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Hierarchical 3-Dimensional Nickel-Iron Nanosheet Arrays On Carbon Fiber Paper As A Novel Electrode For Non-Enzymatic Glucose Sensing
Hierarchical 3-Dimensional Nickel-Iron Nanosheet Arrays On Carbon Fiber Paper As A Novel Electrode For Non-Enzymatic Glucose Sensing
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metry method. Further, the 3-D/NiFe hierarchical nanosheet array modied CFP electrode can be
demonstrated to have excellent selectivity towards the detection of glucose in the presence of 500-fold
DOI: 10.1039/c5nr06802a
excess of major important interferents. All these results indicate that 3-D/NiFe hierarchical nanosheet
www.rsc.org/nanoscale
1.
Introduction
a
Institute of Physical Chemistry, Polish Academy of Sciences, 44/52 ul. Kasprzaka,
01-224 Warsaw, Poland. E-mail: joaniek@ichf.edu.pl, martinj@ichf.edu.pl;
Fax: +48223433333; Tel: +4822333433130
b
School of Chemistry, University of East Anglia, Norwich NR4 7TJ, UK
c
Singapore Centre on Environmental Life Sciences Engineering (SCELSE), Nanyang
Technological University, 60 Nanyang Drive, SBS-01N-27, Singapore.
E-mail: emarsili@ntu.edu.sg; Fax: +65-6515-6751; Tel: +65-6592-7895
d
Department of Chemical, Biological and Macromolecular Sciences, S. N. Bose
National Centre for Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata-700098,
India
Electronic supplementary information (ESI) available. See DOI: 10.1039/
c5nr06802a
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able enhancement in the electrocatalytic activity of glucose oxidation, reusability, and stability because of its high
conductivity, large specific surface area and mesopores on its
walls. The 3-D/NiFe hierarchical nanospheres and porous
nanospheres were also tested under similar experimental conditions used for comparing the electrochemical activity. The
3-D/NiFe hierarchical nanosheet arrays showed higher sensitivity (7.90 A M1 cm2) with wide linear response of glucose
concentration ranging from 0.05 M to 0.2 mM, and the low
detection limit (LOD) of 0.031 M (S/N = 3) is achieved by the
amperometry method. These results show the potential of
these materials for use as electrodes for ultrasensitive electrochemical experiments. We anticipate that they can be used in
many dierent systems in the future.
2. Experimental section
2.1.
Materials
Pre-treatment of CFP
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2.4.
Instrumentation
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Fig. 1 FE-SEM images of interconnected hierarchical 3-D/NiFe nanosheets (A), and the corresponding dierent enlarged views (B, C), and close
up view of a single nanosheet array showing the interconnected nano wall block nanostructure (D).
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Fig. 2 FE-SEM images of extended views of interconnected 3-D hierarchical nanosheets (A), and view of mesopores in the nanosheets (B), and
photographs (C) of carbon ber paper before (i) and after (ii) growing the NiFe hierarchical nanosheet arrays.
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Scheme 1 Schematic representation of the formation of freestanding 3-D/NiFe interconnected hierarchical nanosheets (1), hierarchical nanospheres (2), and porous nanospheres (3) on a exible carbon ber paper (CFP) substrate.
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Fig. 3 FE-SEM images of hierarchical 3-D/NiFe nanospheres (A), porous 3-D/NiFe nanospheres (C) and the corresponding enlarged views (B, D),
and insets showing the close up view of hierarchical nanosphere (B) and porous nanosphere (D) morphologies.
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CFP were composed of ultrathin nanoflakelets with a dimension of 400 nm (image E), and close assemblies of NiFe
porous nanospheres (image F) with a size of 300 nm were
further confirmed by HRTEM analysis. The results obtained
from HRTEM were highly consistent with the FESEM analysis.
