Hierarchical 3-Dimensional Nickel-Iron Nanosheet Arrays On Carbon Fiber Paper As A Novel Electrode For Non-Enzymatic Glucose Sensing

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Cite this: DOI: 10.1039/c5nr06802a
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Hierarchical 3-dimensional nickeliron nanosheet

arrays on carbon ber paper as a novel electrode
for non-enzymatic glucose sensing
Palanisamy Kannan,a,c Thandavarayan Maiyalagan,b Enrico Marsili,*c Srabanti Ghosh,d
Joanna Niedziolka-Jnsson*a and Martin Jnsson-Niedziolka*a
Three-dimensional nickeliron (3-D/NiFe) nanostructures are exciting candidates for various applications because they produce more reaction-active sites than 1-D and 2-D nanostructured materials and
exhibit attractive optical, electrical and catalytic properties. In this work, freestanding 3-D/NiFe interconnected hierarchical nanosheets, hierarchical nanospheres, and porous nanospheres are directly grown
on a exible carbon ber paper (CFP) substrate by a single-step hydrothermal process. Among the nanostructures, 3-D/NiFe interconnected hierarchical nanosheets show excellent electrochemical properties
because of its high conductivity, large specic active surface area, and mesopores on its walls (vide infra).
The 3-D/NiFe hierarchical nanosheet array modied CFP substrate is further explored as a novel electrode for electrochemical non-enzymatic glucose sensor application. The 3-D/NiFe hierarchical
nanosheet arrays exhibit signicant catalytic activity towards the electrochemical oxidation of glucose, as
compared to the 3-D/NiFe hierarchical nanospheres, and porous nanospheres. The 3-D/NiFe hierarchical nanosheet arrays can access a large amount of glucose molecules on their surface (mesopore walls)
for an ecient electrocatalytic oxidation process. Moreover, 3-D/NiFe hierarchical nanosheet arrays
showed higher sensitivity (7.90 A M1 cm2) with wide linear 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 ampero-
Received 1st October 2015,

Accepted 26th October 2015
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
arrays are promising candidates for non-enzymatic glucose sensing.
1.
Introduction
Hierarchical nanostructures assembled by low-dimensional

building blocks including nanoparticles,1,2 nanorods,3,4 and
nanoplates5,6 often exhibit significant morphology and/or size
dependent properties.711 Considered as an important functional nanomaterial, nickeliron (NiFe) nanostructures
exhibit extraordinary electrical, catalytic, and magnetic
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
This journal is The Royal Society of Chemistry 2015
properties and have potential technological applications in

electromagnetic shielding, absorbing materials, catalysis, and
sensors.10,1214 Great attention has been focused on the
fabrication of NiFe micro-/nanostructures by using various
physical and chemical methods.10,1518 For instance, low
dimensional NiFe nanostructures including nanochains10
and nanorods15,19 have been synthesized by hydrothermal and
calcination methods. Three dimensional (3-D) NiFe nanostructures such as flowers,18 dendrites,20 and NiFe layered
double hydroxide films8 have also been reported. The 3-D Ni
Fe hierarchical nanostructures are preferable for various technological applications because they produce more reactionactive sites than 1-D and 2-D nanostructured materials and
exhibit attractive optical, electronic, magnetic, and catalytic
properties.7,18
The formation of hierarchical nanostructures is a selfassembly process, in which the ordered superstructures are
formed by small building blocks, i.e., 0-D nanoparticles,
1-dimensional nanorods or nanowires, and 2-D nanoflakes.2123 Moreover, it is well known that templates and/or
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shape modifiers and controllers are usually used to prepare

