Highly sensitive amperometric hydrazine sensor based on novel Sb2S3-CuTβPc composite modified platinum disk electrode

Article abstract of DOI:10.1246/cl.180524

A novel composite material composed of inorganic semiconductor antimony sulphide (Sb₂S₃) and organic semiconductor copper tetra-β-(4-carboxyphenoxy) phthalocyanine (CuTβPc) was prepared by a simple solution deposition process. The crystallite structure and properties of Sb₂S₃-CuTβPc composites were analyzed by XRD, SEM, FTIR and UVvis. The electrochemical behavior of the sensor was investigated using cyclic voltammetry (CV) and amperometry. For the development of a potential chemical sensor, Sb₂S₃-CuTβPc composites were deposited on flat platinum disk electrodes to give sensors that responded quickly and selectively to hydrazine in phosphate buffer phase. The hydrazine sensor showed a linear detection range from 10 nM to 0.5 ˉM and detection limit of 0.9 nM at a signal-to-noise ratio of 3. Thus this novel composite may be potentially applied in the field of catalysis and environment.

Full text of DOI:10.1246/cl.180524

Advance Publication Cover Page
Highly Sensitive Amperometric Hydrazine Sensor Based on Novel Sb2S3-CuTβPc
Composites Modified Platinum Disk Electrode
Wenlong Hou, Huiyun Guo, Jianping Zhang, Jing Xu, Lu Liu, Gengwen Yin,
Jingkai Yang, Bo Liang,* and Haiquan Zhang*
Advance Publication on the web July 20, 2018
doi:10.1246/cl.180524
© 2018 The Chemical Society of Japan
Advance Publication is a service for online publication of manuscripts prior to releasing fully edited, printed versions. Entire
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Publication manuscripts.

