Download as pdf or txt
Download as pdf or txt
You are on page 1of 7

Applied Surface Science 408 (2017) 96–102

Contents lists available at ScienceDirect

Applied Surface Science


journal homepage: www.elsevier.com/locate/apsusc

Full Length Article

Amperometric glucose sensor based on the Ni(OH)2 /Al(OH)4 −


electrode obtained from a thin Ni3 Al foil
Magdalena Jarosz a,∗ , Robert P. Socha b , Paweł Jóźwik c , Grzegorz D. Sulka a
a
Department of Physical Chemistry and Electrochemistry, Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30060 Krakow, Poland
b
Jerzy Haber Institute of Catalysis and Surface Chemistry Polish Academy of Sciences, Niezapominajek 8, 30239 Krakow, Poland
c
Faculty of Advanced Technology and Chemistry, Military University of Technology, Kaliskiego 2, 00908 Warsaw, Poland

a r t i c l e i n f o a b s t r a c t

Article history: In this report, we present a facile and relatively fast method to roughen the surface of Ni3 Al–based inter-
Received 7 December 2016 metallic foil, and test it as an amperometric non-enzymatic glucose sensor. The alloy samples underwent
Received in revised form 8 February 2017 chemical etching in a H3 PO4 :CH3 COOH (HAc):HNO3 :H2 O (24:1:1:7 in volume) solution in order to achieve
Accepted 20 February 2017
a high surface area with more electroactive sites. The Ni(OH)2 /Al(OH)4 − electrode was fabricated using
Available online 22 February 2017
potential cycling technique in a highly concentrated alkaline solution. The electrodes were tested elec-
trochemically for oxidation of glucose. We have demonstrated that Ni(OH)2 /Al(OH)4 − electrodes exhibit
Keywords:
high sensitivity towards glucose detection (796 ␮AmM-1 cm-2 ) and short response time (3 s) upon suc-
Ni3 Al alloy
Chemical etching
cessive addition of glucose. Moreover, as for a non-nanometric material, prepared electrodes show a
Amperometric sensor relatively good linear correlation between current density and glucose concentration (0.025–0.45 mM)
Glucose sensor and limit of detection (47.6 ␮M). For more in-depth characterization of presented material, electrodes
were examined using scanning electron microscopy (SEM) with energy-dispersive spectroscopy (EDS),
X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS).
© 2017 Elsevier B.V. All rights reserved.

1. Introduction types of metals (e.g., Pt, Au, Ni, Cu) and binary alloys (e.g., Ni-Cu,
Pt-Pb, Ni-Al, Ni-Pd) [5,11–15], as well as transition metal oxides
Nowadays, one of the most common and problematic diseases and hydroxides (e.g., NiO, Ni(OH)2 , Cu(OH)2 ) [16–18] have been
affecting hundreds of millions of people is a diabetic mellitus [1]. tested. In particular, Ni-based materials, due to a very high elec-
Therefore, many studies have been focused on the fabrication of trocatalytic activity towards glucose oxidation and relatively low
fast responding and highly sensitive glucose sensors, not only for production costs, have been extensively exploited.
medical applications but also for biotechnology and food industry The mechanism of glucose oxidation on Ni was first reported
[2,3]. Currently, two different types of electrochemical glucose sen- by Fleischmann et al. in 1971 [19]. It is based on Ni2+ /Ni3+ redox
sors are developed, namely, enzymatic [4] and nonenzymatic [5,6]. couple in an alkaline solution. Up to now, different forms of Ni com-
Former are based on the various types of materials to which glu- pounds in a form of nanowires, nanoparticles, and microspheres
cose oxidase (GOx ) is immobilized [7]. Such sensors possess very were used for glucose oxidation [20–22]. Some of those materials
high sensitivity and selectivity, and low detection limit. However, were also attached to carbon-based nanomaterials, namely carbon
enzyme-immobilized electrodes are extremely sensitive towards nanotubes (CNTs) [21,23]. Although CNTs may improve detection
thermal and chemical conditions, such as pH, humidity, and tem- of glucose, fabrication of such sensors implies necessity of immobi-
perature [8,9], which make them impossible to apply commercially. lization of nanotubes onto conventional electrodes, such as glassy
Due to the aforementioned drawbacks, extensive efforts have been carbon electrode (GCE) [20,21]. The problem in this approach may
made in order to find an enzyme-free glucose sensor. The main be a proper adhesion between the electrode and active material, as
idea for such sensor, was to fabricate an electrode from electroac- well as higher costs and time consuming preparations.
tive material that would have an ability to oxidize glucose directly A lately developed solution to the problems mentioned above,
on the electrode surface [6,10]. As an electroactive material, various is the in situ synthesis of the electroactive Ni-based materials.
Research area involves different kinds of Ni-based alloys, such
as NiTi or Ni3 Al [18,25]. The latter having a unique mechanical
∗ Corresponding author. and physical properties, such as good mechanical strength, high
E-mail address: jarosz@chemia.uj.edu.pl (M. Jarosz). temperature resistance, good corrosion resistance in oxygen and