such hierarchical and complexed micro/nanostructures.24,25 In
addition, hierarchically nanostructured materials have also
been fabricated by physically constrained crystal growth with
the assistance of templates,26,27 which need to be completely
removed after synthesis. Template-free methods, including
solution phase reduction,28 chemical vapour deposition,29
thermal decomposition,30 electrochemical deposition,31 and
hydrothermal methods,32 were widely explored to synthesize
hierarchical nanostructured materials. Among them, the
hydrothermal method has received huge attention because of
its simplicity, and suitability for large-scale production, which
oers abundant control parameters and can be used for electrode modifications. Although dierent nanoarchitectures
have been successfully prepared by the hydrothermal method
(vide supra), we show that it is possible to directly grow 3-D
NiFe hierarchical nanosheet arrays, hierarchical nanospheres,
and porous nanospheres through the hydrothermal process on
a flexible substrate.
To accurately detect glucose is of immense scientific technological importance for clinical diagnostics in diabetes
control and analytical applications in biotechnology, environmental pollution control, and the food industry.3337 Since
enzyme based amperometric sensors have significant drawbacks in stability because of the intrinsic nature of
enzymes,3841 some methods have been developed to determine the glucose concentration without using them.4246
However, because of the surface poisoning from the adsorbed
intermediates and chloride, most of the non-enzymatic
sensors have distinct problems with low sensitivity and poor
selectivity.4749 Interferential eects from endogenous species
including ascorbic acid, uric acid, and dopamine cannot be
totally eliminated. As a result, a major consideration in practical non-enzymatic glucose sensing is focused on fabricating
high-performance devices using resourceful transition-metal
catalysts.5059 Now, diabetes mellitus is a public health
problem, and this metabolic disorder results from insulin
deficiency and hyperglycemia and is reflected by blood glucose
concentrations higher or lower than the normal range of
80120 mg dL1 (4.46.6 mM). Good glycemic control is the
cornerstone for proper diabetes management. Hence, it is pertinent to explore and develop non-enzymatic sensors with a
high sensitivity and a low detection limit to achieve convincing
clinical measurements.
In this work, three-dimensional nickeliron (3-D/NiFe)
interconnected hierarchical nanosheets, hierarchical nanospheres, and porous nanospheres are directly grown on flexible
carbon fiber paper (CFP) collectors by a single-step hydrothermal process. Our approach utilizes small amounts of Fe
metal as a doping agent for growing various morphologies. It
is supposed that the ratio of urea and metal salts can assist
the formation of hierarchical nanostructures, which is confirmed by the experimental results (vide infra). Further, we
study the enzyme-free electrochemical sensing of glucose as a
model system by using 3-D/NiFe nanostructures. Interestingly,
3-D/NiFe hierarchical nanosheet arrays resulted in a remark-
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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
FeCl24H2O and Ni(NO3)26H2O, NaOH were obtained from

Sigma-Aldrich Chemical Company. Urea (>99%) was received
from Merck Company. The nitric acid (HNO3) solution was
obtained from Aldrich Company. All other chemicals used in
this investigation were of analytical grade. All the solutions
were prepared with Millipore water (18 m) obtained from a
Millipore system. Argon (99.99%) was supplied by Multax
Company, Poland.
2.2.
Pre-treatment of CFP
The CFP substrate was washed repeatedly with 0.1 M HNO3

solution, and then subjected to 5 min ultra-sonication treatment in solvents such as acetone, ethanol and water, respectively. Next, the CFP substrate was rinsed with Millipore water,
followed by drying with a stream of argon gas. Finally, the
above pre-treated CFP substrate was used as collectors for preparing various morphologies of 3-D/NiFe nanostructures.
2.3. Synthesis of 3-D/NiFe hierarchical nanosheet array
nanostructures
The typical synthesis of 3-D/NiFe hierarchical nanosheet
arrays on carbon fiber paper can be explained as follows (optimized ratio as 2 : 1): 2 mM of FeCl24H2O and 1 mM of
Ni(NO3)26H2O were added to 20 mL of Millipore water, and
then stirred for 15 min to obtain a homogeneous solution.
Thereafter, 25 mM of urea was added quickly to the reaction
mixture, and then the reaction mixture was stirred again for
10 minutes; next, the above reaction mixture was transferred to
a Teflon-lined stainless steel autoclave vessel. Finally, the pretreated CFP substrate was placed in the reaction mixture, and
then continuously heated at 90 C for 6 h. After completion of
the reaction, the CFP was carefully removed from the reaction
vessel, and then thoroughly washed with Millipore water, followed by drying at 40 C for 812 h for further studies. The
other 3-D/NiFe nanostructures such as hierarchical nanospheres and porous nanospheres were obtained by repeating
the above procedure by changing the NiFe ratio to 1 : 1, and
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1 : 2, respectively. The mass loading for all samples of NiFe