1
Highly Sensitive Amperometric Hydrazine Sensor Based on Novel Sb2S3-CuTβPc Composites
Modified Platinum Disk Electrode
Wenlong Hou,1,2 Huiyun Guo, 1 Jianping Zhang,1,2 Jing Xu,1 Lu Liu,1,2 Gengwen Yin,1,2 Jingkai Yang, 1 Bo Liang,*1 Haiquan Zhang,*1
1 State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, PR China
2 Hebei Normal University of Science and Technology, Qinhuangdao 066004, PR China
E-mail: liangbo@ysu.edu.cn, hqzhang@ysu.edu.cn
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A novel composite material composed of inorganic
semiconductor antimony sulphide (Sb2S3) and organic
semiconductor copper tetra-β-(4-carboxyphenoxy)
phthalocyanine (CuTβPc) was prepared by a simple solution
deposition process. The crystallite structure and properties
of Sb2S3-CuTβPc composites were analyzed by XRD, SEM,
FTIR and UV–vis. The electrochemical behavior of sensor
was investigated using cyclic voltammetry(CV) and
amperometry. For the development of potential chemical
52 Another potential material is phthalocyanines (Pcs) that
53 exhibits high chemical and thermal stability to its strongly
54 delocalized 18 π-electronic structure. It is reported that Pcs
55 show good electrochemical performance for the detection of
56 hydrazine.16 But it have a restricted practical application as a
57 result of tendency to aggregate (by attractive π-π stacking
58 interactions) in solution and low solubility in common
59 organic solvents. A promising approach towarded soluble
60 Pcs is inserting diverse bulky groups such as alkyl, alkoxy
61 and aryl groups at the periphery of macrocycle positions can
62 highly prevent the aggregation and improve solubility of Pcs
63 because of their steric hindrance. The design and
64 preparation of organic-inorganic composite sensing
65 materials is a promising strategy, which combines the
66 advantages of good stability of inorganic materials, low
67 operating temperature, good selectivity and high sensitivity
68 of organic materials. In the present work, we prepared
69 Sb2S3-CuTβPc composites through a strong molecular
70 interaction between CuTβPc macrocycles and Sb2S3 atom
71 layers and fabricated a hydrazine sensor. The Sb2S3 structure
72 acts as a good support material for immobilizing CuTβPc,
73 which can prevent the aggregation. Then the Sb2S3-CuTβPc
74 composites supported on platinum disk electrode was
75 applied to determination of hydrazine and exhibited good
76 electrochemical sensing activity.
10 sensor, Sb2S3-CuTβPc composites were deposited on flat
11 platinum disk electrode to give sensors that responded
12 quickly to selective hydrazine in the phosphate buffer phase.
13 The hydrazine sensor showed linear detection range from 10
14 nM to 0.5 μM and detection limit of 0.9 nM at a signal-to-
15 noise of 3. Thus this novel composite may be potentially
16 applied in the field of catalysis and environmental.
17 Keywords: Sb2S3-CuTβPc Composites, Hydrazine,
18 Electrochemical Sensors
19
Hydrazine hydrate (N2H4) is a strong reducing agent,
20 which is a raw material for pharmaceuticals, pesticides, dyes,
21 antioxidants, fuel cell, manufacture rocket materials and
22 explosives.1,2 However, it also involves many health
23 disorders as a neurotoxin and a carcinogen.3 Therefore, there
24 is an urgent need to develop a sensitive, selective and
25 reliable analytical quantitative method. To date various
26 methods of hydrazine detection have been reported, in
27 which electrochemical methods aroused considerable
28 attention for its portability, low cost and high sensitivity.4
29 The major concern with electrochemical detection at bare
30 electrode is their high overpotential for the hydrazine
31 oxidation and poor selectivity. An alternative is chemical
32 modification of electrode surface with catalysts. So the
33 electrochemical performance is highly dependent on the
34 materials used for electrode surface modification. As
35 reported in most literature, diverse metallic electrodes for
36 the same purpose are explored because a low overpotential
37 for hydrazine oxidation was observed. However, noble
38 metals (such as Au5 and Pd6 nanoparticles) and other
39 metallic oxysulfides (such as CuO,7,8 ZnO9, ZnS10 and
40 MnO211) are usually expensive or insufficiently sensitive.
41 Thus the enhancements of good electrical conductivity and
42 catalytic activity as well as low-cost materials are required
43 for sensitive hydrazine detection in practical application.
77
CuTβPc(S1) was synthesized according to the
78 literature.15 Sb2S3-CuTβPc hybrid was prepared by a simple
79 solution deposition process: Sb2S3 and CuTβPc in equimolar
80 ratio were put into 10 mL dimethylformamide (DMF)
81 solvent with 0.2 mL trifluoroacetic acid (TFA) and then the
82 mixture was stirred for 2 h after being ultrasonically
83 dispersed for 1 h, then heated in the oil bath at 363 K for 4 h.
84 The powdered product was obtained after removed the
85 solvent by distillation and washed with ethanol until the
86 filtrate was colorless. Finally, the powder was dried at 323
87 K for 12 h to get final Sb2S3-CuTβPc catalyst. 5 mg Sb2S3-
88 CuTβPc was dispersed in 1 mL alcohol to form a stable
89 suspension. A 3 μL aliquot of this dispersion was spread on
90 the cleaned electrode surface. The solvent was evaporated at
91 40 ℃ in a drying oven and a thin film was coated on the
92 surface of electrode (Sb2S3-CuTβPc/Pt).
93
The XRD patterns of CuTβPc, Sb2S3 and Sb2S3-
94 CuTβPc composites were shown in Figure 1(a). The
95 diffraction peaks of pure Sb2S3 matched well with the
96 characteristic peaks of the standard orthorhombic Sb2S3
97 (JCPDS No. 42-1393). Meanwhile, CuTβPc showed two
98 strong feature diffraction peaks at 2θ of 7.9° and 27.4°. The
99 XRD results of Sb2S3-CuTβPc composites exhibited
100 diffraction peaks corresponding to the orthorhombic Sb2S3
101 as well as a broad peak of CuTβPc produced the coexistence
44
Antimony sulfide (Sb2S3) is an important binary
45 chalcogenides with infinite layer-structure in its
46 orthorhombic lattice, which is regarded as a potential
47 material applied in thermoelectric devices,12 photosensors,13
48 hybrid solar cells,14 photocatalysts.15 In our previous
49 research,4 Sb2S3 film on indium-tin oxide (ITO) substrate
50 has been used as an efficient electron transfer mediator for
51 the fabrication of chemical sensor towards hydrazine.

