Electrocatalytic oxidation of hydrazine and hydroxylamine at gold nanoparticle—polypyrrole nanowire modified glassy carbon electrode

doi:10.1016/j.snb.2007.03.044

Sensors and Actuators B: Chemical

Volume 126, Issue 2, 1 October 2007, Pages 527-535

https://doi.org/10.1016/j.snb.2007.03.044 Get rights and content

Abstract

A novel electrochemical sensor was fabricated by electrodeposition of gold nanoparticle on pre-synthesized polypyrrole (PPy) nanowire, forming an Au/PPy composite matrix on glassy carbon electrode (Au/PPy/GCE). Field emission scanning electron microscope (FE-SEM), X-ray photoelectron spectroscopy (XPS) and powder X-ray diffraction (XRD) techniques were used for characterization of the composite. As an electrochemical sensor, the Au/PPy/GCE exhibited strongly catalytic activity toward the oxidation of hydrazine and hydroxylamine. The kinetic parameters such as the electron transfer coefficient (α) and charge transfer rate constant (k) for the oxidation of hydrazine and hydroxylamine were determined utilizing cyclic voltammetry (CV). The diffusion coefficient (D) of both two species was also estimated using chronoamperometry. Furthermore, the linear range, current sensitivity and detection limit for hydrazine and hydroxylamine were evaluated by differential pulse voltammetry (DPV). The detection limit of hydrazine and hydroxylamine was 0.20 and 0.21 μM (s/n = 3), respectively. In addition, the sensor showed excellent sensitivity, selectivity, reproducibility and stability properties.

Introduction

Hydrazine is widely used as a raw material in the manufacture of agricultural chemicals, a powerful reducing agent in fuel cells [1], intermediates in industrial preparations of pesticides, plant-growth regulators, polymerization catalysts, corrosion inhibitor and antioxidant [2]. It is also very important in pharmacology, because it is recognized as a carcinogenic, hepatotoxic and mutagenic substance [3], [4]. It has been reported that hydrazine and its derivatives have adverse health effects [5]. Therefore, sensitive detection of hydrazine is practically important for environmental and biological analysis [6].

Hydroxylamine is known as a kind of reducing agents, which is widely used in industry and pharmacy. It is identified as a key intermediate in the nitrogen cycles and production of nitrous oxide [7]. Although hydroxylamine is a well-known mutagen, moderately toxic and harmful to human, animals, and even plants [8], it is widely used as a raw material for the synthesis of pharmaceutical intermediates and final drug substances. Thus, quantitative determination of hydroxylamine is also very important both in studies of biological processes and for industrial purposes [9].

Numerous methods have been developed for the determination of hydrazine [10], [11], [12], [13], [14], [15], [16] and hydroxylamine [17], [18], [19], [20], [21]. However, these methods had high detection limit and low precision, thus development of more sensitive and reliable method is necessary. Electroanalytical techniques were proven to be relatively direct and effective for the detection of hydrazine [22]. Unfortunately, both of hydrazine and hydroxylamine exhibited irreversible oxidation required large overpotentials at bare carbon electrodes. Recently, various chemically modified electrodes (CMEs) have been prepared and applied in the determination of hydrazine [23], [24], [25], [26], [27], [28], [29] and hydroxylamine [28], [29], [30], [31], [32], which can significantly lower the overpotentials and increase the oxidation current response.

Noble metal nanoparticles have been extensively utilized in recent years, owing to their extraordinarily catalytic activities for both oxidation and reduction reactions. Due to the unique properties of gold nanoparticles, such as good conductivity, useful electrocatalytic ability and biocompatibility, several researchers have been devoted to fabricate electrochemical sensors and biosensors [33], [34], [35], [36]. The gold nanoparticles dispersed on various substrates have been reported, such as carbon paste electrode, self-assembled monolayer, conducting and non-conducting polymers. Among them, conducting polymers are suitable host matrices because they have advantages of permitting a facile electronic charge flow through the polymer matrix in electrochemical processes [37]. Conducting polymers can provide not only low ohmic drops but also enhance the rate constant of electron transfer (et) process for some electroactive species. Polypyrrole (PPy) is one of most important organic conducting polymers, which have been found in wide applications in analytical chemistry. PPy nanowire has attracted much attention because of its well-ordered polymer chain structure with very high surface-to-volume ratio and small cross dimensions and highly electronic conductivity than ordinary PPy films.