nanostructures on the CFP substrate was calculated as
0.42 mg cm2. The 3-D/NiFe hierarchical nanostructures
grown over the CFP substrate can be used as a working
electrode for electrochemical non-enzymatic glucose sensor
experiments.
2.4.
Instrumentation
The morphologies of NiFe nanostructures were characterized

by field emission-scanning electron microscopy (FE-SEM JEOL
JSM-6700F). High-resolution transmission electron microscopy
(HRTEM) was carried out using a JEOL JEM 3010 instrument
with an acceleration voltage of 200 kV. The samples were
placed on a carbon-coated copper grid for morphology and
size analyses. The crystallographic information was obtained
by the powder X-ray diraction technique (XRD, Shimadzu
XRD-6000, Ni filtered CuK ( = 1.54 ) radiation operating at
30 kV/40 mA). The specific surface area of the nanostructures
was determined using the classic BET method (the Brunauer
EmmettTeller isotherm). The BET isotherm is the basis for
determining the extent of nitrogen adsorption on a given
surface. XPS analysis was performed on a VG ESCALAB MK II
with an Mg-K (1253.6 eV) achromatic X-ray source. Nitrogen
adsorption data were collected using a Quantachrome autosorb automated gas sorption system. The electrochemical
measurements were performed with a two compartment cell
with a CFP (exposed geometric area = 0.16 cm2), a Pt wire, and
Ag/AgCl (3 M KCl) as the working, auxiliary and reference
electrodes, respectively. Cyclic voltammograms were recorded
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using a computer controlled Autolab PGSTAT30 (Metrohm

Autolab) electrochemical analyser. All electrochemical experiments were carried out under an argon atmosphere.
3. Results and discussion

3.1 Synthesis and characterization of 3-D/NiFe hierarchical
nanostructures on CFP
The 3-D/NiFe hierarchical nanosheet arrays with high density
could be easily grown on CFP by a facile and one step hydrothermal route. The CFP was chosen here because of its fine
groove-like skeleton and high porosity, which helped to
increase the active surface area of nanostructures.6062 The
morphology of as-synthesized 3-D/NiFe hierarchical
nanosheet arrays/CFP was characterized by the FE-SEM technique, as shown in Fig. 1. It can be seen that the smart 3-D/
NiFe hierarchical nanosheet arrays were quite uniform,
upright, outward, densely packed and well aligned, hierarchical wall-like nanosheets grown on the surface of the CFP substrate and were ultrathin, which is favorable for the full
utilization of active materials (Fig. 1AD) for technological
applications. Such hierarchical wall-like nanosheets were composed of several individual nano-walls with the lengths of 57
m (Fig. 1A). Each wall appeared to grow from the same
origin/center of the CFP substrate. This indicates that the hierarchical wall-like 3-D/NiFe bimetallic nanosheets were successfully synthesized by the surfactant-free hydrothermal
reduction method. Interestingly, from the enlarged views
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.
(Fig. 1B and C), the nanosheets are interconnected with each

other to form a wall-like nanostructure, which might possess
better mechanical strength and durability. Further, these crystalline nanosheets well-retained their hierarchical nanosheet
morphology without any calcination/annealing process. As
shown in the high-magnification FE-SEM image (Fig. 1D), the
interconnected nanosheets form a highly open and mesoporous structure. Thus, a large specific (active) surface of 3-D/
NiFe hierarchical nanosheets is highly accessible by the electrolyte/analyte when it is employed as an electrode material for
electrochemical sensing.
It can be observed from Fig. 2 that in situ growth of hierarchical NiFe nanosheet arrays resulted in 3-D interconnected
and oriented nanoarchitectures, the length is more than
60 m (Fig. 2A), which can help overcome the problem of low
conductivity in conventional nanosheet arrays. Further, it has
already been pointed out that numerous 3-D/NiFe hierarchical nanosheets were grown uniformly on the CFP surface.
Importantly, wall-like 3-D/NiFe hierarchical nanosheet arrays
cannot be destroyed into discrete walls even under ultrasonication for a long period of time (20 min), indicating that
the complexed nanostructures are actually integrated and not
made up of loosely grown nano-walls through magnetic dipole
interactions. The 3-D/NiFe hierarchical nanosheet arrays were
synthesized using nickel nitrate and iron chloride as metal
sources and urea as the precipitant under hydrothermal conditions at 90 C (see the Experimental section). At this temperature, urea was decomposed into ammonia, the reason for
creating an alkaline environment, and carbonate, which served
as an intercalated anion. Now, Ni2+ and Fe3+ cations released
from the reaction mixture are simultaneously reduced to
metallic atoms, and then spontaneously formed 3-D/NiFe
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bimetallic nanoparticle nuclei. The formed nuclei (Ni cations)