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of Sb2S3 and CuTβPc. A new diffraction peak at 2θ of 9.9°
indicated the formation of a β-phase CuTβPc stacking
structure.18 Figure 1(b) showed the morphology of Sb2S3-
CuTβPc composites with stacked lamellar structure. The
SEM image (Figure S1) and the corresponding elemental
mapping of C (Figure S1a), O (Figure S1b), F (Figure S1c),
Sb (Figure S1d), S (Figure S1e), and Cu (Figure S1f)
revealed that the Sb2S3 micro-nanoparticles were
homogenously dispersed in the TβPcCu molecules.
34 Moreover, the peak of CuTβPc at 619 nm shifted to 625 nm
35 and 690 nm disappeared at Sb2S3-CuTβPc composites. It
36 indicated that insertion of micro-nanoparticles of Sb2S3 had
37 the effect on the doping of CuTβPc, while this effect was
38 attributed to an interaction at the interface of CuTβPc and
39 micro-nanoparticles of Sb2S3.19
Sb2S3
(a)
TβPcCu
Sb2S3-T
β
PcCu
Sb2S3-CuTβPc
(a)
Sb2S3
1600
1200
800
400
CuTβPc
-1
Wavenumber/cm
40
10
20
30
40
50
60
Sb2S3
PcCu
Sb2S3-T
(b)
2-Theta/degree
10
T
β
β
PcCu
300
400
500
600
700
Wavelength/nm
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Figure 2. (a) FTIR and (b) UV–visible spectra of Sb2S3, CuTβPc and
Sb2S3-CuTβPc composites
The (CV) analysis was performed to investigate the
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Figure 1. (a) XRD patterns of and CuTβPc, Sb2S3 and Sb2S3-
CuTβPc composites (b) SEM micrographs of Sb2S3-CuTβPc
composites
45 electro-catalytic parameters of fabricated chemical sensor
46 CuTβPc/Pt, Sb2S3/Pt and Sb2S3-CuTβPc/Pt electrode, shown
47 in Figure 3(a). Compared with bare Pt, CuTβPc/Pt and
48 Sb2S3/Pt, the Sb2S3-CuTβPc/Pt electrode exhibited a clear
49 oxidation peak at +0.25 V. In order to further test the current
50 change of fabricated chemical electrodes, the amperometric
51 test was performed by successive addition of hydrazine to
52 0.1 M PBS (pH=7.4) at an applied potential of 0.25 V under
53 continuously stirred condition. As shown in Figure 3(b), a
54 marked increase in the amperometric response was observed
55 after consecutive addition of hydrazine into 0.1 M PBS
56 solution. It could be shown from Figure 3(c) that the
57 amperometric response was linear with hydrazine
58 concentration ranging from 10 nM to 0.5 μM (R = 0.995)
59 with the detection limit of 0.9 nM (S/N=3). It seemed that
60 chemical electrodes based on Sb2S3-CuTβPc film would
61 have rapid current change in low concentration of hydrazine.
62 We believed the sensitivity and low detection limit was due
63 to the excellent material structure of Sb2S3-CuTβPc/Pt,
64 which was better than a separate interface structure
65 (CuTβPc/Pt or Sb2S3/Pt). The Sb2S3 structure acted as a
66 good support material for immobilizing CuTβPc, which
15
Figure 2(a) displayed the FTIR spectra of Sb2S3 micro-
16 nanoparticles, CuTβPc and Sb2S3-CuTβPc composites.
17 Three observed bands at 520, 799 and 836 cm-1 correspond
18 to the characteristic peaks of Sb2S3 micro-nanoparticles in
19 Sb2S3-CuTβPc composites. In case of Sb2S3-CuTβPc
20 composites, the characteristic peaks related to the CuTβPc
21 molecule had the same positions. Additional peaks were
22 observed at 1132 and 1203 cm-1 duo to the CF3COOH
23 molecule. The peaks at 1132 cm-1 and 1203 cm-1 correspond
24 to the C-F stretching modes. The peak at 1682 cm-1 was
25 stronger assigned to the C=O stretching modes of CF3COO-
26 ions.18 The UV–visible absorption spectra of Sb2S3, CuTβPc
27 and Sb2S3-CuTβPc composites were shown in Figure 2(b).
28 The three characteristic peaks of CuTβPc appear at about
29 335 nm, 619 nm and 690 nm, which were typical of copper
30 phthalocyanine B-band and Q-band absorption peaks.18 It
31 could be noted that the characteristic peaks of Sb2S3 micro-
32 nanoparticles at 389 nm and 535 nm, and the characteristic
33 peaks of CuTβPc appeared in the Sb2S3-CuTβPc composites.

