fuel cell, a better power performance was obtained (result
shown herein).
3. Conclusions
We have investigated the effect of hydrogen insertion into the
palladium structure and correlated this finding with electro-
chemical properties by using two different reducing agents. In
contrast to NaBH4, the use of ascorbic acid (AA) as reducing
agent slowed down the reduction process of the Pd nanoparti-
cles, whereas borohydride ions led to narrower nanomaterial
size. The latter particles catalyze the decomposition of the re-
ducing agent to hydrogen, which is inserted into the palladi-
um crystallographic structure, as evidenced by in situ XRD
measurements. Transmission electron microscopy analysis has
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shown that NaBH4 promotes the formation of very small nano-
particles (1–7 nm), whereas AA leads to larger particles (3–
18 nm). These trends have been explained in detail by examin-
ing the difference in their reduction properties, with NaBH4
being a more powerful reducing agent than AA. In the pres-
ence of a small probing molecule such as CO, the catalytic ac-
tivity of Pd/C was affected to a greater or lesser extent accord-
ing to the reducing agent used during the synthesis. Actually,
CO oxidation is less sensitive to the Pd/C-NaBH4 surface, be-
cause the dilation of the lattice parameter by the hydride indu-
ces CO oxidative removal at higher potentials. Inversely, for
a larger molecule such as glucose, the beneficial effect of AA
on the lattice parameter is canceled by a larger particle size,
which decreases the electrode surface area of Pd/C-AA. Never-
theless, the present study reinforces the conclusion that suita-
ble reducing agents must be used for the synthesis of ad-
vanced metal nanoparticles for heterogeneous catalysis, and
that a clear fundamental comprehension of their structure is
crucial.
Experimental Section
Chemicals
Potassium tetrachloropalladate(II) (K2PdCl4, 99 %), sodium borohy-
dride (NaBH4, 99 %), potassium bromide (KBr,  99 %), and l-ascor-
bic acid ( 99 %) were purchased from Sigma–Aldrich. These chem-
icals were analytical grade and were used without further purifica-
tion. Vulcan XC 72R carbon black was provided by Cabot and ther-
mally activated (see section below). Ultra-pure water from Milli-Q
Millipore source (18.2 MW cm at 20 8C) was used in all experiments.
Nanocatalyst Synthesis by Bromide Anion Exchange
Prior to its use as a nanoparticle supporting material, Vulcan XC
72R carbon black was treated at 400 8C under a nitrogen atmos-
phere with the primary aim of removing undesired contaminants
(sulfur) coming from its industrial manufacture.[1] For the pretreat-
ment, an amount of commercial material was placed in a Pyrex
crucible and introduced into a closed furnace under a nitrogen at-
mosphere. The temperature was then elevated at rate of 5 8C min1
up to 400 8C and kept at 400 8C for 4 h. Finally, the sample was
cooled. We selected a temperature of 400 8C to avoid carbon com-
bustion at higher temperature. The nitrogen adsorption-desorption
isotherm measurements (performed with Micrometrics ASAP 2010
instruments) highlighted a surprising enhancement of the specific
surface area, calculated from the Brunauer–Emmett–Teller (BET)
theory,[28] which increases from 262 m2 g1 (for pristine Vulcan) to
322 m2 g1 for our thermal annealed material, meaning a 23 %
gain.[17] The supported palladium nanoparticles were then pre-
pared according to the recently reported method for tailoring of
palladium-based nanoscale active materials.[2b] This BAE method
was slightly modified, herein, to synthesize two kinds of palladium
nanomaterials supported on carbon Vulcan XC 72R (Pd/C). Briefly,
the BAE method consists of the reduction of PdII in aqueous solu-
tion in the presence of bromide ion. Firstly, K2PdCl4 (61.4 mg) was
dissolved in ultrapure water (100 mL) in a thermostatted bath at
25 8C. KBr (32.7 mg) was then added under vigorous stirring and
Vulcan XC 72R carbon black (80 mg) was added under constant ul-
trasonic homogenization for 45 min to obtain a metal loading of
20 wt. %. The reducing agent, NaBH4 (0.1 mol L1, 15 mL) or l-ascor-
& ChemElectroChem 0000, 00, 0 – 0 www.chemelectrochem.org
Articles
bic acid (AA; 0.1 mol L1, 13 mL), was then added dropwise under
vigorous stirring to synthesize the Pd/C-NaBH4 or Pd/C-AA nano-
materials, respectively. Finally, the supported materials were fil-
tered, rinsed several times with ultrapure water, and dried in an
oven at 40 8C for 12 h.
Physicochemical Characterization of the Abiotic Catalysts
To confirm the metal loading, differential and thermogravimetric
analysis (DTA/TGA) were performed under air atmosphere. During
the analysis, TGA provides metal loading whereas DTA gives infor-
mation about the thermodynamics of the reaction. TA Instruments
SDT Q600 apparatus equipped with TA Universal Analysis software
was used for DTA/TGA analysis. Two alumina crucibles, one con-
taining approximately 7 mg of the sample and a second empty
(reference) were thermally heated under air atmosphere (flow
100 mL min1) from 25 8C to 900 8C with a temperature rate of 5 8C
min1.
The XRD experiments performed in situ at different temperatures
were conducted with a Bruker D8 Advance (BRUKER AXS) diffrac-
tometer in a Bragg–Brentano (q-q) configuration with a copper
tube powdered at 40 kV and 40 mA (Cu-Ka1 = 1.54060  and Cu-
Ka2 = 1.54443 ). A nickel filter was installed in a secondary optic to
eliminate the kb component. Diffraction angle (in 2q) ranging from
208 to 1308 were investigated by using a step of 0.0998. To further
explore the possible modification of palladium structure by hydro-
gen absorption during the reduction step, XRD experiments were
performed in situ at different temperatures (30, 50, 70, 100, 150 8C)
as illustrated in Figure 7. Between two temperature values, the
Figure 7. Experimental setup for in situ XRD measurements at control
temperature.
temperature increase ramp was 5 8C min1. The experiments were
conducted under a helium atmosphere at a constant flow of
500 mL min1. Before the analysis, a purge was done under helium
atmosphere for 90 min at 30 8C. The accumulating time was of 5 s
for the initial temperature and 2.5 s for the higher temperature
values to avoid long exposure time. Basically, the sample (Pd/AA or
Pd/C-NaBH4) was mounted on a ribbon in kanthal (Iron-Chrome-
Aluminum alloy) and heated by Joule effect. In all cases, the diver-
gence slit was of 0.38 and the opening window of the detector
was of 38. The analysis of the position and crystallite size values
were both obtained by fitting the experimental angular range of
interest with the HighScorePlus software using the pseudo-Voigt
function.[29]
6  0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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 Articles
To obtain further information, in particular on particle dispersion
and particle size distribution, the materials were also characterized
by TEM with a TEM/STEM JEOL 2100 UHR (200 kV) equipped with
a LaB6 filament. The mean particle size and particle size distribu-
tion were determined by measuring the diameter of isolated parti-
cles (more than 400 particles) using ImageJ free software.[30]