http://dx.doi.org/10.1016/j.apsusc.2017.02.188
0169-4332/© 2017 Elsevier B.V. All rights reserved.
M. Jarosz et al. / Applied Surface Science 408 (2017) 96–102 97

carbon enriched atmospheres and its catalytic activity [24,25] is a Table 1


EDS analyses of main components of the as-received Ni3 Al alloy and samples after
very promising material towards sensor production. That is why,
chemical etching for 2 h in H3 PO4 : HAc: HNO3 : H2 O (24:1:1:7).
in this work we propose an amperometric glucose sensor based
on Ni3 Al alloy. Alloy samples were first etched chemically in order Element % wt.
to enlarge surface area and enhance their electroactivity. Further- As-received Ni3 Al alloy Al 11.8 ± 0.2
more, as-prepared samples were used to fabricate a non-enzymatic Ni 87.2 ± 0.9
glucose sensor. Using a simple oxidation process in an alkaline solu- Ni3 Al after chemical Al 10.9 ± 0.2
etching Ni 82.8 ± 1.0
tion, an electroactive Ni(OH)2 /Al(OH)4 − film was formed, and such
O 3.8 ± 0.3
an electrode was used as a direct nonenzymatic glucose sensor. The
proposed sensor exhibits a relatively good sensitivity, fast response
speed, satisfying detection limit and linear range. 3 s. The present phase was identified by use of the JCPDS library
(PDF card No 650144).
The morphological observations of Ni3 Al-based foil surface
2. Experimental
before and after chemical etching were carried out using a
Quanta 3D FEG scanning electron microscope (SEM). The chemi-
2.1. Preparation of Ni3 Al alloy samples
cal composition analyses were performed with energy dispersive
spectrometry (EDS) using an EDAX Apollo X detector. Addition-
A microcrystalline Ni3 Al-based foil with a chemical composition
ally, in order to determine the surface roughening of the Ni3 Al foil
of Ni-22.1Al-0.26Zr-0.1B at.% produced by a multistage process of
after chemical etching, the analyses of intensity profiles of SEM sur-
heat treatment and cold rolling was used as a starting material.
face were performed by using Nikon NIS-Elements AR microscope
Detailed information about production technology of the foil was
imaging software.
described previously by Jozwik et. al [26]. Prior to chemical etching,
X-ray photoelectron spectroscopy (ESCA/XPS) measurements
Ni3 Al foil was polished using a 1000 grit SiC abrasive paper in order
on as-received, etched and oxidized samples were performed using
to obtain the same starting situation prior to etching of foils.
a system equipped with the hemispherical analyzer SES R4000
As-prepared samples were cut into coupons (1 × 0.5 cm) and
(Gammadata Scienta) with a Mg K␣ X-ray source (1253.6 eV,
degreased in acetone and ethanol, then dried in air. In order to opti-
200 W). The energy resolution of the system for an Ag 3d5/2 excita-
mize the etching procedure of Ni3 Al foil, eight different solutions
tion line was 0.9 eV. The analyzer was calibrated according to ISO
and different etching times were tested. The best results in terms of
15472:2010 standard. During the measurements, vacuum was kept
enlarged surface roughness of the alloy were observed for etching
at approximately 5 × 10−10 mbar. The samples were mounted in the
in a mixture of H3 PO4 : HAc: HNO3 : H2 O (24:1:1:7 in volume) for
dedicated holder. The analyzed surface area was about 3 mm2 . The
2 h at 30 ◦ C. Finally, the samples were rinsed with distilled water
electron binding energy (BE) scale of the acquired spectra was cal-
and dried in air.
ibrated for a maximum of C 1s core excitation at BE of 285 eV. The
spectra were processed in CasaXPS 2.3.12 program. In the spec-
2.2. Electrochemical detection of glucose tra, the background was approximated by a Shirley profile. The
spectra deconvolution into a minimum number of the components
For an electrochemical detection of glucose, the samples etched was done by application of the Voigt-type line shapes (70:30 Gaus-
