RETRACTED ARTICLE: Carbon black hybrid material furnished monodisperse platinum nanoparticles as highly efficient and reusable electrocatalysts for formic acid electro-oxidation

Article abstract of DOI:10.1039/c6ra00232c

Monodisperse platinum nanoparticles (Pt NPs) furnished with a Vulcan Carbon-Activated Carbon (VC-AC) hybrid have been prepared in the presence of tripropylamine (TPrA) and used as novel catalysts (Pt NPs/TPrA@VC-AC) for formic acid oxidation (FAO) reactio

Full text of DOI:10.1039/c6ra00232c

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Carbon black hybrid material furnished monodisperse
Platinum nanoparticles as highly efficient and reusable
electrocatalysts for formic acid electro-oxidation
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
‡
‡
www.rsc.org/
Yunus Yıldız , Handan Pamuk , Özlem Karatepe, Zeynep Dasdelen, Fatih Sen*
Monodisperse platinum nanoparticles (Pt NPs), furnished by Vulcan Carbon-Activated Carbon (VC-AC) hybrid
have been prepared in the presence of tripropylamine (TPrA) and used as novel catalysts (Pt NPs/TPrA@VC-
AC) for formic acid oxidation (FAO) reactions at room temperature. The characteristics of the novel catalysts
have been characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), high resolution
transmission electron microscopy (HRTEM), cyclic voltammetry (CV) and chronoamperometry (CA). The X-ray
diffractogram of the all prepared electrocatalysts showed the typical face-centered cubic (FCC) structure.
Chronoamperometry and cylic voltammetry measurements showed a strong increase of performance of Pt
NPs/TPrA@VC, Pt NPs/TPrA@AC and Pt NPs/TPrA@VC-AC hybrid material electrocatalysts after formic acid
addition; but Pt NPs@VC-AC electrocatalyst showed the best performance compared to the Pt
NPs/TPrA@VC, Pt NPs/TPrA@AC.
this purpose, platinum has been widely used as electrocatalyst due
to its highest catalytic activity among the anode metal catalysts for
Introduction
Formic acid is a liquid at room temperature, which makes it to be
more convenient and less dangerous than gaseous hydrogen when
handled, stored, and transported. Direct formic acid fuel cells
electro-oxidation of small organic fuels and the cathode catalysts
9
-13
for oxygen reduction . However, the surface of Pt is usually
heavily poisoned by the strong adsorption of CO intermediates
during the oxidation of organic fuels, resulting in the lowering of
catalytic performance with platinum as an anode catalyst. Also, the
high cost and limited resources of this precious metal prevent the
(
DFAFCs), are considered to be one of the promising clean energy
sources with high energy conversion efficiency and low
1
-8
environmental pollution . Although DFAFCs offer an exciting
potential for use in future micro-electronic devices, more research
is needed in developing a better formic acid electrooxidation. For
1
4,15
commercialization of the DFAFCs
. In order to make the most
use of this precious metal and reduce the cost, Pt nanoparticles
(
NPs) are usually loaded on high surface area supporting
1
6,17
materials
. By the way, it is also well known that the
performance of a catalyst layer in a fuel cell is influenced by
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dispersivity and stability of NPs on the surface of support ethanol and mixed in a 1:1 ratio with Vulcan carbon (VC), activated
1
8
materials . Therefore, homogeneous distribution of NPs on the carbon (AC) and the mixture of VC and AC (VC-AC ) as supporting
surface of support materials is a prerequisite to obtain high materials by the help of ultrasonic tip sonicator.
1
9
performance of catalysts . In this context, it is essential to mention
some of the recent studies, which have been able to achieve well-
dispersed nanoparticles over the supporting materials such as
carbon black, carbon nanotubes, carbon nanospheres, and carbon
.
16-20
fiber nanocomposites
.
Herein,
a
facile synthesis of
monodisperse ultrafine platinum nanoparticles supported on
Vulcan XC-72 (VC), Activated Carbon (AC) and VC-AC hybrid, their
excellent electrocatalytic activity toward formic acid oxidation have
been reported. The synthesis relies on the usage of VC-AC hybrid
material as supporting agent and dimethyl ammine-borane (DMAB)
Fig.1. Schematic illustration of the synthesis process of Pt
NPs/TPrA@VC-AC in THF.
as the reducing agent. The synthesis process is schematically Results and discussion
presented in Fig. 1.