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could improve electrochemical active surface area and the
selective utilization of CuTβPc for hydrazine oxidation.
Each CuTβPc molecule had four carboxyl groups, which
could quickly capture hydrazine hydrate in aqueous solution.
(a)0.15
0.12
j
0.09
0.06
0.03
0.00
-0.03
0.15
(a)
a
0.12
0.09
d
0.06
-0.2
0.0
0.2
0.4
0.6
0.8
c
Potential/V
b
16
0.03
(b)0.12
a
0.00
0.10
-0.2
0.0
0.2
0.4
0.6
0.8
0.08
0.06
0.04
0.02
Potential/V
5
(b) 30
[Ipa] = 0.0058 [V1/2] -0.0239
R2 = 0.993
1.0 mM
750 μM
0.5
2 μM
0.4
0.3
0.2
0.1
1.5 μM
20
700 nM
300 nM
100 nM
350 μM
150 μM
20 nM
0
6
8
10
12
14
16
18
20
22
24
200 400 600 800
V1/2/(mV/s)
10
0
17
70 μM
30 μM
10 μM
18
16
14
12
10
8
(c)
2 μM
hydrazine
0
400
800
1200
1600
2000
Time/s
6
(c) 30
6
25
4
2
20
15
10
5
0
-2
0.21
[I] = 0.2190 [C] + 0.0903
0
1000
2000
3000
2
Time/s
0.18
0.15
0.12
0.09
R = 0.995
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Figure 4. (a) CVs of the TβPcCu-Sb2S3/Pt in 0.1 M PBS (pH =
7.4) containing 0.2 mM hydrazine with different scan rates: (a)
50, (b) 100, (c) 150, (d) 200, (e)250, (f) 300, (g) 350, (h) 400, (i)
450 and (j) 500 mV/s (b) The calibration plot for the linear
dependence of oxidation peak current vs square root of scan rate
(c) I–t curves of Sb2S3-CuTβPc/Pt electrodes for the addition of
0.2 mM hydrazine into constantly stirred PBS up to 3000 s at
+0.25 V
0
0.0 0.1 0.2 0.3 0.4 0.5
0
200
400
600
800
1000
Hydrazine concentration/µM
7
8
9
Figure 3. (a) CV for hydrazine oxidation at bare Pt (curve a),
CuTβPc/Pt (curve b), Sb2S3 /Pt (curve c) and Sb2S3-CuTβPc/Pt
(curve d) electrodes (b) I–t curves of Sb2S3-CuTβPc/Pt electrodes
with successive addition of hydrazine into PBS at +0.25 V (c) the
plot of electro-catalytic current of hydrazine versus the
corresponding concentrations of hydrazine. The inset shows
corresponding calibration curve. Error bars represent the standard
deviations from the mean of three replicates.
27 The synergistic combination of Sb2S3 and CuTβPc in the
28 composite material effectively promoted the electron
29 transport rate of hydrazine hydrate and the electrode surface,
30 and improved the electrochemical oxidation activity of
31 hydrazine hydrate. Figure 4(a) showed the oxidation peak
32 potential of the CV moving forward with the increase of the
33 scanning rate, and Figure 4(b)displayed the oxidation peak
34 current was proportional to the square root of scan rates,
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15

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3
4
5
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suggesting that the electro oxidation of hydrazine on the
38 College and University Science and Technology Research
39 Project of Hebei Province (No: QN2016130) and Talent
40 Engineering Training Fund for scientific research Project of
41 Hebei Province (No: A2016002029).
CuTβPc-Sb2S3/Pt electrode was
a
typical diffusion-
controlled process. 6,8
In addition, the chemical sensor electrode in present
study was compared with other reported hydrazine
determination as listed in Table 1. This comparison showed
that our chemical sensor of Sb2S3-CuTβPc/Pt electrode
shows outstanding sensing performance in terms of high
linear range and low detection limit. The stability of the
42
43 Supporting
Information
is
available
on
44 http://dx.doi.org/10.1246/cl.******.
45 References and Notes
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3
4
5
6
7
21
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8
9
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82 21
83
AG/Au-NPs/SPCE
GR–Bi nanocomposite
GR/CCLP-GNPs/GCE
SrO.CNT NCs/GCE
Tungstophosphate-PAni/silver NCs
CuNPs-PANI-GO
0.6
5
up to 936
0.02-280
0.01-0.6
20
21
22
23
24
25
26
27
28
29
84 22
85
1.6
0.036
2.8
4.5
5
86 23
87
0.0002-0.2
0.01-10000
0.04-0.48
0.01-98.6
0.02-11
88 24
89
90 25
91
92 26
93
ZnO NRs/Ag
γ-Fe2O3/Au/GCE
6
94 27
95
AuNPs@NC-ZnO/ITO
Au@NPC-700/GCE
This work
4.1
8
0.05-10
96 28
97
0.08-466.28
0.01-1000
98 29
0.9
34
The authors gratefully acknowledge the financial
35 support from National Natural Science Foundation of China
36 (No: 51472214, 51602278), Natural Science Foundation of
37 Hebei Province (No: E2016203149，B2018407058), the