pubs.acs.org/ac
Materials Science and Engineering Program, The University of Texas at Austin, 204 East Dean Keeton Street, Austin, Texas 78712,
United States
Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warsaw, Poland
S Supporting Information
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Figure 1. High-resolution FE-SEM and TEM images of before (A and C) and after (B and D) loading of Pt nanoparticles into the surface walls of
WC NTs. A uniform dispersion of PtNPs (black dots) is clearly visible on the surface of WC NTs (D). The corresponding schematic representation
of PtNPs loaded on the surface of WC NTs (E).
0.5 and 1.0 m. The formation mechanism of the nanotubestructured porous WC very likely starts from the aggregation of
initially formed WC nanoparticles (nanospheres) in the AAM
membrane, which are involved in self-assembly process during
the course of nucleation reaction (bundles of tube-like
nanostructures due to strong intratube van der Waals binding
interactions). The steps involved in the formation are
schematically shown in Figure 1E (steps a and b). The
homogeneous aqueous solution of glucose and AMT were
placed into the porous AAM membrane, which allows
hydrothermal treatment at 180 C for 24 h (Figure 1E; step
a). During this treatment, initially carbonized tungsten
nanospheres were formed within the AAM membrane, which
are stabilized by the glucose molecules. The porous tube-like
nanostructures were then formed by the self-assembling of the
glucose stabilized nanospheres, probably through the charge
density match during evaporation of the solvent in a vacuum
oven.50 Finally, the WC NTs product was obtained through
carbonization treatment at 900 C for 4 h in H2/N2 ow
(Figure 1E; step b). BrunauerEmmettTeller (BET) surface
area measurement conrms the high porosity of the WC NTs
material. The nitrogen adsorption/desorption isotherms
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readily accessible to the inner and outer surface walls; (iii) the
WC NTs/PtNPs possesses a large active surface area (vide
supra); (iv) the ecient conductivity of WC (exhibits its
platinum-like42,65 behavior) and its robust adhesion to PtNPs
to facilitate electron conduction were well-manifested toward
the oxidation of OA. These results armed that the WC NTs/
PtNPs modied GC electrode has proved to be an excellent
electrocatalyst nanomaterial. Chollier-Brym et.al., reported57
that the catalytic activity of Pt is lower in H2SO4 at a pH value
<2.5 than in HClO4, though our WC NTs/PtNPs modied GC
electrode showed better catalytic activity in H2SO4 (Figure S4
in Supporting Information) as a result of the platinum-like65
behavior of WC NTs; it can also be highly supportive for
PtNPs in electrocatalytic process (vide supra). Further,
oxidation of OA was tested with dierent loading of Pt
nanoparticles (0.2, 0.3, 0.4, and 0.5 mg cm2) into the WC
nanotubes (Figure S5 in Supporting Information). We noticed
that for higher loading than 0.4 mg, there is no improvement in
overpotential toward the oxidation of OA, which is why this
loading was chosen for all experiments.
Amperometric Detection of OA. The next important
objective of the present investigation is to utilize the Pt
nanoparticle-based platform for amperometric sensing of OA at
low concentration levels under optimized conditions. Specically, for practical application of any sensor, it is desirable to use
constant potential amperometry, which is a method that can
evaluate the performance of the transducer. Figure 4A displays
the amperometric responses observed for sensing of OA in
nanomolar ranges at the WC NTs/PtNPs (Figure 4A: curve a)
and Pt/C (Figure 4A: curve b) modied electrodes at an
applied potential of 1.20 V. The addition of 5 nM, that is, 50 L
of 0.5 M OA into a homogeneously stirred cell with 5 mL 0.1
(iii)
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CONCLUSIONS
In this work, we presented the synthesis of tube-like
nanostructures of WC with a surface area of 339 m2/g,
followed by the accumulation of large amount of PtNPs on its
surface walls. To the best of our knowledge, this is the rst
report that describes the synthesis of this novel hybrid
nanomaterial (i.e., tube-like nanostructured WC), and it can
serve as an ideal support for anchoring PtNPs. This novel
PtNPs/WC NTs nanomaterial was explored as high-performance nanocatalysts toward electrochemical oxidation of OA.
The presented sensor method is simple and highly reproducible. The WC NTs/PtNPs modied GC electrode has shown
lower onset oxidation potential and enhanced catalytic response
observed than the other supports such as PtNPs/Graphene and
PtNPs/CNTs modied electrodes. Moreover, the WC NTs/
PtNPs modied electrode possessed OA with a wide
concentration range (0125 nM), and higher sensitivity (80
nA/nM) was achieved by the amperometry method. The WC
NTs supported PtNPs electrode showed an excellent sensitivity
for OA detection, with a detection limit (LOD) of 12 nM (S/N
= 3) and excellent reproducibility. The WC NTs/PtNPs
electrode can be demonstrated to have an excellent selectivity
toward electrochemical oxidation of OA in the presence of 200fold excess of major important interferents. Finally, the practical
application of WC NTs supported PtNPs nanomaterial has also
been demonstrated for the detection of OA in tomato fruit
sample, by the DPV method under optimized conditions. Our
ndings show that WC NTs supported PtNPs can be
developed as a high-performance and versatile electrocatalyst
for electrochemical sensor applications.
ASSOCIATED CONTENT
S Supporting Information
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AUTHOR INFORMATION
Corresponding Authors
Notes
ACKNOWLEDGMENTS
Palanisamy Kannan thanks the European Union FP7, under the
grant REGPOT-CT-2011-285949-NOBLESSE, for nancial
support.
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