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Author's Accepted Manuscript: Biosensors and Bioelectronic
Author's Accepted Manuscript: Biosensors and Bioelectronic
Author's Accepted Manuscript: Biosensors and Bioelectronic
PII: S0956-5663(18)30103-9
DOI: https://doi.org/10.1016/j.bios.2018.02.016
Reference: BIOS10278
To appear in: Biosensors and Bioelectronic
Received date: 30 November 2017
Revised date: 25 January 2018
Accepted date: 4 February 2018
Cite this article as: Fatemeh Amiripour, Seyed Naser Azizi and Shahram
Ghasemi, Gold-copper bimetallic nanoparticles supported on nano P zeolite
modified carbon paste electrode as an efficient electrocatalyst and sensitive
sensor for determination of hydrazine, Biosensors and Bioelectronic,
https://doi.org/10.1016/j.bios.2018.02.016
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Gold-copper bimetallic nanoparticles supported on nano P zeolite modified
carbon paste electrode as an efficient electrocatalyst and sensitive sensor for
determination of hydrazine
In this report, a facile, efficient and low cost electrochemical sensor based bimetallic Au-
Cu nanoparticles supported on P nanozeolite modified carbon paste electrode (Au-Cu/NPZ/CPE)
was constructed and its efficiency for determination of hydrazine in trace level was studied. For
this purpose, agro waste material, stem sweep ash (SSA) was employed as the starting material
(silica source) for the synthesis of nano P zeolite (NPZ). After characterization of the synthesized
NPZ by analytical instruments (scanning electronic microscopy (SEM), transmission electron
microscopy (TEM), X-ray diffraction (XRD) and fourier transform infrared (FT-IR)),
construction of Au-Cu/NPZ/CPE was performed by three steps procedure involving preparation
of nano P zeolite modified carbon paste electrode (NPZ/CPE) and introducing Cu+2 ions into
nano zeolite structure by ion exchange and electrochemical reduction of Cu+2 ions upon applying
constant potential. This procedure is followed by partial replacement of Cu species by Au
species due to galvanic replacement reaction (GRR). The electrochemical properties of hydrazine
at the surface of Au-Cu/NPZ/CPE was evaluated using cyclic voltammetry (CV), amperometric
i-t response, and chronoamperometry methods in 0.1 M phosphate buffer solution (PBS). It was
found that the prepared sensor showed higher electrocatalytic activity at a relatively lower
potential compared to other modified electrodes including Au/NPZ/CPE, Cu/NPZ/CPE, Au-
Cu/CPE and etc. Moreover, the proposed electrochemical sensor presented the favorable
analytical properties for determination of hydrazine such as low detection limit (0.04 µM), rapid
response time (3 s), wide linear range (0.01–150 mM), and high sensitivity (99.53 µA mM−1)
that are related to the synergic effect of bimetallic of Au-Cu, porous structure and enough surface
area of NPZ. In addition, capability of Au-Cu/NPZ/CPE sensor was successfully tested in real
sample with good accuracy and precision.
1
Keywords: Au-Cu bimetallic, SSA, Galvanic replacement reaction, Sensor, Hydrazine.
1. Introduction
2
active components demonstrating promising high electrocatalytic activity towards the oxidation
of hydrazine )Dong et al., 2010). Nanozeolites as porous crystalline aluminosilicates materials
with open structures and dimensions less than 100 nm with higher surface area as well as better
accessibility to internal micropores than traditional zeolites comprise a promising class of new
support and present attractive materials in the electrode surface modification for designing new
electrochemical sensors. The driving force for widespread utilization of zeolites is the mobility
of cations in zeolite structure achieving unique ion-exchange and the catalytic properties of
zeolite. Among zeolites, P zeolite, as one of the oldest synthesized zeolites, possess high
exchange ability and adsorption capacity and is easily adapted to the needs of industry without
the use of anticoagulation agents )Behin., 2016(.
Recently, Ahmed et al. (2018) prepared bimetallic and three metallic zeolite-supported
catalysts in steam reforming of tar using simulated-toluene as model compound. Also, up to now,
zeolite-supported bimetallic electrodes such as Pt-Ru(HY) (Samant et al.,2004) and Ni(II)Co(II)
salen complexes encapsulated in mesoporous zeolite A (Wang et al., 2015) have been used in
methanol electrooxidation. Therefore, it seems that zeolite-supported bimetallic modified
electrodes can provide interesting electrochemical sensors and biosensors with favorable
analytical and electrochemical properties due to the high catalytic activity of bimetallic species
and porous architecture endowed by zeolites.