Recently, we have studied PPy nanowires and Pt nanoclusters composite for glucose determination, in which the electrochemically generated Pt nanoclusters were embedded in the PPy nanowires [38]. In this paper, we investigated the synthesis of Au/PPy composite by a similar electrochemical method on glassy carbon electrode surface. The generated gold nanoparticles were not embedded in the PPy nanowires, but rather dispersed well on the surface of PPy nanowires in neutral electrodeposition solution. Through a suitable combination of PPy nanowires and gold nanoparticles, the Au/PPy composite can provide a porous structure with large effective surface area and highly electrocatalytic activities toward the oxidation of hydrazine and hydroxylamine.

Section snippets

Reagents

Pyrrole was obtained from Aldrich and purified twice by distillation under the protection of high purity nitrogen and then kept in a refrigerator before use. Hydrazine, hydroxylamine and HAuCl₄ were obtained from Chemical Reagent Company of Shanghai (Shanghai, China). All other chemicals were of analytical-reagent grade and used without further purification. Doubly distilled water and high purity N₂ were used. The 0.1 M phosphate buffer solutions of different pH values (PBSs) were prepared for

Characterization of electrode surface

FE-SEM images of the synthesized PPy nanowires matrix and the Au/PPy nanocomposite on GCE were shown in Fig. 1. Fig. 1A shows the image of deposited PPy nanowire matrix, which is a sponge-like nano-matrix consisted of PPy nanowires of about 60 nm in diameter. Fig. 1B shows the morphology of the Au/PPy composite, in which the CV deposition of gold nanoparticle of about 15 nm in diameter is attached on the surface and aligned along the PPy nanowires.

The generated gold nanoparticles were mainly

Conclusions

A novel electrochemical sensor for determination of hydrazine and hydroxylamine was fabricated by two electrodeposition steps: pre-synthesized 3D PPy nanowires matrix on GCE surface and electrodeposition of gold nanoparticles on the PPy nanowires. The constructed Au/PPy/GCE exhibited a strongly electrocatalytic activity toward the oxidation of hydrazine and hydroxylamine. The modified electrode was used for sensitive determination of hydrazine and hydroxylamine using DPV technique. The lower

Acknowledgement

The authors appreciate the financial support from National Natural Science Foundation of China (No. 20575062) and the Specialized Research Fund for the Doctoral Program of Higher Education (No. 20040358021).

Jing Li received her BSc degree in chemistry (2003) from Huaibei Coal Industry Teachers College in Anhui, China. Now, she is a graduate student in University of Science and Technology of China. Her current research interests include the preparation of metal nanoparticles and the development of their applications to chemical sensors and biosensors.

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Xiang-Qin Lin received his PhD in 1965 from University of Houston (USA), and is a professor of analytical chemistry in the present university. His research interest is mainly in the area of electrochemistry and electroanalytical chemistry.

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Electrocatalytic oxidation of hydrazine and hydroxylamine at gold nanoparticle—polypyrrole nanowire modified glassy carbon electrode

Abstract

Introduction

Section snippets

Reagents

Characterization of electrode surface

Conclusions

Acknowledgement

Electrochem. Commun.

J. Electroanal. Chem.

Mutat. Res.

Chemosphere

Talanta

Talanta

J. Chromatogr. A

J. Chromatogr. A

J. Electroanal. Chem.

Sens. Actuators B

Anal. Chim. Acta

Anal. Chim. Acta

Talanta

Electrochim. Acta

Electrochem. Commun.

Electrochem. Commun.

Sens. Actuators B

J. Catal.

Biosens. Bioelectron.

J. Electroanal. Chem.

Spectrophotometric determination of trace amounts of hydrazine in polluted water

Analyst