Short Articles
studied in different applications,16­18 this effect has not been
Size Effect of Carbon-Supported Pd
Nanoparticles in the Hydrogen
Production from Formic Acid
Miriam Navlani-García,1 Kohsuke Mori,*1,2
Meicheng Wen,1 Yasutaka Kuwahara,1,2
and Hiromi Yamashita*1,2
1 strongly dependent on the size of Pd NPs and that this catalytic
Division of Materials and Manufacturing Science,
Graduate School of Engineering, Osaka University,
2-1 Yamada-oka, Suita, Osaka 565-0871
2
Unit of Elements Strategy Initiative for Catalysts and
Batteries, Kyoto University, Katsura, Kyoto 615-8520
E-mail: yamashita@mat.eng.osaka-u.ac.jp
Received: June 27, 2015; Accepted: July 21, 2015;
Web Released: August 3, 2015
Particle size dependence in the H2 production from
formic acid was investigated over Pd/C catalysts with
nanoparticle sizes ranging from 2.7 to 5.5 nm. A volcano
type relationship between catalytic activity and nanoparticle
size was obtained and the average size of 3.9 nm exhibited
the highest activity under mild reaction conditions.
Formic acid (FA) has recently received important attention
as a stable and readily available liquid-phase chemical hydro-
gen (H2) storage material, as it is one of the major products
formed during biomass processing, it is non-toxic and non-
flammable at room temperature and it is suitable for easy trans-
portation, handling, and storage.1 The FA decomposition can
follow two possible pathways:2
Dehydrogenation: HCOOH ! H2 þ CO2 ð1Þ
Dehydration: HCOOH ! CO þ H2 O ð2Þ
Great efforts have been devoted to the development of an
optimum catalyst for FA decomposition, which must be able to
boost only the H2 production through the FA dehydrogena-
tion reaction since the CO impurity is toxic to Pt catalysts in
fuel cells. Although there have been extensive studies on FA
decomposition using homogeneous metal complex catalysts
at ambient temperatures, current research has been focused on
the exploitation of practical heterogeneous catalysts,3­10 where-
in especially Pd nanoparticles (NPs) exhibit excellent catalytic
activity.11,12 These materials at the nanoscale exhibit unique
physicochemical properties compared to the bulk metals, which
are attributed to the extremely small sizes that result in large
surface areas.12­15 As a consequence of the excellent catalytic
properties displayed by metal NPs, important efforts have been
dedicated to prepare metal NPs with tuned shape and size as
well as to study the influence of both parameters in the final
catalytic performance in different reactions. Although the size-
dependent catalytic performances of NPs have been widely
1500 | Bull. Chem. Soc. Jpn. 2015, 88, 1500–1502 | doi:10.1246/bcsj.20150223
reported for the FA decomposition reaction and the under-
standing of the optimal Pd NP size still remains uncertain.19
In the present study, the effect of the particle size in the H2
production from FA has been investigated over carbon-sup-
ported Pd NP catalysts (Pd/C) with various sizes. The size-
controlled colloidal Pd NPs were first prepared by the polyol
method, which were subsequently deposited on the carbon
support. Polyol method is one of the most convenient method-
ologies to prepare metal NPs due to lack of additional tem-
plating materials, low cost and simplicity of the process.20 The
results obtained revealed that the FA dehydrogenation was
performance did not follow a conventional monotone trend
with the metal NP size, and the optimal catalytic activity was
attained with an average NP sized of 3.9 nm.
The colloidal Pd NPs were synthesized by polyol method
using palladium(II) acetate as Pd precursor, poly(vinyl-
pyrrolidone) (PVP, 30 K) as NPs stabilizing agent and ethylene
glycol as solvent and reductant agent. Different experimental
conditions, in terms of PVP/Pd molar ratio, Pd NPs reduction
temperature, reaction time and Pd precursor concentration were
used (See Supporting Information for experimental details).
As it can be seen in Figure 1, all the metallic colloids show-
ed UV absorption at ­max = 250­300 nm, which, according to
theoretical calculation, was ascribed to the surface plasmon
resonance (SPR) absorption of spherical palladium NPs.21 In
addition, the lack of absorption peak at ­ = 325 nm indicated
that all the palladium is reduced during the synthesis of the col-
loids, as this band would be ascribed to the Pd ions interacting
with PVP molecules.22
According to the TEM micrograph analysis of the metallic
colloids (See Supporting Information and Table 1 for details),
the Pd NPs showed small average NP size in the colloids,
together with very narrow size distribution. Pd NPs had spheri-
cal shape and agglomeration was not observed except for
colloid 6, prepared at 180 °C. In this case, a non-stable colloid
was obtained as some of the Pd NPs flocculated to the bottom of
the vessel after NPs redispersion in methanol. This fact can be
attributed to a sintering process occurring in the metallic colloid
as a consequence of the less controlled synthesis conditions
which led to fast NPs nucleation and growth kinetics.23
Nevertheless, in order to ensure that the supported NPs were
representative of the colloid 6, ultrasonic treatment was used
while taking the aliquot of this colloid to prepare the counterpart
catalyst. As expected, the Pd NPs had different NPs size
Colloid 1
Colloid 2
Colloid 3
Absorption (a.u.)
Colloid 4
Colloid 5
Colloid 6
200 300 400 500 600
Wavelength/nm
Figure 1. UV­vis spectra of the metallic colloids.
© 2015 The Chemical Society of Japan
Table 1. Particle size (d) colloids and catalysts