The present study presents a simple, economic, fast, selective and precise sensor with
remarkable electrocatalytic activity for the detection the trace amount of hydrazine. Previously,
we introduced for the first time a facile and effective cost value synthesis of nano P zeolite
(NPZ) from stem sweep ash (SSA) as silica source and prepared modified electrode based on Ni
doped NPZ to study the oxidation of methanol and formaldehyde (Azizi et al., 2016; Azizi et al.,
2014( . In the present article to make the process more cost effective, we persuaded to use agro
waste as a starting material in zeolite synthesis procedure and then, bimetallic Au-Cu
nanoparticles supported on P nanozeolite modified carbon paste electrode (Au-Cu/NPZ/CPE)
was prepared via a simple galvanic replacement technique for determination of hydrazine
(Tamasauskaite-Tamasiunaite et al., 2013a, 2013b, 2013c). To the best of our knowledge, there
is no report on P zeolite loaded with bimetallic Au-Cu as electrode material toward the detection
of hydrazine.
3
2. Experimental
The detailed information about the chemical and reagents, apparatus and procedures,
support preparation can be accessed in with in Supporting data Section S1 .Construction of the
sensor is achieved by immersion of nano P zeolite modified carbon paste electrode (NPZ/CPE)
in copper sulfate solution (0.5 M) for 10 min to enter Cu+2 into nanozeolite structure through the
diffusion of Cu2+ into the pores of zeolite during the exchange with Na+. The mechanism of ions
exchange was investigated and the following mechanism was suggested (Rolison and Bessel,
2000):
Cu 2 ( z ) 2E s Cu 2 (int) 2E ( z ) (1)
Where the descriptors z, s and int describe for zeolites, solution and zeolite-solution
interface, respectively. Also E+ is referred to electrolyte cation. The electrode surface was
washed with double distilled water several times to acquire surface without any adsorbed species
or occluded material. Then, by applying the constant potential (-0.17 V vs. Ag|AgCl|KCl (3M)),
the reduction of Cu+2 was carried out which leads to the formation Cu0 (Cu-NPZ/CPE). To create
Au -Cu alloy, Cu-NPZ/CPE was immersed into slowly stirring H2SO4 (0.5 M) solution
containing 5 mM of HAuCl4 C to perform galvanic replacement reaction (GRR) between
Cu species and Au+3 ions (Fig. S1). Finally, the prepared Au-Cu/NPZ/CPE was rinsed with
double distilled water. According to following GRR, the deposition of Au particles is occurred
on the surface of the electrode:
4
supporting data (Section S.2.1.1 and Fig. S2 A, B and C). To more investigate the structural
information, TEM images of synthesized zeolite are shown in Fig. 1A and 1B. They indicate the
synthesis of nanoparticles in the range of 30-70 nm.
5
Fig. 1. (A) and (B) TEM image of synthesized NPZ at different magnifications. FESEM images of (C)
NPZ/CPE, (D) Au-Cu/NPZ/CPE. EDS analysis of (E) NPZ/CPE, (F) Au-Cu/NPZ/CPE.
6
-5
The number of Cu moles is found to be 2.34 × 10 by substituting the charge related to
the first Cu stripping peak (QCu) and the Faraday constant (F) which is considered to be 96500 C
mol-1. Then, based on the ratio between atomic percentage of total Cu (Cu replaced with Au +
residual Cu) and Au which is 1.19%/1.15%, the number of Au mole at the electrode surface is
-5
obtained to be 2.2613 ×10 (according to the EDS). Finally, the amount of Au obtained from
these considerations is calculated to be 57.93 mg cm-2.
From GRR in Eq. (2), the reduction of Au needs three electrons per atom while the
oxidation of Cu creates two electrons per atom, so the amount of Au replaced on the electrode
surface is restricted to 2/3 of the initial Cu metallic layer.
Fig. 2. (A) 1st and upper cyclic voltammograms (up to 30 th) of Cu/NPZ/CPE in 0.5 M H2SO4 solution.
Cyclic voltammograms were measured in 0.1 M PBS (pH 7.4) (B) in the absence of hydrazine using: (a)
7
CPE and (b) Au-Cu/NPZ-CPE and in the presence of 9 mM hydrazine (C) using: (a) CPE, (b) Au-
Cu/CPE, (c) Cu/NPZ/CPE, (d) Au/NPZ/CPE and (E)Au-Cu/NPZ/CPE. Scan rate: 50 mV s-1.
In order to create the main sight about electrocatalytic property of the Au-Cu/NPZ/CPE
electrode, CV studies were performed on different electrodes in 0.1 M PBS (pH 7.4) as
supporting electrolyte at the scan rate of 50 mV s-1 and the results are summarized in supporting
data Section S.2.2.1 and Table S2. At CPE and in the absence of hydrazine, no oxidation peak
was detected (Fig. 2B-a) during the positive potential scan, whereas, the CV profile of the Au-
Cu/NPZ/CPE catalysts prepared by GRR shows an oxidation peak at 0.19 V and a reduction
peak emerges at -0.15 V (graph b) which is related to Au oxide formation and its corresponding
reduction (Gupta and Ganesan, 2015). It should be considered that due to overlapping the
oxidation of remain Cu and reduction of Cu oxides with Au oxidation and reduction peaks, a
broad peak was observed (Wael et al., 2007).