for 2 h in H3 PO4 : HAc: HNO3 : H2 O (24:1:1:7) were chosen. Prior to sian/Lorentzian product). The chemical states were ascribed to the
the electrochemical tests, the samples were kept in a dessicator in deconvoluted components of the spectra according to the data
order to avoid any contamination or oxidation of alloy samples. found in the literature [27–29].
Electrochemical experiments were conducted using a Reference
3000 potentiostat (Gamry, USA) in a conventional three electrode 3. Results and discussion
configuration. As a working electrode, etched Ni3 Al samples were
used, whereas a Pt grid and silver chloride electrode (Ag/AgCl) were 3.1. Surface characterization of Ni3 Al alloy prior and after
used as a counter and reference electrodes, respectively. All of the chemical etching
measurements were conducted at room temperature (20 ± 2 ◦ C)
and the potentials were referenced against Ag/AgCl electrode. The investigated foil exhibits a single phase structure—an
In order to fabricate the Ni(OH)2 /Al(OH)4 − electrode, cyclic 
ordered secondary solution ␥ based on the intermetallic Ni3 Al
voltammetry measurements were conducted in a 6 M NaOH solu- phase (Fig. 1a) with a mean grain size of approximately 10 ␮m.
tion using a scan rate of 100 mV s−1 . The potential range and The EDS analyses (Table 1) showed that the composition of an alloy
number of cycles were set from 0.0 to 0.6 V and 50, respectively. consists mainly of Ni and Al. On the contrary, the surface of Ni3 Al
During the sensor testing, the cyclic voltammetry measure- foil after chemical etching showed a significant surface develop-
ments were performed in the same three-electrode configuration ment (Fig. 1d). A surface development was also confirmed by the
in a 0.1 M NaOH solution containing 5.5 mM glucose. The CVs were intensity profiles for each sample (Fig. 1b and e for as-received
registered within the potential range of −0.6–0.9 V at different and etched, respectively). The analysis of intensity profiles and 3D
scanning rates ranging from 10 to 400 mVs-1 . Chronoamperomet- images of surfaces proved that, the surface roughness of Ni3 Al alloy
ric measurements were performed in a 0.1 M NaOH solution at was significantly increased by chemical etching. As expected, the
a potential step of 0.5 V. Measurements were conducted for the analysis of chemical composition (Table 1) demonstrated existence
period of 900 s and every 50 s, 50 ␮l additions of glucose at the of nickel and aluminum as main alloy components. Moreover, small
concentration of 4.8 ␮M were injected in the solution. amounts of oxygen were found.
The distribution of chemical elements on the Ni3 Al alloy surface
2.3. Surface characterization of the alloy samples did not show clear chemical segregations of the main components
of the alloy (Fig. 2). The oxygen exists on the surface like a uniformly
At the initial stage, a phase composition analysis of Ni3 Al-based distributed thin layer.
foil was performed by X-ray diffraction using a Seifert 3003 diffrac- The XRD analysis of examined foil before chemical etching
tometer equipped with a monochromated Co K␣ radiation source showed a single Ni3 Al- ordered phase composition with existence
at operating parameters of 30 mA, 50 kV and a step size 0.02◦ per both fundamental and superlattice lines (Fig. 3a).
98 M. Jarosz et al. / Applied Surface Science 408 (2017) 96–102

Fig. 1. SEM microstructures of as-received (a–c) and etched (d–f) Ni3 Al-based alloys: (a, d) top views of the alloy surface, (b, e) top views of alloy surfaces along with the
intensity profiles (arrows indicate the direction of scanning), (c, f) 3D intensity profiles of examined structures. Etching was performed for 2 h in the H3 PO4 : HAc: HNO3 : H2 O
(24:1:1:7) solution.

Fig. 2. Distribution of the chemical elements on the surface of the Ni3 Al-based foil after chemical etching in the mixture of H3 PO4 :HAc: HNO3 :H2 O (24:1:1:7 in volume) for
2 h at 30 ◦ C.