occupy the center of the octahedral arrangement to grow into
a small sheet-like structure, with OH groups forming the vertices of octahedra; then the octahedra share edges to form
two-dimensional sheets, which rely on the hydrogen bonding
between the hydroxyl groups of adjacent sheets. Next, the
sheets can further grow three-dimensional network-like sheets
by self-assembly and then reconstruction as well as a further
growth step process. The grown hierarchical NiFe nanosheets
characteristics will potentially exhibit superior performance in
the electrochemical non-enzymatic glucose sensor (see below).
During the reaction, the urea not only acts as the stabilizing or
complexing regent but also plays a key role in the formation of
the hierarchical morphology. Because of the urea, the
nanosheets becomes flexible,63 and can be wrinkled and bent,
which will help nanosheets connect with each other and leads
to the formation of ordered arrays (Scheme 1-1).
The synergistic eect of Fe in the reaction mixture also
highly influences the formation of 3-D/NiFe hierarchical
nanosheet arrays under these conditions, i.e., Fe acted as a
nucleating agent inducing the reduction of Ni at this (90 C)
reaction temperature and assists the formation of such hierarchical 3-D/NiFe nanostructures. As a result, sheet-like NiFe
hierarchical nanostructures formed, and simultaneously, rapid
release of water molecules during the conversion process
resulted in the generation of mesopores over the surface of
nanosheets (Fig. 2B), which resulted in the growth (in situ) of
mesoporous 3-D/NiFe hierarchical nanosheets on the CFP
surface (Scheme 1-1). The distance between nanosheets was
250 nm and the film thickness was approximately 50100 nm
(Fig. 2B). To conclude, a yellowish-brown film was coated on
the surface of CFP (Fig. 2C, ii), indicating the successful
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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.
growth of 3-D/NiFe hierarchical nanosheet arrays. The masses

of all the NiFe nanostructures were determined by cutting the
CFP with grown samples into smaller pieces with the diameter
of 15 mm. Then CFP with grown samples and CFP were
weighed with a high-precision analytical balance (Sartorius,
max. weight 5100 mg, d = 0.001 mg) from which the exact
mass of the samples was then determined. The loading
density of the 3-D/NiFe active material is calculated to be
0.42 mg cm2 (vide supra).
Next we used the NiFe ratio of 1 : 1 for preparation; interestingly we observed that 3-D/NiFe has a hierarchical nanosphere morphology. The FE-SEM image obviously shows that
the as prepared 3-D/NiFe nanoparticles have a hierarchical
nanospheres (flower-like) morphology (Fig. 3A and B). The particles are uniform in size, 400 nm (Fig. 3B). The inset of
Fig. 3B shows that the hierarchical nanospheres with a flowerlike architecture are assembled by several interconnected tiny
sheet-like petals with a smooth surface and the thickness ca.
150 nm. Such hierarchical nanosphere architectures follow a
stepwise growth mechanism; at first, the generation of tiny
crystalline nanoparticle nuclei occurs in a reaction mixture
(vide infra) and subsequently, site-specific anisotropic growth
occurred due to a non-symmetrical assembly process