The phase structure and purity of the as-synthesized 3-D/
NiFe samples were examined by the XRD method. Fig. 5
shows the XRD pattern of all NiFe samples. It can be seen
from Fig. 5 that all of the diraction peaks can be indexed to
pure nanocrystalline structures. The XRD profile of the 3-D/Ni
Fe hierarchical nanosheet arrays (Fig. 5A), hierarchical nanospheres (Fig. 5B), and porous nanospheres (Fig. 5C) on the
CFP substrate shows that the peaks at 43.1, 53.3, 62.7, 76.4,
79.6, and 96.0 could be indexed as the (111), (200), (220),
(311), (222), and (400) crystalline planes of the fcc (face centered-cubic) Ni phase (JCPDS No. 04-0850), respectively.1,6769
The peak corresponding to the (111) plane is more intense
than the other planes. The ratio between the intensities of the
(200) and (111) diraction peaks is lower (0.51) than the usual
value (0.60), suggesting that the (111) plane is the predominant orientation. Interestingly the ratios of the relative peak
intensities of the high index planes (311) and (222) are higher
(0.62 versus 0.42) and (0.67 versus 0.55) than the standard
values (dotted box in Fig. 5A). This observation reveals that the
3-D/NiFe hierarchical nanosheets were more abundant in
high index facets than 3-D/NiFe hierarchical nanospheres
(Fig. 5B) and 3-D/NiFe porous nanospheres (Fig. 5C). The
absence of NiO peaks mainly at 37.2 and 44.3 corresponds to
the (111) and (220) planes, indicating that no oxide product
was observed in the samples. Furthermore, the diraction
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Fig. 4 High-resolution TEM images of hierarchical NiFe nanosheets with dierent magnications (AC), and the corresponding SAED pattern
(image D). Images E and F represent hierarchical NiFe nanospheres and porous NiFe nanospheres, respectively.
peaks at 35.4, 53.1 and 62.5 can be indexed as the (311), (511),
and (440) planes corresponding to the Fe component in all the
NiFe nanostructures.70 Their XRD patterns dier only in the
relative intensities of given crystalline planes. The intensity of
Fe peaks gets better (Fig. 5C) when the mole ratio 1 : 2 (NiFe)
is used for the synthesis of 3-D/NiFe porous nanospheres
rather than equal (Fig. 5B) or lower (Fig. 5A) mole ratios.
It has also been reported that the high concentration of the
Fe precursor (in the case of the 1 : 2 ratio) resulted in the formation of oxide phases,68 though in our synthetic protocol we
have not observed any oxide phases. Except for NiFe phases,
the small broad diraction peak observed at 26.5 in
Fig. 5(AC) corresponds to the (002) plane of the graphitic
carbon of the CFP substrate.71 No additional peaks apart from
the carbon fiber substrate were observed; this indicates that
high-purity 3-D/NiFe nanostructures were obtained during
the synthesis. The strong, sharp peaks and very low backgrounds reveal that the as-synthesized NiFe bimetallic nanoparticles had a high degree of crystallinity (vide supra). As we
discussed, Fe acted as a nucleating agent during the reaction
and assisted the formation of highly crystalline 3-D/NiFe
nanostructures.
X-ray photoelectron spectroscopy (XPS) is a powerful tool to
identify the elements states in bulk material.72 By the analysis
of binding energy (BE) values, we have confirmed the nature of
Ni and Fe metals in the 3-D/NiFe hierarchical nanostructures.
Core-level high-resolution XPS spectra of NiFe hierarchical
nanosheets exhibit two peaks present at 855.4 and 873.1 eV
with a spin-energy separation of 17.7 eV, corresponding to
Ni 2p3/2 and Ni 2p1/2, respectively (Fig. S3A).73 The binding
energy of the Ni 2p3/2 peaks is dierent from that in other
reports of NiO (853.7 eV), NiS (853.1 eV) and Ni (852.6 eV),74,75
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Fig. 5 XRD patterns of as-synthesized 3-D/NiFe hierarchical nanosheet (A), hierarchical NiFe nanosphere (B), and porous NiFe nanosphere (C)
morphologies.