The monodisperse Pt NPs/TPrA@VC-AC, Pt NPs/TPrA@VC and Pt
NPs/TPrA@AC have been characterized by the use of XRD, TEM,
HRTEM and XPS techniques. Spectroscopies and applications of the
prepared catalysts were conducted by cyclic voltammetry (CV) and
chronoamperometry (CA) for formic acid oxidation (FOA) reaction.
The structure and morphology of the monodisperse Pt
NPs/TPrA@VC, Pt NPs/TPrA@AC and Pt NPs/TPrA@VC-AC were
first characterized by TEM as shown in Fig. S1, S2 and 2,
respectively. The monodisperse Pt NPs/TPrA@VC-AC (3.63 ± 0.39
nm) were uniformly distributed on the surface of VC-AC hybrid
material (Fig. 2) and the average particle size of all prepared
catalysts have been summarized in Table S1.
Material and methods
Chemicals and materials
PtCl (99 %) was purchased from Alfa, tetrahydrofuran (THF) (99.5
4
%
2 4
), formic acid and H SO were bought from Merck, DMAB,
tripropylamine (TPrA) were purchased from Sigma-Aldrich, Vulcan
and Activated Carbon were obtained from Cabot Europa Ltd. All
chemicals were used as received. De-ionized water was purified by
Millipore water purification system (18 MΩ) analytical grade. All
glassware and Teflon-coated magnetic stir bars were cleaned with
aqua regia, followed by washing with distilled water before drying
in an oven.
Preparation of Pt NPs/TPrA
Sonochemical double reduction method using tripropylamine (TPrA)
as a stabilizer ligand was applied to synthesized Pt(0)/TPrA. Briefly,
4
firstly, 0.25 mmoles of PtCl and TPrA were completely involved in
anhydrous tetrahydrofuran (about 10 mL). Then, 1.0 mmole DMAB
was added to diminish the amine stabilized platinum complex until
a brown color was observed in the solution, which indicated the
formation of platinum nanoparticle. All reactions were performed
in an inert atmosphere. Lastly, after centrifugation of the Pt(0)/TPrA
nanoparticles, they were washed several times with ethanol in
order to remove unreacted species and dried under a vacuum at
room temperature. The prepared Pt(0)/TPrA were dissolved in
Fig. 2. TEM image and particle size distributions for Pt
NPs/TPrA@VC-AC
2
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λ= the wavelength of X-ray used (1.54056 Ǻ)
The XRD patterns of all prepared catalysts were presented in Fig. 3 β= the full width half-maximum of respective diffraction peak (rad)
and it can be said that the Pt NPs/TPrA@VC-AC shows a broader Pt
θ= the angle at the position of peak maximum (rad)
(
220) peak relative to others, indicating that the Pt nanoparticles
have smaller sizes. The diffraction peak located at 2θ of 24.8 in the
XRD pattern corresponds to the (002) reflection of carbon black
support. Fig. 3 also displays the bulk analysis of the XRD peaks at
about 2θ = 39.80, 46.50, 67.50, 81.20 and 86.10 that are associated
with the (111), (200), (220), (311) and (222) planes crystallographic
plane, respectively in face-centered cubic (fcc) Pt crystallite. The 2θ
value of (111) diffraction peak shows a slight negative shift relative
to the bulk Pt (2θ= 40.12). This indicates the Pt-Pt interatomic
X-ray photoelectron spectroscopy (XPS) was performed to see the
effect of the surface oxidation state of platinum in monodisperse Pt
NPs/TPrA@VC-AC, Pt NPs/TPrA@VC, Pt NPs/TPrA@AC. For this
purpose, the Pt 4f region of spectrum was analyzed in all prepared
catalysts. The fittings of XPS peaks were performed by Gaussian-
Lorentzian method and the relative intensities of the species were
estimated by calculating the integral of each peak, after smoothing,
subtraction of the Shirley-shaped background. The deconvulation of
the high resolution Pt 4f region (Fig. 4) contains two pairs of
doublet. The ratio of the 4f7/2/4f5/2 signals for all prepared catalysts
21,22
distance
increases
in
the
Pt
NPs
.
