- Research article
- Open Access
Facile synthesis of flower like copper oxide and their application to hydrogen peroxide and nitrite sensing
© Zhang et al; licensee Chemistry Central Ltd. 2011
- Received: 17 September 2011
- Accepted: 2 December 2011
- Published: 2 December 2011
The detection of hydrogen peroxide (H2O2) and nitrite ion () is of great important in various fields including clinic, food, pharmaceutical and environmental analyses. Compared with many methods that have been developed for the determination of them, the electrochemical detection method has attracted much attention. In recent years, with the development of nanotechnology, many kinds of micro/nano-scale materials have been used in the construction of electrochemical biosensors because of their unique and particular properties. Among these catalysts, copper oxide (CuO), as a well known p-type semiconductor, has gained increasing attention not only for its unique properties but also for its applications in many fields such as gas sensors, photocatalyst and electrochemistry sensors. Continuing our previous investigations on transition-metal oxide including cuprous oxide and α-Fe2O3 modified electrode, in the present paper we examine the electrochemical and electrocatalytical behavior of flower like copper oxide modified glass carbon electrodes (CuO/GCE).
Flower like copper oxide (CuO) composed of many nanoflake was synthesized by a simple hydrothermal reaction and characterized using field-emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD). CuO modified glass carbon electrode (CuO/GCE) was fabricated and characterized electrochemically. A highly sensitive method for the rapid amperometric detection of hydrogen peroxide (H2O2) and nitrite () was reported.
Due to the large specific surface area and inner characteristic of the flower like CuO, the resulting electrode show excellent electrocatalytic reduction for H2O2 and oxidation of . Its sensitivity, low detection limit, fast response time and simplicity are satisfactory. Furthermore, this synthetic approach can also be applied for the synthesis of other inorganic oxides with improved performances and they can also be extended to construct other micro/nano-structured functional surfaces.
- Phosphate Buffer Solution
- Copper Oxide
- Layered Double Hydroxide
- Prussian Blue
- Electrochemical Sensor
The detection of hydrogen peroxide (H2O2) is of great important in various fields including clinic, food, pharmaceutical and environmental analyses, because H2O2 is a chemical threat to the environment and the production of enzymatic reactions . Many methods have been developed for the determination of H2O2, such as titrimetry , spectrophotometry , chromatography  and chemiluminescence . Compared with the above detection methods, the electrochemical detection of H2O2 was introduced to achieve a low detection limit and a low cost compared with the other detection methods. In recent years, with the development of nanotechnology, many kinds of micro/nano-scale materials have been used in the construction of electrochemical biosensors because of their unique and particular properties. A number of excellent reports have focused on the electrochemical determination of H2O2 utilizing noble metals including gold , silver , platinum [8, 9], palladium , and graphene-Pt nanoparticle hybrid material , transition metals and their oxides or complexes, such as MnO2 , Mn-nitrilotriacetate acid nanowires , CuO nanoparticles , Cu-Ni(OH)2 , layered double hydroxide , prussian blue , conducting polymers  and nanocomposite MnO2/MWNTs, Ag/GO [19, 20], as well as enzyme and protein modified electrodes [21, 22]. The low detection limit achieved with such platforms especially metal nanoparticle based electrodes is due to the enhancement in the signal-to-noise (S/N) ratio and increased mass transport to the electrode surface [11, 21]. Although some chemically modified electrodes have been proposed to reduce the large overpotential required for the direct oxidation or reduction of H2O2, it is still interesting to develop new materials with high efficiency and small dimensions for the detection of H2O2.
Like H2O2, nitrite ion () is another often studied analyte in various fields including clinic, food, and environmental analyses because its excess level in the blood has been proved to lead to haemoglobin oxidation [23–26]. Also it may interact in the stomach with amines and amides forming highly carcinogenic N-nitrosamine, many of which are known to be carcinogens [27, 28]. Therefore, determination is important for environment security and public health. Although is electroactive at carbon electrodes, its oxidation requires undesirably high overpotential and the voltammetric determination of it suffers from interference from other compounds. In order to improve the selectivity of sensor, the operating potential should be efficiently lowered. Modified electrodes with suitable electro-catalysts on the surface of carbon electrodes can achieve the purpose with an improved oxidation response of [29–31].
Metal oxide electrodes possess some unique electrochemical properties compared to metal ones. Their advantages include enhancement of reaction rate due to redox couples of oxide species of two different states, as well as weak adsorption or complete exclusion of hydrogen species on an oxide surface . Among these catalysts, copper oxide (CuO), as a well known p-type semiconductor, has gained increasing attention not only for its unique properties but also for its applications in many fields such as gas sensors, photocatalyst and electrochemistry sensors [30, 32–36]. Continuing our previous investigations on transition-metal oxide including cuprous oxide and α-Fe2O3 [37, 38] modified electrode, in the present paper we examine the electrochemical and electrocatalytical behavior of flower like copper oxide modified glass carbon electrodes (CuO/GCE). CuO was characterized by Powder X-ray diffraction (XRD), Field emission scanning electron microscopes (SEM) and cyclic voltammetry (CV) measurements. The electrochemical properties of the modified electrode were evaluated with regards to electrocatalytical reduction of H2O2 and electrocatalytical oxidation of .