(Scheme 1-2). Then, the particles continue to grow as striking
hierarchical nanospheres (inset of Fig. 3B) with few nanoleaves sharing their originating center through coarsening,
also known as Ostwald ripening (Scheme 1-2).64,65
On the other hand, for the NiFe ratio of 1 : 2, the nanoparticle nuclei undergo random aggregation, followed by
growth of interconnected porous nanosphere particles (Fig. 3A
and B) due to nanoparticle-face attraction through van der
Waals forces (Scheme 1-3). Further, CO2 decomposed from
CO(NH2)2 can also act as soft template to induce the verity of
3-D/NiFe nanostructure morphologies, since no other surfactant, templates and emulsions were used in this work (vide
supra). As can be seen from the enlarged view (Fig. 3B and
inset), the porous nanospheres were uniform with a size of
300 nm (Fig. 3B). Importantly, no calcination treatment
process was required in this work for preparing hierarchical Ni
Fe nanostructures. It should be noted here that this procedure
establishes a universal protocol for the synthesis of 3-D/NiFe
hierarchical nanostructures without adopting dierent strategies, reaction conditions, or injection of foreign reagents
(vide supra). Changing the ratio of the stabilizer and the pre-
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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.
cursor or vice versa resulted in the formation of 3-D/NiFe

nanostructures of dierent morphologies (Fig. S1 in the ESI).
The HRTEM images (Fig. 4; image A) show that the nanostructure of NiFe grown on CFP is composed of a well-defined
nanosheet morphology with the length of 1 m; the NiFe
nanosheet oers abundant catalytic sites, which contributes to
the high electrocatalytic activity of the composite material. The
HRTEM image of the NiFe hierarchical nanosheet (image B)
shows mesoporous architectures. A large amount of well-distributed pores (on the surface) can be clearly seen, which is
well-consistent with the results observed from FESEM. The
hierarchical NiFe nanosheet together with the mesoporous
structure provides a large specific surface area, which was estimated by the BrunauerEmmettTeller (BET) method66 to be
337.9 m2 g1, much higher than those for hierarchical NiFe
nanospheres (211.3 m2 g1) and porous NiFe nanospheres
(136.4 m2 g1), respectively (Fig. S2). The improved surface
area allows for the rapid access of electrolyte ions, provides
abundant active sites for the electrocatalytic reactions, and
facilitates fast electron transport between the electrode
materials and the analytes. The close up view of the HRTEM
image (image C) clearly shows that the interplanar spacing of
0.14 nm corresponds to the (111) crystalline plane. Further, a
selected area electron diraction (SAED) pattern analysis of
hierarchical 3-D NiFe nanosheets showed several well-defined
rings with discrete dots in the diraction pattern illustrating
the crystalline nature of the sample (image D). This SAED
diraction pattern was well aligned with the XRD spectra,
suggesting the crystalline nature of hierarchical NiFe nanostructures. Next, the NiFe hierarchical nanospheres grown on
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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
which reveals that the Ni exist in the form of divalent. Next,

the high-resolution Fe 2p spectrum (Fig. S3B) shows two distinct peaks with binding energies of about 707.8 eV for
Fe 2p3/2 and 722.4 eV for Fe 2p1/2.76 The shakeup satellite peak
present at 860870 eV and 712720 eV is characteristic of
Ni2+ and Fe3+ ions, respectively, in hierarchical NiFe nanostructures. It also shows that the synthesized NiFe nanostructures contain both Fe3+ and Fe2+ ions, but it is obvious
that the amount of Fe3+ is higher than the amount of the Fe2+
ions. Generally, the Fe3+ and Fe2+ ions are found in its lattice
due to its inverse spinel structure. The XPS result confirms
that the Fe exists as Fe2+/Fe3+ and Ni as Ni2+ in the prepared
samples. The chemical composition (atomic percent) of the asprepared 3-D/NiFe hierarchical nanosheets was determined
by energy-dispersive X-ray (EDX) spectrometry as shown in
Fig. S3C. The only detectable elements are iron, nickel,
carbon, and oxygen. While the carbon and oxygen should arise
from the carbon fiber paper, and oxidation from the surface of
the samples, the corresponding elementary analysis reveals
that the atomic ratio (%) of Ni to Fe is 63.3 : 31.2, which is very
close to the initial set ratio of Fe : Ni = 2 : 1. The atomic ratios
(%) of other morphologies such as 3-D/NiFe hierarchical
nanospheres and 3-D/NiFe porous nanospheres were
47.7 : 46.9% and 32.4 : 63.1%, respectively, which is consistent
with their ratios 1 : 1 and 1 : 2. The above EDS results matched
with the XRD pattern analysis, which revealed the crystallinity
of the as-prepared hierarchical NiFe nanostructures.
3.2 Electrochemical behaviour of the 3-D/NiFe hierarchical
nanostructures on CFP electrode
To take advantage of its (3-D/NiFe hierarchical nanosheet
arrays) mesopores and large specific (active) surface area
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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.
(Fig. S2), we decided to study enzyme-free electrochemical