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The significant increase of the anodic peak current contributes to the excellent electrocatalytic activity of Ni(OH)2 in the
3-D/NiFe hierarchical nanosheet arrays on glucose oxidation,
which is accompanied by the oxidation of Ni2+ to Ni3+, as in
eqn (3). In addition, because of the absorption of glucose and
the oxidized intermediates on the active sites in mesopores of
the 3-D/NiFe hierarchical nanosheet array based electrode,
the anodic peak potential shifts to a little positive direction.81
It is also ascribed to the diusion limitation of glucose at the
electrode surface;67 these results are consistent with the previous Ni based literature.67,80,81
Further, Fe acted as a synergistic catalyst to enhance the
electrocatalytic oxidation of glucose in the bimetallic NiFe
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Fig. 6 (A) CVs of the 3-D/NiFe hierarchical nanosheet array CFP electrode in 0.1 M NaOH solution with (a) and without (b) 0.25 mM glucose. The
CVs obtained for the bare CFP electrode in 0.1 M NaOH containing 0.25 mM glucose for comparison (c). (B) CVs of the 3-D/NiFe hierarchical
nanosheet array CFP electrode in a 0.1 M NaOH solution containing dierent concentrations of glucose. The scan rate of 50 mV s1 is used for the
above (A) and (B) experiments. (C) CVs of the 3-D/NiFe hierarchical nanosheet array CFP electrode in 0.25 mM glucose at various scan rates, and
the inset shows plots of peak currents versus the square root of the scan rate. (D) CVs of 3-D/NiFe hierarchical nanosheet array CFP (a), 3-D/NiFe
hierarchical nanosphere CFP (b), and 3-D/NiFe porous nanosphere CFP (c) electrodes in 0.1 M NaOH solution containing 0.25 mM glucose.
based nanoparticle system.1,2,8 Importantly, the increased concentration of Fe content in the bimetallic system has increased
the overall electrocatalytic reaction to some extent;1,2,8 however
in our case the morphology of NiFe nanostructures has also
played an important role. We further conducted chronoamperometric measurements to evaluate the catalytic rate constant (kcat); when the oxidation current is dominated by the
rate of the electrocatalytic reaction, the catalytic current (Icat)
can be written as eqn (5).
I cat =I L 1=2 kcat C0 t1=2
where Icat and IL are the currents in the presence and absence
of glucose, respectively; kcat is the catalytic rate constant
(M1 s1), C0 the bulk concentration (M) of glucose, and t the
elapsed time (s). Based on the slope of Icat/IL vs. t1/2, the kcat
value is calculated to be 1.80 103 M1 s1 taking the glucose
concentration C0 = 0.25 mM into account for the 3-D/NiFe
hierarchical nanosheet array CFP electrode, while the kcat
obtained on the bare CFP electrode is calculated to be 0.31
103 M1 s1. Fig. 6B displays the CVs of the 3-D/NiFe hierarchical nanosheet array CFP electrode in 0.1 M NaOH containing
dierent concentrations of glucose (from 0.05 to 0.5 mM) at a
scan rate of 50 mV s1. Upon successive additions of glucose, a
remarkable current and potential increase of the anodic peak
is obviously observed; this indicates that the 3-D/NiFe hierarchical nanosheet array CFP electrode has good sensitivity.