Reagents and apparatus
Cu(NO3)2·3H2O, NH3·H2O and hexamethylenetetramine was purchased from Shanghai Chemical Reagent Factory (Shanghai, China). NaNO2 and 30% H2O2 solution was purchased from Beijing Chemical Reagent Factory (Beijing, China). All of the other chemicals used were analytical grade and used without further purification. Double-distilled water was used for preparation of buffer and standard solutions. All solutions were purged with high-purity nitrogen for at least 30 min to remove oxygen. NaNO2 and H2O2 solution was diluted daily before the electrochemical measurements.
Electrochemical experiments were performed with CHI 440a electrochemical analyzer (ChenHua Instruments Co. Ltd., Shanghai, China) with a conventional three-electrode cell. The CuO/GCE, an Ag/AgCl and a platinum electrode was used as the working electrode, the reference and the auxiliary electrode, respectively.
Synthesis of flower like CuO
In a typical synthesis, 0.7345 g Cu(NO3)2·3H2O and 0.8230 g hexamethylenetetramine (HMT) were dissolved into 25 ml distilled water under magnetic stirring. After 5.0 ml NH3•H2O (5%) was introduced into the mixture under stirring, the clear solution was transferred into a Teflon-lined steel-stainless autoclave of 40 ml. The autoclave was allowed to cool down to room temperature naturally after the system had been hydrothermally treated at 160°C for 6 h. Black precipitates were collected, washed with distilled water and ethanol several times to remove impurities. Finally, the precipitates were dried in air at 50°C for 6 h.
Characterization of the samples
Powder X-ray diffraction (XRD) of the product was carried out on a Shimadzu XRD-6000 X-ray diffractometer equipped with Cu Kα radiation (λ = 0.154060 nm), employing a scanning rate of 0.02°s-1 and 2θ ranges from 20° to 70°. Field emission scanning electron microscopes (SEM) was obtained by JEOL JSM-6700 FESEM (operating at 10 kV).
The dispersed flower like CuO on the electrode were fabricated by the following way: Firstly, the glass carbon electrode (GCE, Φ = 3 mm) was polished with a 1700# diamond paper and washed successively with double distilled water and ethanol in an ultrasonic bath, then 15 cyclic scans were carried out in the potential of 2.0 to -2.0 V (vs. SCE) in the solution of 1.0 mol/l H2SO4. Secondly, 4 mg CuO was dispersed in 2 ml ethanol solution. Then 20 μl of CuO solution (2 mg/ml) was cast on the surface of GCE and dried in air. Thus flower like CuO modified GCE was obtained.
Structures and morphology characterization
Electrochemical property of flower like CuO modified GCE
Electroreduction behavior and amperometric response of H2O2on the CuO/GCE
The catalytic mechanism for the reduction of H2O2 can be assumed as Cu (II) was first electrochemically reduced to Cu (I), which reacted chemically with H2O2 and resulted in the conversion of H2O2 to H2O and in the regeneration of the catalyst .
Comparison of performances of different electrochemical sensors for hydrogen peroxide.
0.5 nM-4 mM
Enzyme integrated silicate-Pt nanoparticle
Redox protein based EC
4.0 μM -16.0 mM
Electrooxidation behavior and amperometric response of on the CuO/GCE
First, nitrite loses an electron to form NO2 [reaction (1)]. Second, this step is followed by a homogeneous disproportionation [reaction (2)] of NO2 into nitrate and nitrite, which can be written as the total reaction (3) [45, 46].
Regarding the oxidation peak of at CuO/GCE, the potential scan rate was investigated clearly as shown in Figure 5(B). The peak current is proportional to the square root of scan rate in the range of 10-200 mV/s, ipa/μA = -3.5542 - 1.9517 v1/2/mV·s-1, R = 0.9995, while the Epa shifted positively. The results suggested that the oxidation of was undergoing a diffusion controlled process .
Comparison of performances of different electrochemical sensors for nitrites.
The potential interference for the detection of nitrite using this electrochemical sensor was also examined by adding the following ions into the PBS solution at the same concentration that was used for nitrite: K+, Na+, Mg2+, Zn2+, Cl-, and . None of the ions caused interference. The potential of nitrite oxidation is high and, as a result, other electroactive species present in complex like dopamine and ascorbic acid can in principle be oxidized as well, interfering with the nitrite analysis. However, the detection of nitrite was examined in presence of 20-fold amount of dopamine and ascorbic acid and showed no interference. This result is similar to that of the previous report , which demonstrates the selectivity of CuO based electrochemical sensor towards nitrite.
In summary, flower like CuO composed of many nanoflake with average thickness of 40 nm was synthesized by a simple hydrothermal reaction. Then a novel electrochemical sensor made of CuO onto GCE had been constructed. Due to the large specific surface area and inner characteristic of the flower like CuO, the resulting electrode show excellent electrocatalytic reduction for H2O2 and oxidation of . Its sensitivity, low detection limit, fast response time and simplicity are satisfactory. Furthermore, this synthetic approach can also be applied for the synthesis of other inorganic oxides with improved performances and they can also be extended to construct other micro/nano-structured functional surfaces.
The authors thank the National Natural Science Foundation of China (21001004), Young Fund of Anhui Normal University (2008xqn61) for fund support. This work is also supported by the innovation lab platform of Anhui Normal University.
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