The intensity of fundamental peak (200) can be attributed to superlattice lines (100), (110) and (210) suggest a decrease in struc-
a texture deformation due to the forming process of as-received ture ordering, what can be a consequence of top surface changes.
samples. After chemical etching, structural homogeneity and tex- More detailed information about the samples was obtained from
ture is preserved, though the intensity of characteristic peaks is XPS measurements. The survey spectra confirmed that both etch-
significantly decreased (Fig. 3b). The observed intensity changes of ing and electrochemical oxidation in the alkaline solution led to
M. Jarosz et al. / Applied Surface Science 408 (2017) 96–102 99

Fig. 3. XRD diffraction pattern of (a) the as-received Ni3 Al-based intermetallic alloy foil and (b) an alloy after chemical etching for 2 h in H3 PO4 : HAc: HNO3 : H2 O (24:1:1:7).

a decrease in the Al content in samples (Fig. S1, Supplementary sity significantly and gradually decreases. It can be attributed to the
information). fact that after oxidation in concentrated NaOH, Ni(OH)2 is formed
Further information was obtained from the specific spectra, on the surface and consequently the intensity of the Ni2+ -OH peak
namely Ni 2p (Fig. 4a), Al 2p (Fig. 4b) and O 1s (Fig. 4c). increases. Therefore, we can assume that both etching and oxida-
The O 1s spectra were deconvoluted into four component tion processes reduce the contribution of the metallic component
peaks: (A) O-metal contribution from metal oxides, (B) O H con- on the surface of the alloy. Moreover, the oxide component rep-
tribution from hydroxyl group, (C) O C component from organic resented by B spectrum component in Fig. 4b disappears when
carbon compounds (short aliphatic compounds) and (D) O C + H2 O the oxidized sample is considered. This also proves that nickel
component also from organic (aromatic or coupled) compounds hydroxide was successfully obtained on the surface of the alloy. The
(Fig. 4a). The assignation of peak components on a basis of elec- component D may be ascribed to the Ni2+ -O bond that comes from
tron binding energies is collected in Table S1 (Supplementary the salt, e.g., Al2 NiO4 . The intensity of this peak increases for the
information). The oxygen-metal bonds are observed at all surfaces etched and oxidized samples, which may be caused by the chemical
covered by nickel oxides and their intensities (surface concentra- reactions occurring on the surface of the alloy leading to a formation
tion) remain independent of the Ni3 Al alloy treatment. The most of the aluminum-nickel salt.
significant changes are observed for the O H peak. In comparison Finally, the Al 2p (partly overlapped with Ni 3p) spectra for
to the as-received and etched samples, the O H component for the as-received, etched and oxidized samples are shown in Fig. 4c.
the oxidized sample is significantly greater. It is due to the oxida- After deconvolution of the spectra, two doublet electronic states
tion/hydroxylation process occurring in 6 M NaOH and resulting are observed for all samples, i.e. (A) Al-Ni, and (B) Al3+ -O. The one
in formation of Ni(OH)2 and Al(OH)4 − on the surface of the alloy. at lower BE can be ascribed to metallic Al in the alloy. Its inten-
The process will be described later on. The components C and D, sity increases for the etched and oxidized samples, but the binding
ascribed to organic compounds, can be a result of using the etching energy is shifted slightly towards lower energies (from 71.66 to
mixture containing acetic acid. 71.16 eV). The latter represents the component ascribed to the pres-
The Ni 2p spectra can be deconvoluted into four doublets (fol- ence of Al2 O3 on the surface of the alloy. The intensity of this
lowed by respective shake-up satellites) related to the following component decreases for the etched and oxidized samples. In addi-
components: (A) Ni-Al, (B) Ni2+ -O (oxide component), (C) Ni2+ - tion, for the oxidized sample there is one more component that can
OH, and (D) Ni2+ -O (salt related component) (Fig. 4b). For the be assigned to Al3+ -OH type of bonding. Most likely, it represents
as-received sample, there is a clearly observed component related Al(OH)4 − ions that are formed due to oxidation of the alloy in con-
to nickel in the alloy, whereas after etching and oxidation its inten- centrated NaOH. However, it may also be described as a component