dcolloid Pd/C dPd/C

Pd colloid
/nm catalyst /nm
Colloid 1 1.9 « 0.4 Pd/C(1) 2.7 « 0.7
Colloid 2 2.4 « 0.4 Pd/C(2) 3.6 « 0.8
Colloid 3 2.1 « 0.4 Pd/C(3) 3.9 « 0.9
Colloid 4 2.5 « 0.5 Pd/C(4) 4.2 « 0.6
Colloid 5 3.2 « 0.4 Pd/C(5) 5.5 « 1.6
Colloid 6 ®a) Pd/C(6) ®a)
a) Sample Pd/C(6) prepared with the colloid synthesized at
180 °C showed heavy agglomeration, which hampered the
accurate Pd NPs size determination.

depending on the experimental condition used, and the PVP/

Pd ratio and the reduction temperature are the most important
parameters in controlling the size of Pd NPs in this work, which
is in good agreement with studies reported elsewhere.23 The
effect of the PVP/Pd molar ratio can be clearly assessed by
comparing colloid 3 and colloid 5 (with average NPs size of 2.1
and 3.2 nm, respectively), while the evaluation of the reduction
temperature was notably pointed out from the observation of
colloid 6, where Pd NPs ranged from a few nanometers to larger
and sintered Pd NPs were detected.
The obtained size-controlled NPs were successfully depos-
ited on the carbon support (SBET: 1051 m2 g¹1, Vp: 0.65 cm3 g¹1)
to prepare various Pd/C catalysts with different Pd NPs sizes
denoted as Pd/C(1)­Pd/C(6). The ICP results confirmed that Figure 2. TEM images and the corresponding histograms
the final metal loading was 0.5 wt % for all the catalyst (the for the Pd/C catalysts: a) Pd/C(1); b) Pd/C(2); c) Pd/C(3);
difference among them being no more than 0.05 wt %). Figure 2 d) Pd/C(4); e) Pd/C(5); f ) Pd/C(6).
shows the TEM micrographs of the Pd/C catalysts together with
the pertinent histograms. From the results in Figure 2 and 200 Pd/C(1)
Pd/C(2)
Table 1, it can be concluded that Pd NPs preserved their Pd/C(3)
H2 amount/µ mol

spherical shape even after the deposition on the carbon support, 150 Pd/C(4)
Pd/C(5)
while slight increases in the average diameter of Pd NPs were Pd/C(6)
observed when the palladium NPs were loaded onto the support. 100
This NPs size increase is consistent with previous results report-
ed for the Pd NPs synthesized by following similar exper-
50
imental conditions15,24 and could be due to a partial flattening
of the original spherical shape, which led to the observation of
apparent larger metal NPs. In addition, all the catalysts, apart 0
0 30 60 90 120 150 180
from Pd/C(6), showed a homogeneous distribution of the Pd
Time/min
nanoparticles on the support. The nitrogen isotherms obtained
for the inherent carbon support and the Pd/C(1)­Pd/C(6) Figure 3. Evolution of the H2 from FA dehydrogenation
showed Type I isotherms (Figure S2), which is characteristic of at 30 °C using Pd/C-based catalysts with different Pd
microporous materials according to the IUPAC classification.25 NPs size.
The result obtained from the porous characterization analysis
is summarized in Table S2. As expected, a slight decrease in the fixed times (Figure 3). Turnover Frequency (TOF, defined as the
specific surface area and micropore volume was observed com- amount of H2 produced per mol of Pd metal), together with the
pared to those of the original carbon support when palladium Pd dispersion (DTEM) for each catalyst is included in Table 2.
was loaded on its surface. The highest BET surface decrease The H2 production proceeded smoothly without induction
(ca. 13%) was observed for sample Pd/C(6), whose particle size period, and the catalytic activity was different for the Pd/C-
is largest among investigated, indicating that the decrease of based catalysts with different Pd NPs size. Among them,
pore volumes observed for the Pd/C catalysts originated from sample Pd/C(3) with average particle size of 3.9 nm showed
the blocking of a fraction of pores by the supported small NPs. the best catalytic performance, generating 183 ¯mol of H2 after
In order to assess the effect of the Pd NPs size in the FA 3 h of reaction. Samples Pd/C(5), Pd/C(4), and Pd/C(2), with
decomposition reaction, catalytic tests were performed at 30 °C average NPs size of 5.5, 4.2, and 3.6 nm, respectively, showed
for all the as-prepared Pd/C-based catalysts and the progress of similar H2 evolution profiles, although the H2 generated after
the reaction was monitored by quantifying the H2 output after 3 h was slightly higher in sample Pd/C(4) (158 ¯mol) than