Electrochemical Measurements
An analogue potentiostat EG&G PARC Model 362 (Princeton Ap-
plied Research) monitored by a computer and a conventional
three-electrode cell served for all electrochemical experiments.[31] Figure 8. Illustration of the methods used for electrochemical active surface
We used a slab of glassy carbon with a geometrical surface area of area determination by cyclic voltammetry on Pd/C-AA. a) The blue solid line
6.48 cm2 as counter electrode and an Hg/HgO (0.1 m NaOH, MMO, represents the complete steady-state CV whereas the shaded curve shows
0.158 V vs. standard hydrogen electrode) as reference electrode. the integrated region. The experiments were recorded at 20 mV s1 in
The working electrode was composed of a catalytic ink (3 mL) de- 0.1 mol L1 NaOH and 25 8C. b) The “weighing method” showing the cut
region; the inset shows the tracing paper used as reference for weighing on
posited on a 3 mm diameter glassy carbon disk used as conductive
an ultra-sensitive balance.
carrier. The catalytic ink was prepared according to our standard
method[7] by ultrasonic mixing ultrapure water (375 mL), Nafion sus-
pension (5 wt. %, 50 mL), and catalytic powder (4 mg). All cyclic vol- active surface area in cm2, whereas Equation (7) gives the SECSA in
tammetry[6, 8] experiments were performed in 0.1 mol L1 NaOH as m2 g1:
supporting electrolyte, provided by Sigma–Aldrich (ReagentPlus,
97 %) and prepared with ultra-pure water. To avoid dissolved
oxygen interference during the electrochemical experiments, the Qex
SAðcm2 Þ ¼ ð4Þ
electrolytic solution was systematically deoxygenated by bubbling Qm
high quality nitrogen (from Air Liquide) for 30 min prior to any Z Eend