Fig. 4. XPS O 1s (a), Ni 2p (b) and Al 2p with Ni 3p (c) spectra of Ni3 Al alloy: as-received (blue line), etched for 2 h in H3 PO4 : HAc: HNO3 : H2 O (24:1:1:7) (green line) and
oxidized in 6 M NaOH (red line). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.).
100 M. Jarosz et al. / Applied Surface Science 408 (2017) 96–102

Fig. 5. Successive cyclic voltammograms (50 cycles) obtained at the Ni3 Al alloy electrode cycled between 0 and 0.45 V vs. Ag/AgCl in 6 M NaOH at a scan rate of 100 mV s−1
(for the clarity of the figure, only 1st, 5th, and then every tenth cycle are shown).

from Al2 NiO4 . Nonetheless, XPS measurements proved that after


chemical etching of Ni3 Al samples, metallic components of the alloy
are reduced. Moreover, oxidation of etched samples allows form-
ing nickel and aluminum hydroxides species on the surface of the
alloy.

3.2. Fabrication of the Ni(OH)2 /Al(OH)4 − electrode

The Ni(OH)2 /Al(OH)4 − electrode was fabricated by cyclic


voltammetry using the Ni3 Al alloy electrode in a concentrated alka-
line solution. Fig. 5 shows the voltammograms acquired in 6 M
NaOH at a scan rate of 100 mV s−1 for 50 cycles.
Cyclic voltammograms show two characteristic peaks visible at
the potentials of about 0.26 V and 0.18 V, respectively. They may be
ascribed to the redox couple of Ni2+ /Ni3+ , and the reaction occurring
in the system is as follows [19]:

Ni(OH)2 + OH − ↔ NiOOH + H2 O + e− (1)

Contrary to the previously reported studies [18,30], due to the


presence of hydroxides on the surface of etched samples, no peak
representing an irreversible oxidation of Ni to Ni(OH)2 in the alka-
line solution was observed, though during the first cycle, anodic
and cathodic peaks are slightly shifted towards positive potentials.
At the same time, hydrolysis of Al2 O3 and dissociation of Al(OH)3
occur at the surface of Ni3 Al alloy, accordingly to the reactions Fig. 6. (a) Cyclic voltammograms of the Ni(OH)2 /Al(OH)4 − electrode without an
represented below [30]: addition of glucose at a scan rate 10 mV s−1 (black line) and at different scan rates
(10–400 mV s−1 ) in 0.1 M NaOH containing 5.5 mM of glucose. (b) Linear dependence
Al2 O3 + 3H2 O ↔ 2Al(OH)3 (2) of the cathodic and anodic peak currents vs. the square root of the scan rate.

Al(OH)3 + OH ↔ −
Al(OH)−
4 (3)

In the as-received and etched Ni3 Al samples, Al2 O3 component NaOH solution without an addition of glucose and in the presence
was the most significant one (see Fig. 4c). It suggested that initially of 5.5 mM of glucose at different scan rates are shown in Fig. 6a. As
aluminum oxide was present on the sample surface and then it can be seen, in the absence of glucose no ameprometric response
underwent the reaction presented in Eq. (2). On the other hand, was observed. On the other hand, when glucose is added to the solu-
when samples were treated in the concentrated NaOH solution, tion, both cathodic and anodic peaks are observed. Moreover, for
Al(OH)−4 species appeared (Eq. (3)). According to Xu et al. [30], in an
both cathodic and anodic peaks a linear relationship between the
alkaline solution, the predominant Al species was Al(OH)− 4 which
peak current and the square root of the scan rate was observed. Lin-
was confirmed by XPS measurements (component C in Fig. 4c). earity was sustained for the scanning rates from 10 to 100 mVs-1 For
To sum up, the Ni(OH)2 /Al(OH)4 − system was successfully higher sweep rates (200 and 400 mVs-1 ), some deviations from lin-
obtained by oxidation of the Ni3 Al alloy in an alkaline solution using earity were observed. It may be assumed that at relatively low scan
a cyclic voltammetry method. rates, a diffusion-controlled charge transfer occurs. An enlarged
view of oxidation part of the cyclic voltammograms is presented
3.3. Electrocatalytic oxidation of glucose in Fig. S2 (Supporting information).
The oxidation of glucose on the Ni(OH)2 /Al(OH)4 − electrode
Electrocatalytic activity of the Ni(OH)2 /Al(OH)4 − electrode pre- occurs accordingly to the reaction below [18,31]:
pared electrochemically from the Ni3 Al alloy were tested towards
glucose oxidation. Cyclic voltammetry measurements in a 0.1 M Ni3+ + glucose → Ni2+ + gluconolactone (4)
M. Jarosz et al. / Applied Surface Science 408 (2017) 96–102 101

Table 2
Properties of non-enzymatic Ni-based electrodes used for glucose detection.