Bull. Chem. Soc. Jpn. 2015, 88, 1500–1502 | doi:10.1246/bcsj.20150223 © 2015 The Chemical Society of Japan | 1501
Table 2. Dispersion (DTEM) and TOF (h¹1)
Pd/C DTEM TOF Pd/C DTEM TOF
catalyst /% /h¹1 catalyst /% /h¹1
Pd/C(1) 33.3 14.2 Pd/C(4) 21.4 22.0
Pd/C(2) 25.0 19.1 Pd/C(5) 16.4 19.9
Pd/C(3) 23.1 26.0 Pd/C(6) ® ®
those values obtained with Pd/C(5) and Pd/C(2) (142 and
134 ¯mol, respectively).
Generally, the catalytic activity increased with the decrease
of NP size, because smaller metal NPs possess a larger number
of exposed surface atoms as well as more low-coordinated metal
sites i.e. vertices and edges. Interestingly, the sample with the
smallest average NPs size (Pd/C(1)) displayed inferior catalytic
activity to those samples with larger Pd NPs sizes (samples
Pd/C(2)­Pd/C(5)), which is in sharp contrast to that expected
from traditional trends observed in other catalytic reactions. In
addition, samples Pd/C(6), where aggregates of Pd NPs were
detected, exhibited the lowest activity among all the catalysts
examined in this work; only 0.3 ¯mol of H2 were produced after
3 h under the same conditions. We believe that the Pd surface
structure, surface-adsorption property, and possible electronic
effects have all contributed to the H2 production from FA. It
is clear that the change of average Pd NPs size plays a crucial
role in optimizing such important factors and the best catalytic
activity was attained by Pd NP with average particle size of
3.9 nm. The TOF (defined as the amount of H2 produced per mol
of surface metal) of the best-performing catalyst (Pd/C(3)) at
30 °C was 112.5 h¹1, which is much higher than those values
reported in the literature for different Pd/C-based systems, such
as Ag@Pd/C (49 h¹1, 40 °C),2 Pd­Au/C (27 h¹1, 92 °C)26 or
commercial Pd/C (50 h¹1, 30 °C).19 The outstanding catalytic
performance of the Pd/C-based catalytic system studied in
this work is also demonstrated when its catalytic activity is
compared with those observed for different Pd-based catalysts
studied in our research group. In this regard, the best performing
Pd/C catalyst (sample Pd/C(3)) generated 183 ¯mol of H2 after
3 h of reaction, which is considerably higher than those values
previously achieved by basic resin with Pd NPs,11 amine-
functionalized MIL-125 with imbedded Pd NPs14 or Pd/H-
BETA15 (111.1, 48.1, and 99.1 ¯mol of H2, respectively) under
almost the same or identical experimental conditions.
In conclusion, the investigation of the catalysis over a Pd/C-
based system with different Pd NPs sizes proved that the FA
dehydrogenation reaction was dependent on the size of Pd NPs
and the highest catalytic activity was obtained by an optimum
Pd NP with average particle size of 3.9 nm. The features of
the catalytic system demonstrated in this work opens the new
pathway for the design of further nanostructured catalysts with
tailored particles size in the H2 production from FA dehydro-
genation. Further studies are currently ongoing to elucidate the
particle size effects.
The present work was partially supported by Grants-in-Aid
for Scientific Research (Nos. 26220911, 25289289, 26630409,
and 26620194) from the Japan Society for the Promotion of
Science (JSPS) and MEXT. We acknowledge Dr. Eiji Taguchi
and Prof. H. Yasuda at the Research Center for Ultra-High
1502 | Bull. Chem. Soc. Jpn. 2015, 88, 1500–1502 | doi:10.1246/bcsj.20150223
Voltage Electron Microscopy, Osaka University, for their assis-
tance with the TEM measurements. KM, YK, and HY thank
MEXT program “Elements Strategy Initiative to Form Core
Research Center”.
Supporting Information
Experimental details and characterization results obtained by
means of TEM and nitrogen adsorption­desorption isotherms.
This material is available electronically on J-STAGE.
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© 2015 The Chemical Society of Japan