2
4
was found to be 4/3, which agrees with the literature . In the
entire Pt spectra, the 4f7/2 signal at around 71.10 eV in all prepared
25
catalyst is assigned to zero-valent Pt . The other doublets of Pt are
2
6
occured in even higher binding energies (∼72.3 and 74.6 eV)
.
4
+
They are most likely caused by very small fraction of oxidized Pt
species possibly due to unreduced Pt precursor or PtOx species
formed during the catalyst exposure to the atmosphere (Table S2).
By integrating the relative peak areas, the percentage of Pt(0)
species in the prepared nanoparticles were calculated to be about
≥80 %, which suggested that a large portion of the surface atoms on
2
7,28
Pt nanoparticles were not oxidized
.
The cyclic voltammogram (CV) measurements have been performed
in the absence of formic acid as blank CVs (Fig. S3) of the
monodisperse Pt NPs/TPrA@AC (a), Pt NPs/TPrA@VC (b) and Pt
2 4
NPs/TPrA@VC-AC (c) catalysts in 0.1 M H SO solution (see the
Fig. 3. XRD patterns of the Pt NPs/TPrA@AC (a), Pt NPs/TPrA@VC
b) and Pt NPs/TPrA@VC-AC (c) catalysts.
Experimental section for details) and showed that the well-defined
oxygen and hydrogen adsorption/desorption regions in the
electrocatalyst reflect the electrochemical surface area (ECSA) of
the prepared catalysts. Generally, ECSA is the one of the most
important parameters in the catalyst to specify the catalytic
properties of nanomaterials for alcohol electro-oxidation, due to
(
The average crystallite particle size of all prepared catalysts were
2
3
found by using the Debye-Scherrer equation as shown in Table
S1
.
2
−1
ꢆꢇ
being surface-sensitive. The ECSA of the catalysts in m g could be
ꢀ
ꢁꢂꢃꢄ ꢅ
ꢈꢉꢊꢋꢌ
29-31
calculated from the following formula
.
where
QꢁꢍmCꢎ
ECSA ꢅ
PtꢁloadingꢁonꢁelectrodeꢁXꢁ0.21ꢁmC/cmꢏ
k= a coefficient (0.9)
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where
Q is the amount of charge exchanged during the
-2
electroadsorption of hydrogen atoms on Pt and 0.21 mC cm
Fig. 4. XPS spectra for Pt in the Pt NPs/TPrA@AC (a), Pt NPs/TPrA@VC (b) and Pt NPs/TPrA@VC-AC hybrid material (c).
represents the charge required to oxidize a monolayer of H on
species on the surface of Pt. As can be seen in Fig. 5, in the
2
platinum.
positive scan direction (forward scan), the main oxidation peak
of formic acid on the monodisperse Pt NPs/TPrA@VC-AC which
is located at potential about 0.52 V with oxidation peak current
The chemical surface areas (CSA) of the prepared catalyst was
calculated using XRD data as shown following equation,
2
density of 38.90 mA/cm , corresponds to the direct oxidation
32
assuming homogenously distributed and spherical particles
,
+
- 34
2
pathway of formic acid (HCOOH→CO +2H +2e ) . The oxidation
ꢁ ꢐ 10ꢑꢁ
current on the monodisperse Pt NPs/TPrA@VC-AC decreases
apparently at potential about 0.7 V because the Pt oxides are
formed at these potentials and they are not active to formic acid
oxidation. In the negative scan direction (backward scan), main
oxidation peak at potential about 0.29 V due to electrooxidation
of formic acid and removal of the incompletely oxidized
carbonaceous species formed during the positive scan direction,
which takes place on the clean and very active Pt NPs surface,
6
CSA ꢅ
ꢒ ꢐ ꢀ
where d is the mean Pt crystalline size in Ǻ (from the XRD
-2
results) and ρ is the density of Pt metal (21.4 g cm ). Comparing
these two areas (ECSA and CSA), it is possible to estimate the
3
3
catalyst utilization efficiency (%) using
,
ECSA
CSA
Utilizationꢁꢍ%ꢎ ꢅ
∗ 100
3
5–36
were observed
. In comparison with Pt NPs/TPrA@VC and Pt
NPs/TPrA@AC, the potential of the main peak for the
electrooxidation of formic acid on the Pt NPs/TPrA@VC-AC
electrocatalyst shifted about 150 mV in the positive direction
and the peak current density was increased by 2.72 times. On
the other hand, the onset potential which is related to the
breaking of C–H bonds and the subsequent removal of
intermediates by the oxidation with OHad supplied by Pt–OH
Table S3 summarizes all results of the CSA, ECSA, and % Pt utility
for the prepared catalyst and it can be concluded that Pt
NPs/TPrA@VC-AC has higher active surface areas, and %Pt utility
than the other prepared catalyst.