Fig. 6C shows the eect of the scan rate on glucose oxidation
at the 3-D/NiFe hierarchical nanosheet array CFP electrode in
0.1 M NaOH containing 0.25 mM glucose. It can be seen that
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the anodic peak shows a slightly positive shift, and the cathodic peak shifts negatively with the increase in scan rate. These
results indicate that the redox reaction of Ni(OH)2 on the
surface of carbon fiber is rapid and reversible. Moreover, the
anodic peak potential shifts positively, suggesting that there is
a kinetic limitation in the reaction of glucose oxidation.44 The
inset of Fig. 6C shows that both anodic and cathodic peak currents from the 3-D/NiFe hierarchical nanosheet array CFP
electrode linearly scale with the square root of the scan rate,
indicating that the redox reaction of Ni(OH)2 at the CFP
surface is a typical diusion-controlled electrochemical
process.82 To compare the electrochemical performance of the
3-D/NiFe hierarchical nanosheet array based CFP electrode,
CVs of the 3-D/NiFe hierarchical nanosphere CFP and 3-D/Ni
Fe porous nanosphere CFP electrodes were measured in 0.1 M
NaOH electrolyte containing 0.25 mM glucose at a scan rate of
50 mV s1, and the corresponding CV is shown in Fig. 6D. The
CV analysis shows three peaks at 0.57, 0.60, and 0.62 V for 3-D/
NiFe interconnected hierarchical nanosheets, NiFe nanospheres and porous NiFe nanospheres, respectively. The 3-D/
NiFe interconnected hierarchical nanosheets show the lowest
overpotential and the highest oxidation current, 310 A vs. 260
and 230 A for NiFe nanospheres and porous NiFe nanospheres, respectively. It can be seen that the 3-D/NiFe hierarchical nanosheet array CFP electrode (Fig. 6D, curve a)
showed enhanced electrocatalytic response towards the oxidation of glucose in contrast to the 3-D/NiFe hierarchical
nanosphere CFP (Fig. 6D, curve b), and 3-D/NiFe porous
nanosphere CFP (Fig. 6D, curve c) electrodes due to a large
specific (active) surface area, and the interconnected wall-like
configuration of nanosheets provided an ideal platform for
accessing a large amount of glucose molecules. Overall, the
observed higher electrocatalytic activity of 3-D/NiFe hierarchical nanosheet arrays can be explained as: (i) the nanostructure
of 3-D/NiFe hierarchical nanosheet arrays oers a large
specific (active) surface area; (ii) the interconnected wall-like
configuration and good electronic conductivity of 3-D/NiFe
nanosheets could support and provide reliable electrical connections towards the glucose molecules; (iii) their compatibility, i.e. 3-D/NiFe nanosheets can be directly grown on the
current collector (CFP), makes them self-supporting nanostructures, (iv) 3-D/NiFe hierarchical nanosheets as active
materials possess high electrochemical activity and contribute
considerably compared to the other morphologies.
3.3 Application of the 3-D/NiFe hierarchical nanosheet array
CFP electrode in non-enzymatic glucose sensing
The simple fabrication procedure makes the as-prepared electrode an eective platform for the amperometric determination of glucose. Considering that the applied potential can
strongly aect the amperometric response of biosensors, we
have systemically investigated the impact of applied potential
on the amperometric response at the hierarchical 3-D/NiFe
nanosheet array CFP electrode to glucose. The results indicate
that with the applied potential shifting from 0.60 to 0.70 V (in
0.05 V steps), the steady-state current increases and reaches a
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Fig. 7 Amperometric response of the 3-D/NiFe hierarchical nanosheet array CFP electrode at an applied potential of 0.65 V in 0.1 M NaOH with
the dropwise addition of 0.5 M glucose (A), and the corresponding calibration plot of the obtained current response vs. glucose concentration (B).
Typical amperometric response of the 3-D/NiFe hierarchical nanosheet array CFP electrode at 0.65 V with the successive additions of glucose up
to 200 M in 0.1 M NaOH (C) and the corresponding calibration plot of the obtained current response vs. glucose concentration (D).
4.
Conclusions
We demonstrated the direct growth of 3-D/NiFe interconnected hierarchical nanosheets, hierarchical nanospheres, and
porous nanospheres on a flexible CFP substrate by a singlestep hydrothermal process. Among the nanostructures, 3-D/
NiFe interconnected hierarchical nanosheets showed excellent electrochemical properties because of their high conductivity, large specific surface area and mesopores on their walls.
The 3-D/NiFe hierarchical nanosheet array modified CFP substrate was successfully explored as a novel electrode for electrochemical non-enzymatic glucose sensor application. The 3-D/
NiFe hierarchical nanosheet arrays exhibit significant
improvement in the electrochemical oxidation of glucose,
as compared to the 3-D/NiFe hierarchical nanospheres, and
porous nanospheres. Moreover, 3-D/NiFe hierarchical
nanosheet arrays possessed wide linear glucose concentration
ranging from 0.05 M to 200 M, higher sensitivity
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Acknowledgements
Palanisamy Kannan thanks the NanOtechnology Biomaterials
and aLternative Energy Source for ERA Integration [FP7REGPOT-CT-2011-285949-NOBLESSE] project for financial
support.
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