sensing of glucose as a model system. The electrocatalytic behavior of 3-D/NiFe hierarchical nanostructures towards
glucose oxidation was studied by cyclic voltammetry (CV) in
0.1 M NaOH solution. As shown in Fig. 6A, a couple of sensitive redox peaks for the 3-D/NiFe hierarchical nanosheet array
CFP electrode is observed at potentials of 0.43 and 0.58 V
(Fig. 6A, curve a), which could be mainly attributed to the
Ni(II)/Ni(III) redox couple in alkaline medium.77,78 It has been
known that when nickel is immersed in alkaline solutions,
spontaneous dissolution of the metal occurs followed by the
formation of Ni(OH)2 and finally NiOOH (eqn (1) and (2)).79
Ni 2OH ! NiO H2 O 2e or
Ni 2OH ! NiOH2 2e
NiO OH ! NiOOH e or
NiOH2 OH $ NiOOH H2 O e
Furthermore, the electrochemical signal of the 3-D/NiFe

hierarchical nanosheet array CFP electrode is much larger
than that of the bare CFP electrode (Fig. 6A, curve b),
suggesting that the former electrode is highly suitable for electrochemical detection. Next, on the injection of 0.25 mM
glucose, the sharp anodic peak current recorded from the
3-D/NiFe hierarchical nanosheet array CFP electrode is significantly higher than that from the same electrode without
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glucose. In addition, the behaviour of the cathodic peak

current is slightly increased due to the glucose oxidation
(Fig. 6A, curve c). These experimental results suggest the excellent electrocatalytic properties of 3-D/NiFe hierarchical
nanosheet arrays toward the oxidation of glucose. The oxidation of glucose at the 3-D/NiFe hierarchical nanosheet array
CFP electrode was electrocatalyzed by the NiO(OH)/Ni(OH)2
redox couple, according to the following reactions (eqn (3)
and (4)):80
NiOH2 OH $ NiOOH H2 O e
NiOOH glucose ! NiOH2 glucolactone
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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maximum at 0.65 V; at the same time, applied potentials of