Fig. 5 compares the electrocatalytic performance of the Pt
NPs/TPrA@VC-AC, Pt NPs/TPrA@VC and Pt NPs/TPrA@AC for
3
7
FAO in 0.5 M H
2
SO
4
. There were two well-defined oxidation
sites or other sources for formic acid electrooxidation on the
Pt NPs/TPrA@VC-AC is comparable with other prepared
catalysts. The higher peak current density and comparable onset
potential of the formic acid electrooxidation on the Pt
peaks which appear in the forward and reverse potential scans
respectively. Formic acid oxidation during forward scan from 0.0
to 1.0 V is accompanied with the formation of oxygenated
4
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NPs/TPrA@VC-AC electrocatalyst as compared to the others
indicate that the Pt NPs/TPrA@VC-AC is kinetically more active
for formic acid electrooxidation. These results demonstrate that
the VC-AC hybrid, as a supporter of Pt NPs facilitates the
electron transfer kinetics for the electrode reactions. The high
electronic and ionic transport capacity of the VC-AC on the
electrode surface highly favors the electron transfer for the
electrooxidation of formic acid. On the other hand, the
enhanced performance of Pt NPs is attributed to the better mass
transport inside the VC-AC hybrid, well dispersion of ultrafine Pt
NPs on/in the VC-AC hybrid, higher utilization of PtNPs and
finally higher electrochemical activity of the single crystals of Pt
NPs/TPrA@VC-AC, Pt NPs/TPrA@VC, Pt NPs/TPrA@AC is a
necessary factor for formic acid electrooxidation.
To investigate the stability of all prepared catalysts,
chronoamperometric measurements were performed for formic
acid oxidation as shown in Fig. 6 that shows representative CA
2 4
curves obtained in 1 M formic acid + 0.5 M H SO at a potential
of 0.52 V (which is close to peak maxima seen in Fig. 6) for 1500
s. It can be seen that the oxidation currents decreased rapidly at
the early stage of the chronoamperometric measurements and
gradually became steady with time going on. The dramatic drop
of the current at the beginning of the chronoamperometric
measurements should be mainly due to two reasons. First, there
NPs, suggesting that Pt NPs/TPrA@VC-AC is
a
good
would be
a electric-double layer charging process at
electrocatalyst for formic acid electrooxidation. The enhanced
catalytic activity of the Pt NPs/TPrA@VC-AC for formic acid
oxidation was mainly a result of the higher Pt (0) ratio, higher
ECSA, % Pt utility, monodispersity of Pt NPs on VC-AC.
catalysts/electrolyte interface upon stepping the potential to a
new value, which usually gives a rapidly decaying current with
time at the beginning of potential step. Besides, a rapid
accumulation of strongly adsorbed species (e.g., CO,
hydrocarbons and oxygenates) should occur on electrode
3
8,39
surface upon initializing the oxidation of organic molecules
at the beginning of the potential step, which results in rapid
decrease in the numbers of the surface sites. In comparison with
the other prepared catalysts, the Pt NPs/TPrA@VC-AC exhibited
much lower degradation rate and maintained higher oxidation
current along the entire chronoamperometric measurements.