Electrode Sensitivity (␮AmM-1 cm-2) Linear range (mM) LOD (␮M) Response time (s) Reference
a
c-Ni(OH)2 HR 1569 0.002–3.8 0.6 10 [17]
Ni Np/SMWNTsb 1438 0.0001–1 0.5 3 [21]
Ni-CNT 1384.1 0.005–2 2 3 [32]
NiNWAsc 1043 0.0005–7 0.1 <10 [33]
Ni-SWCNTs 907 0.001–0.9 0.3 2 [34]
Ni(OH)2 /TiO2 192 0.03–14 8 <1 [18]
Ni/Al-LDH/CHTd 0.182 Up to 8.6 10 [35]
Ni(OH)2 /Al(OH)4 − 796 0.025–0.45 47.6 3 this work
a
Chemical bath deposited hollow Ni(OH)2 nanorod arrays.
b
Nickel nanoparticles loaded straightly in multi-wall carbon nanotubes.
c
Nickel nanowire arrays.
d
Ni/Al layered double hydroxide nanoflakes with chitosan.

Ni(OH)2 /Al(OH)4 − electrode is quite high, comparing to electrodes


based on NiTi alloys (Table 2). It is probably due to a higher surface
density of electroactive sites at the electrode, provided by Al(OH)4 −
species.

4. Conclusions

The Ni3 Al-based alloy was used to fabricate an amperomet-


ric glucose sensor. In order to obtain high surface roughness and
expose more electroactive sites the alloy was subjected to chem-
ical etching. The performed XPS measurements confirmed that
both etching and oxidation processes lead to the loss of Al com-
ponent. A simple one-step method based on potential cycling in
an alkaline solution was applied to fabricate the amperometric
Ni(OH)2 /Al(OH)4 − glucose sensor. The presence of hydroxides on
the alloy surface was also confirmed by XPS measurements. It was
demonstrated that the electrode showed good sensitivity towards
glucose detection with a relatively fast response time. A linear range
was not as high as for the nanosized materials, though such macro-
scopic Ni(OH)2 /Al(OH)4 − electrodes may be applied as a potential
non-enzymatic glucose sensor.

Acknowledgements

A financial support from the Polish National Centre for Research


and Development under grants No. 209 874 and 246 201 is
Fig. 7. (a) Amperometric response of the Ni(OH)2 /Al(OH)4 − electrode to differ- gratefully acknowledged. The study was also supported by the
ent concentrations of glucose in 0.1 M NaOH at 0.5 V vs. Ag/AgCl. (b) Calibration
curve of the response current vs. glucose concentration according to the chronoam-
Marian Smoluchowski Krakow Research Consortium “Matter-
perometric curve shown in A. Standard deviations were calculated for triplicate Energy-Future” Leading National Research Centre (KNOW). The
measurements. research was partially carried out with the equipment purchased
thanks to the financial support of the European Regional Devel-
opment Fund in the framework of the Polish Innovation Economy
When glucose diffuses to the surface of the electrode, its rapid
Operational Program (contract POIG.02.01.00-12-023/08).
oxidation by Ni3+ occurs. Afterwards, at the applied anodic poten-
tial Ni2+ ions are oxidized to Ni3+ as it was shown in Eq. (1).
Appendix A. Supplementary data