measurement. The effect of hydrogen insertion in Pd nanomateri- 1
Qex ðmCÞ ¼ iðE ÞdE ð5Þ
als on their catalytic properties was probed by using carbon mon- v Eonset

oxide (CO, Air Liquide, ultra-pure). Their catalytic activity was then
examined in 10 mm glucose (d-(+)-glucose, Sigma–Aldrich, 99.5) m1 s0 ab
Qex ðmCÞ ¼ ð6Þ
solution. All experiments were performed at controlled tempera- m0 xy v
ture of 25 8C. For CO stripping experiments, CO was adsorbed at
0.30 V vs. RHE for 5 min and the solution was then deaerated for SA
SECSAðm2 g1 Þ ¼ ð7Þ
a minimum of 30 min. Metal weight

where v is the scan rate, and Eonset and Eend are the limits of integra-
SECSA Evaluation tion (see Figure S5).

Various methods can be used to determine the electrochemical

active surface area of metals: adsorption/desorption of hydrogen,
stripping of a probe molecule (CO), under potential deposition
(UPD), or oxide reduction peak.[32] It is well-known that Pd (and in
particular Pd NPs) has the ability to absorb hydrogen into its crys-
tal lattice.[11b, c, 20b, c, 33] To avoid this phenomenon, we did not use
the hydrogen adsorption-desorption region method but instead
used the reduction peak of palladium oxide (PdO) and CO strip-
ping methods to determine the SECSA. A charge density of
424 mC cm2 (Qm) is associated with the reduction of the formed
PdO monolayer,[2b, 34] whereas the charge associated with the oxida-
tion of the CO monolayer is 420 mC cm2 (Qm). Basically, the electro-
chemical active surface area was evaluated by using Equation (4),
where the exchange charge (Qex) is experimentally determined as
aforementioned. Figure 8 a shows the integrated region using PdO
reduction; Qex was obtained from Equation (5) using Origin8 soft-
ware. To determine confirmation, we used the classical so-called
“weighing method” to obtain this charge. Briefly, this involves cut-
ting a known surface of tracing paper (surface s0) and weighing it
as reference (weight m0). Then, the part of the CV containing the
area of interest (here PdO region) is printed on any paper and
weighed (weight m1). After that, the assessment of Qex is a straight-
forward mathematic task that is summarized in Equation (6). The
variables a, b, x, y and v used in Equation (6) are represented in
Figure 8 b. It is highly recommended to perform at least three
tests. In both scenarios, Equation (4) was used to calculate the
Acknowledgements
This research was financially supported by the French National
Research Agency (ANR) through the ChemBio-Energy program
(2012–2015).
Keywords: crystal engineering · electrochemistry · fuel cells ·
nanoparticles · palladium
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Received: October 20, 2014
Revised: November 17, 2014
Published online on && &&, 2014
8  0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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ARTICLES
The way you make it! Hydrogen inser- Y. Holade, T. W. Napporn,* C. Morais,
tion into palladium nanoparticles during K. Servat, K. B. Kokoh
their chemical synthesis using a hydro-
&& – &&
gen source compound has been high-
lighted by conducting in situ X-ray dif- Probing Structure Modification of
fraction measurements. Subsequent ef- Palladium Nanomaterials during
fects on the catalytic properties of the Chemical Synthesis by using In Situ X-
materials were scrutinized. ray Diffraction: Electrochemical
Properties

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