0.60 and 0.70 V can also cause a notable enhancement of the
current response per addition of glucose. Importantly, the
smaller background current and lower noise observed at an
optimized applied potential due to the glucose oxidation
process was eciently completed at this potential, and thus
the applied potential of 0.65 V was selected for glucose detection. Fig. 7A shows the amperometric response of the 3-D/Ni
Fe hierarchical nanosheet array CFP electrode towards the successive stepwise additions of glucose to a homogeneously
stirred 0.1 M NaOH solution at a working potential of
0.65 V. A steep increase in current responses was obtained
after each addition of 0.5 M glucose solution, and a steadystate current was achieved within 2 s, indicating that the 3-D/
NiFe hierarchical nanosheet array CFP electrode exhibits
extremely sensitive and rapid response characteristics. This
might be due to the fact that 3-D interconnected mesopores in
the walls provide low resistance and promote electron transfer
to reduce the response time.67 The corresponding calibration
curve presented in Fig. 7B is linear over a concentration range
from 0.5 M to 10.5 M glucose with a correlation coecient
of 0.9981. The sensitivity of the hierarchical 3-D/NiFe
nanosheet array CFP electrode is calculated to be
7.90 A M1 cm2. It was further noted that the current
response increases accordingly when the concentration of
glucose continuously increases up to 200 M (Fig. 7C) with a
correlation coecient of 0.9902 (Fig. 7D), indicating that all
active sites of the 3-D/NiFe hierarchical nanosheet array CFP
electrode were highly sensitive at higher concentration of
glucose. Based on a signal-to-noise ratio of 3 (S/N = 3), the
detection limit (LOD) was 0.031 M calculated from the standard deviation of amperometric baseline currents, suggesting
the very good sensitivity of the 3-D/NiFe hierarchical
nanosheet array CFP electrode.
In order to evaluate the performance of the sensor, a comparison of 3-D/NiFe hierarchical nanosphere CFP and 3-D/
NiFe porous nanosphere CFP electrodes towards the nonenzymatic glucose sensor is shown in ESI Fig. S4A. It can be
observed that the sensitivities of 3-D/NiFe hierarchical nanosphere CFP (curve a) and 3-D/NiFe porous nanosphere
(curve b) CFP electrodes were 3.10, and 2.60 A M1 cm2,
respectively. We consider that the excellent electrocatalytic
activity of the 3-D/NiFe hierarchical nanosheet array CFP electrode should be attributed to the fact that the 3-D interconnected wall-like nanostructures with abundant mesopores
and holes expanding from the surface to the bottom not only
facilitate transport of glucose molecules through the electrolyte/electrode interface, but also allow them to come into
contact with more active surfaces (vide supra). Table S1 summarizes the non-enzymatic glucose detection performance
with dierent Ni- or Fe-based electrodes reported so far. It can
be concluded that our 3-D/NiFe hierarchical nanosheet array
CFP electrode possesses a higher sensitivity and a larger linear
range toward glucose detection. These superiorities were
attributed to the fact that the 3-D/NiFe hierarchical nanosheet
arrays combined the synergistic eects from Fe, which results
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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).
in high electrocatalytic activity and the electrical network

formed directly on the CFP surface. Moreover, well dispersed
NiFe nanosheets on the surface of CFP can favour the easy
access of glucose to nanosheets, which significantly enhanced
the electrochemical response towards glucose oxidation. We
recorded the amperometric responses of 0.5 M glucose (steps
a, b, g, k, l, and m), 250 M of ascorbic acid (AA, step c), dopamine (DA, step d), uric acid (UA, step e), acetaminophen (AP,
step f ), fructose (step h), galactose (step i), and lactose (step j)
in homogeneously stirred 0.1 M NaOH solution, as shown in
Fig. S4B. It was found that 3-D/NiFe hierarchical nanosheet
arrays provide remarkable responses only for glucose
oxidation, and there is no obvious amperometric current
response for interfering species as compared to glucose, agreeing well with the Ni based electrodes.53,83
In order to verify the reliability of the non-enzymatic
glucose sensor for routine analysis, the sensor was employed
to determine glucose in blood serum samples. A commercial
One-Touch Ultra glucometer (Johnson & Johnson Medical, Ltd)
was used as the standard tool to check the reliability in hospitals. In the current clinical practice, plasma rather than whole
blood was used to determine the concentration of glucose. The
levels of glucose in plasma are usually 1015% higher than
glucose in the whole blood. In other words, [glucose]blood =
[glucose]plasma/1.14.84 Through conversion, the results are
listed in Tables S2 and S3. It can be found that the values
of glucose in human whole blood with the proposed sensing

electrode compared favourably to results obtained from the
hospital. In general, the proposed method provided decreased
analysis volume and an inexpensive and portable detection
platform. More importantly, it has been shown to oer an
accurate determination of glucose in real samples without any
separation procedure.
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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(7.90 A M1 cm2) and the lowest detection limit (LOD) of

0.031 M (S/N = 3). Further, the 3-D/NiFe hierarchical
nanosheet array modified CFP electrode can be demonstrated
to have excellent selectivity towards the detection of glucose in
the presence of 500-fold excess of major important interferents. All these results indicate that 3-D/NiFe hierarchical
nanosheet arrays are a promising candidate for non-enzymatic
glucose sensing.
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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Hierarchical 3-Dimensional Nickel-Iron Nanosheet Arrays On Carbon Fiber Paper As A Novel Electrode For Non-Enzymatic Glucose Sensing

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Cite this: DOI: 10.1039/c5nr06802a