3.4. Chronoamperometric detection of glucose Supplementary data associated with this article can be found, in

the online version, at http://dx.doi.org/10.1016/j.apsusc.2017.02.
In order to assess the performance of the Ni(OH)2 /Al(OH)4 188.
electrode towards glucose sensing, chronoamperometric measure-
ments were performed. Fig. 7a shows the amperometric response
References
of the studied electrode to successive additions of glucose at the
applied potential of 0.5 V. [1] J.E. Shaw, R.A. Sicree, P.Z. Zimmet, Global estimates of the prevalence of
The Ni(OH)2 /Al(OH)4 − electrode produced a relatively fast cur- diabetes for 2010 and 2030, Diabetes Res. Clin. Pract. 87 (2010) 4–14.
rent response (∼3 s) towards successive additions of glucose. [2] J.D. Newman, A.P.F. Turner, Home blood glucose biosensors: a commercial
perspective, Biosens. Bioelectron. 20 (2005) 2435–2453.
Moreover, the corresponding calibration curve (Fig. 7b) exhibited [3] G.S. Wilson, R. Gifford, Biosensors for real-time in vivo measurements,
a linear range from 0.025 mM to 0.45 mM, and the sensitivity of Biosens. Bioelectron. 20 (2005) 2388–2403.
the electrode was 796 ␮AmM-1 cm-2 . The limit of detection (LOD) [4] H.T. Zhao, H.X. Ju, Multilayer membranes for glucose biosensing via
layer-by-layer assembly of multiwall carbon nanotubes and glucose oxidase,
was 47.6 ␮M at signal-to-noise (S/N) ratio of 3. As for the electrode Anal. Biochem. 350 (2006) 138–144.
based on non-nanosized material, the characteristics of the pro- [5] S. Park, T.D. Chung, H.C. Kim, Nonenzymatic glucose detection using
posed sensor are relatively good. Especially, the sensitivity of the mesoporous platinum, Anal. Chem. 75 (2003) 3046–3049.
102 M. Jarosz et al. / Applied Surface Science 408 (2017) 96–102