Moreover, the electrochemical surface area (ECSA) created on fabricated catalysts was
measured from the charge of the Au surface stripping peak (Q) in the cyclic voltammogram by
integrating the current vs. time under anodic peak. Therefore, by using the charge corresponding
to the Au surface oxide monolayer stripping (400 µC cm-2 (Angerstein-kozlowska et al., 1986)),
ESCA can be expressed according to Eq. (4)
ESCA (cm 2 ) Q(µC ) / 400(µC .cm 2 ) (4)
So, the value of ESCA is calculated to be 5.73 cm2 that suggests an acceptable surface area.
With addition of 9 mM hydrazine, the oxidation of hydrazine at the surface of Au-
Cu/NPZ/CPE produces an relatively high current density (5.00 mA cm -2) at the potential of 0.22
V (Fig. 2C-e) while no signals were observed at unmodified CPE (Fig. 2C-a).
At the surface of Au-Cu/CPE, addition of 9 mM hydrazine causes a small increase in
current which do not provide sensitivity for hydrazine monitoring (Fig. 2C-b). The current
density (ja) obtained at the bimetallic electrode modified with NPZ is 3 times further than the
bimetallic electrode without NPZ. Zeolite provides larger spaces to permit more Cu and Au
loading on it, further probably allows a fast mass transport of hydrazine during reaction and
causes better electrocatalytic effect. The high surface area of NPZ can well disperse the
bimetallic Au-Cu species and avoid the aggregation of them. At this condition, bimetallic Au-Cu
catalysts will have high surface area and they provide more access to them. Hence, the charge
8
transfer of electron from hydrazine to catalyst is facilitated so the oxidation of hydrazine requires
low positive over potentials. Interestingly, when NPZ exists in electrode structure, the oxidation
of hydrazine requires low positive over potentials (100 mV less positive potential than that
observed at Au-Cu/CPE).
Fig. 2C-c and d show the comparison of electrocatalytic behaviors of hydrazine at the
surfaces of Cu-NPZ/CPE and Au-NPZ/CPE with Au-Cu/NPZ/CPE. In the presence of 9 mM
hydrazine, Au-Cu/NPZ/CPE generates the highest current response (Fig. 2C-e) so that its current
densities is 2.54 and 2.28 times greater than that obtained at the Cu-NPZ/CPE and Au-NPZ/CPE
(Fig. 2C-c and d, respectively). Moreover, the oxidation of hydrazine at the surface of Au-
NPZ/CPE and Cu-NPZ/CPE (especially Cu-NPZ/CPE) occurred at a relatively higher potential
(200 mV more positive potentials for Cu/NPZ/CPE than that Au-Cu/NPZ/CPE). These results
show the synergic effect of bimetallic alloy compared to single metals for hydrazine oxidation.
9
Fig. 3. Cyclic voltammograms of the Au-Cu/NPZ/CPE in the presence of hydrazine in 0.1 M PBS (A)
for electrocatalytic oxidation of hydrazine with different concentrations of hydrazine: (a) 0.0, (b) 2, (c) 3,
(d) 5,(e) 7 (f) 9, (g) 13 and (h) 15 mM, scan rate: 50 mV S-1, Inset: Calibration curves of hydrazine, error
bars represent the standard deviations from the mean of three replicates. (B) at different scan rates: (a)
0.005, (b) 0.010, (c) 0.015, (d) 0.025, (e) 0.04, (f) 0.08, (g) 0.1, (h) 0.15, (i) 0.15, (j) 0.2, (k) 0.25 (l) 0.3,
(m) 0.35, (n) 0.4, (o) 0.45, (p) 0.5 and (q) 0.6 V s−1, C hydrazine: 5mM.
It should be mentioned that, some fluctuations appear in peaks at low scan rates probably due to
N2 bubbles evolution at active sites which consequently changes the conditions of catalytic
reaction (Sun et al., 2016.). Simultaneously, oxidation potentials shift to positive direction as
expected for an irreversible oxidation process. Also, a linear relationship between Epa nd log ν
(Epa=61.48 log υ+177.69) wi h correl ion coefficien (R²) of 0.9981 can be observed
(Supporting data Section S.2.2.2 and Fig. S3B).