The enhanced stability of the Pt NPs/TPrA@VC-AC should be
attributed to the relatively monodispersity of Pt nanoparticles
on VC-AC hybrid.
Fig. 5. Cyclic voltammetry curves of formic acid oxidation on
monodisperse Pt NPs deposited on VC, AC, and VC-AC in 1 M
−
1
2 4
HCOOH + 0.5 M H SO solution. Scan rate 50 mV s .
Besides, it should be noted that, GC (Glassy carbon) did not
shows any characteristic response for formic acid
electrooxidation in the studied potential ranges. This indicates
that the GC is not capable of favoring the electrooxidation of
formic acid which signifies that the existence of Pt
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Fig. 6. Chronoamperometric curves of all prepared catalysts.
5 C. Rice, S. Ha, R. I. Masel, P. Waszczuk, A. Wieckowski and T.
The curves were recorded in solutions of (a) 0.5 M H
HCOOH at 0.52 V.
2
SO
4
+ 1 M
Barnard, J. Power Sources, 2002, 111, 83-89.
6
2
C. Rice, S. Ha, R. I. Masel and A. Wieckowski, J. Power Sources,
003, 115, 229-235.
Conclusions
7
Y. W. Rhee, S. Y. Ha and R. I. Masel, J. Power Sources, 2003,
17, 35-38.
1
In summary, facile, one pot, effective and practical synthetic
methods of monodisperse Pt NPs/TPrA@VC-AC, Pt
NPs/TPrA@VC and Pt NPs/TPrA@AC in THF were reported by
dimethyl ammine-boranes as reducing agent for the
electrooxidation of formic acid. Thanks to the ultrasmall sizes,
monodispersity and high % Pt(0) surface, the prepared Pt
8 Y. Zhu, S. Y. Ha and R. I. Masel, J. Power Sources, 2004, 130, 8-
14.
9
3
A. C. Chen and P. Holt-Hindle, Chem. Rev., 2010, 110, 3767-
804.
NPs/TPrA@VC-AC
exhibited
superior
eletrocatalytic
1
0 W. Chen, J. Kim, S. H. Sun and S. W. Chen, Phys. Chem. Chem.
performance for formic acid oxidation compared to the Pt
NPs/TPrA@VC and Pt NPs/TPrA@AC, therefore showing great
prospect as anode electrocatalysts for direct liquid fuel cells.
This facile, straightforward, and controllable method offers a
new pathway for the preparation of new electrode materials
Phys., 2006, 8, 2779-2786.
1
1 W. Chen, J. M. Kim, L. P. Xu, S. H. Sun and S. W. Chen, J. Phys.
Chem. C, 2007, 111, 13452-13459.
1
1
2 D. Chu and S. Gilman, J. Electrochem. Soc., 1996, 143, 1685-
(VC-AC hybrid) with high catalytical activities, which can find
690.
extensive applications in direct liquid fuel cells. The porous
structures of VC-AC electrode materials provide a large surface
area and distance for the electro-oxidation of formic acid.
13 W. Chen, J. M. Kim, S. H. Sun and S. W. Chen, J. Phys. Chem.
C, 2008, 112, 3891-3898.
Acknowledgements
14 W. D Lee, D. H. Lim, H. J. Chun and H. I. Lee, Int. J. Hydrogen
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This research was supported by Dumlupinar University Research
Funding Agency (2014-05 and 2015-35). The partial supports by
Science Academy and FABED are gratefully acknowledged.
1
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DOI: 10.1039/C6RA00232C
Graphical Abstract
Carbon black hybrid material furnished monodisperse Platinum nanoparticles as highly
efficient and reusable electrocatalysts for formic acid electro-oxidation
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Yunus Yıldız , Handan Pamuk , Özlem Karatepe, Zeynep Dasdelen and Fatih Sen*
Sen Research Group, Biochemistry Department, Faculty of Art and Science, Dumlupınar University, 43100 Kütahya, Turkey
*Corresponding author: fatih.sen@dpu.edu.tr
Tel:90 274 265 20 31 -37 02 Fax: 90 274 265 20 56
Carbon Black hybrid material supported monodisperse Pt NPs/TPr have been used as a novel
catalyst for formic acid electro-oxidation reduction