[6] S. Park, H. Boo, T.D. Chung, Electrochemical non-enzymatic glucose sensors, [22] S. Ci, T. Huang, Z. Wen, S. Cui, S. Mao, D.A. Steeber, et al., Nickel oxide hollow
Anal. Chim. Acta 556 (2006) 46–57. microsphere for non-enzyme glucose detection, Biosens. Bioelectron. 54
[7] S.K. Vashist, D. Zheng, K. Al-Rubeaan, J.H.T. Luong, F.S. Sheu, Technology (2014) 251–257.
behind commercial devices for blood glucose monitoring in diabetes [23] A. Walcarius, Electrocatalysis, sensors and biosensors in analytical chemistry
management: a review, Anal. Chim. Acta 703 (2011) 124–136. based on ordered mesoporous and macroporous carbon-modified electrodes,
[8] R. Wilson, A.P.F. Turner, Glucose oxidase: an ideal enzyme, Biosens. TrAC-Trends Anal Chem. 38 (2012) 79–97.
Bioelectron. 7 (1992) 165–185. [24] V.K. Sikka, S.C. Deevi, S. Viswanathan, R.W. Swindeman, M.L. Santella,
[9] C. Chen, Q. Xie, D. Yang, H. Xiao, Y. Fu, Y. Tan, et al., Recent advances in Advances in processing of Ni3 Al-based intermetallics and applications,
electrochemical glucose biosensors, RSC Adv. 3 (2013) 4473–4491. Intermetallics 8 (2000) 1329–1337.
[10] P. Si, Y. Huang, T. Wang, J. Ma, Nanomaterials for electrochemical [25] P. Jozwik, W. Polkowski, Z. Bojar, Applications of Ni3 Al based intermetallic
non-enzymatic glucose biosensors, RSC Adv. 3 (2013) 3487–3502. alloys −current stage and potential perspectives, Materials 8 (2015)
[11] Y. Zhang, L. Su, D. Manuzzi, H.V.E. de los Monteros, W. Jia, D. Huo, et al., 2537–2568.
Ultrasensitive and selective non-enzymatic glucose detection using copper [26] P. Jozwik, Z. Bojar, Analysis of grain size effect on tensile properties of Ni3 Al
nanowires, Biosens. Bioelectron. 31 (2012) 426–432. −based intermetallic strips, Arch. Metall. Mater. 52 (2007) 321–327.
[12] Y. Sun, H. Yang, X. Yu, H. Meng, X. Xu, A novel non-enzymatic amperometric [27] Handbook of X-ray Photoelectron Spectroscopy, in: J.F. Moulder, W.F. Stickle,
glucose sensor based on hollow Pt-Ni alloy nanotubes array electrode with P.E. Sobol, K. Bomben, J. Chastain (Eds.), 2nd ed., Perkin-Elmer Corporation
enhanced sensitivity, RSC Adv. 5 (2015) 70387–70394. (Physical Electronics), 1992.
[13] F. Miao, B. Tao, L. Sun, T. Liu, J. You, L. Wang, P.K. Chu, Amperometric glucose [28] Electron Spectroscopy Database; www.lasurface.com.
sensor based on 3D ordered nickel-palladium nanomaterial supported by [29] NIST X-ray Photoelectron Spectroscopy Database; http://srdata.nist.gov/xps/.
silicon MCP array, Sens. Actuators B 141 (2009) 338–342. [30] Z.P. Xu, G.X. Lu, Hydrothermal synthesis of layered double hydroxides (LDHs)
[14] X. Bo, J. Bai, L. Yang, L. Guo, The nanocomposite of PtPd from mixed MgO and Al2 O3 : LDH formation mechanism, Chem. Mater. 17
nanoparticles/onion-like mesoporous carbon vesicle for nonenzymatic (2005) 1055–1062.
amperometric sensing of glucose, Sens. Actuators B 157 (2011) 662–668. [31] G. Wang, X. Lu, T. Zhai, Y. Ling, H. Wang, Y. Tong, et al., Free-standing nickel
[15] P.F. Luo, T. Kuwana, Nickel-titanium alloy electrode as a sensitive and stable oxide nanoflake arrays: synthesis and application for high sensitive
LCEC detector for carbohydrates, Anal. Chem. 75 (2003) 3046–3049. non-enzymatic glucose sensors, Nanoscale 4 (2012) 3123–3127.
[16] M.M. Rahman, A.J.S. Ahammad, J.H. Jin, S.J. Ahn, J.J. Lee, A comprehensive [32] T. Choi, S.H. Kim, C.W. Lee, H. Kim, S.K. Choi, S.H. Kim, et al., Synthesis of
review of glucose biosensors based on nanpstructured metal-oxides, Sensors carbon nanotube-nickel nanocomposites using atomic layer deposition for
10 (2010) 4855–4886. high-performance non-enzymatic glucose sensing, Biosens. Bioelectron. 63
[17] J. Yang, M. Cho, Y. Lee, Synthesis of hierarchical Ni(OH)2 hollow nanorod via (2015) 325–330.
chemical bath deposition and its glucose sensing performance, Sens. [33] L.M. Lu, L. Zhang, F.L. Qu, H.X. Lu, X.B. Zhang, Z.S. Wu, et al., A nano-Ni based
Actuators B 222 (2016) 674–681. ultrasensitive nonenzymatic electrochemical sensor for glucose: enhancing
[18] A. Gao, X. Zhang, X. Peng, H. Wu, L. Bai, W. Jin, G. Wu, R. Hang, P.K. Chu, In situ sensitivity through a nanowire array strategy, Biosens. Bioelectron. 25 (2009)
synthesis of Ni(OH)2 /TiO2 composite film on NiTi alloy for non-enzymatic 218–223.
glucose sensing, Sens. Actuators B 232 (2016) 150–157. [34] N.Q. Dung, D. Patil, H. Jung, J. Kim, D. Kim, NiO-decorated single-walled
[19] M. Fleischmann, K. Korinek, D. Pletcher, The oxidation of organic compounds carbon nanotubes for high-performance nonenzymatic glucose sensing,
at nickel anode in alkaline solution, J. Electroanal. Chem. Interfacial Sensor. Actuators B 183 (2013) 381–387.
Electrochem. 31 (1971) 39–49. [35] H. Ai, X. Huang, Z. Zhu, J. Liu, Q. Chi, Y. Li, Z. Li, X. Ji, A novel glucose sensor
[20] Y. Mu, D. Jia, Y. He, Y. Miao, H.L. Wu, Nano nickel oxide modified based on monodispersed Ni/Al. layered double hydroxide and chitosan,
non-enzymatic glucose sensors with enhanced sensitivity through an Biosens. Bioelectron. 24 (2008) 1048–1052.
electrochemical process strategy at high potential, Biosens. Bioelectron. 26
(2011) 2948–2952.
[21] H. Nie, Z. Yao, X. Zhou, Z. Yang, S. Huang, Nonenzymatic electrochemical
detection of glucose using well-distributed nickel nanoparticles on straight
multi-walled carbon nanotubes, Biosens. Bioelectron. 30 (2011) 28–34.

You might also like