1/2
Based on the results ob ined from T fel nd I vs. υ plots (Supporting data
Section S.2.2.2, Fig. S3C and S3D), the following mechanism which involves one electron
10
transfer followed by a fast three electrons transfer process can be proposed. In other words for
the oxidation of hydrazine at Au-Cu/NPZ/CPE, the first step (Eq. (5)) is the rate determining step
which is in consistence with the literature report (Hosseini et al., 2013; Liu et al., 2014).
N 2 H 4 H 2O N 2 H 4 e H 3O (Slow) (5)
N 2 H 3 3H 2O N 2 3e 3H 3O (Fast) (6)
11
selectivity performance of the designed sensor, the influence of interfering agents especially
those compounds merged together with hydrazine during the industrial process was also probed
by amperometric techniques. The detailed information containing the condition and results of
selectivity experiment are reported in supporting data Section S.2.2.3 and Fig S4.
Fig. 4. (A) Current–time response of the electrochemical sensor for successive addition of hydrazine at
applied potential of 0.2 V vs. Ag|AgCl |KCl (3 M) in 0.1 M PBS (pH 7.4). (Inset: amplification of part
with low hydrazine concentrations). (B) and (C) calibration curves of steady-state current vs. the
concentration of hydrazine in 0.1 M PBS (pH 7.4). Error bars represent the standard deviations from the
mean of three replicates.
12
Table 1. Comparison of the linear range, detection limit, response time of Au-Cu/NPZ/CPE with other
electrochemical sensors and biosensors
13
3.2.5. Reproducibility, repeatability and stability of the proposed sensor
The fabrication reproducibility and repeatability of Au-Cu/NPZ/CPE were explored using
analysis of the solution containing 5 mM of hydrazine. A series of repetitive CV measurements
of freshly prepared five electrodes showed the relative standard deviation (RSD %) values of
3.8% indicating the excellent reproducibility. The repeatability test during the detection of
hydrazine for five successive runs in the same solution gave a RSD of 4.7%. Also, the working
stability of offered senor was evaluated by monitoring the changes in the catalytic currents
during potential cycling between -0.5 to 0.75 V for 30 min. After continuously testing in 0.1 M
PBS containing 13 mM hydrazine, the currents maintained 92.33% of their initial values for
hydrazine, resulting in acceptable operational stability. In addition, upon the storage of the
modified electrode in ambient conditions for five weeks, the signal current of 13 mM of
hydrazine in PBS solution at Au-Cu/NPZ/CPE retains 97.14% of its original response,
suggesting negligible sensitivity decline and superior long term stability of fabricated sensor.
3.2.6. Application
To demonstrate the feasibility of fabricated sensor in real analysis, amperometric
experiments were carried out with different water samples by using a standard addition method.
For this aim, three water samples from different sources were collected. It should be noted that,
the original concentrations of hydrazine in the samples were found to be free of it, hence the
samples were spiked with known concentrations of hydrazine. Real test was performed under the
same experimental condition with spiking by three different concentrations of hydrazine for
individual sample and repeated for three times. The results with details are presented in in
supporting data (Section S.2.2.5 and Table. S3). As it is obvious, the percentages of recoveries were
found between 96–103.5% and the %RSD (n=3) was below 6.0%. The prepared sensor presents the
acceptable relative standard deviations, satisfactory recoveries with good precision and practical
applicability for determination of hydrazine in real samples.
4. Conclusions
In conclusion, Au-Cu/NPZ/CPE sensor has been designed as an efficient sensor for
hydrazine detection at low concentrations. The sensor was fabricated via simple procedure
including ion exchange method followed by partial GRR method. The results proved that the
14
current developed sensor exhibit better or comparable sensing performance in terms of High
current density (5.00 mA Cm-2), wide linear range (0.01-150 µM), fast response time (3 s), high
sensitivity (99.53 µA mM−1) and good selectivity than several previously reported hydrazine
sensors. Large surface area and porosity architecture endowed by zeolite play an essential role in
enhancing the hydrazine diffusion onto the active sites of Au/Cu, promoting the sensing
performance which leads to achieve favorable analytical and electrochemical properties. In
addition, the use of SSA for the synthesis of NPZ as starting material suggests economic feature
of proposed sensor. The idea for the insertion of Au-Cu bimetallic catalyst into NPZ provides a
new insight for modification of other porous materials such as metal organic frameworks,
mesoporous carbons and etc. to improve their applicability and performance in the preparation of
efficient sensors and biosensors for practical applications in real samples.
15
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Graphical Abstract
18
HighLightS:
P nano zeolite has been synthesized as an efficient support for
preparation of new bimetallic Au-Cu sensor.
Bimetallic sensor was fabricated via a simple galvanic replacement
technique.
Au-Cu/NPZ/CPE shows superior electrocatalytic activity toward
hydrazine oxidation.
Au-Cu/NPZ/CPE has excellent electroanalytical performance
toward the hydrazine detection.
19