Elsevier

Electrochimica Acta

Volume 53, Issue 26, 1 November 2008, Pages 7751-7755
Electrochimica Acta

Prussian blue nanoparticles potentiostatically electrodeposited on indium tin oxide/chitosan nanofibers electrode and their electrocatalysis towards hydrogen peroxide

https://doi.org/10.1016/j.electacta.2008.05.035Get rights and content

Abstract

Chitosan (CS) nanofibers were successfully used to modify indium tin oxide (ITO) electrode by electrospinning technique. Then, Prussian blue (PB) nanoparticles were electrodeposited on the CS nanofibers by potentiostatic technique in an acidic solution containing single ferricyanide. By this method, direct synthesis of PB nanoparticles on the nanofibers that were used for modifying electrode came true. Transmission electronic microscopy (TEM) showed that the average size of PB nanoparticles was about 50 nm. Selected-area electron diffraction (SAED) showed diffusive diffraction spots, indicating the mosaic structure of the PB nanoparticles on the CS nanofibers. X-ray powder diffraction (XRD) displayed the long-range disorder of CS nanofibers and demonstrated the formation of PB nanoparticles. Results of the scanning electron microscope (SEM) images indicated that the PB nanoparticles could be electrodeposited on the CS nanofibers. The amount of the PB nanoparticles on the CS nanofibers increased with increasing potential value of the electrodeposition. In addition, the cyclic voltammetric response displayed two characteristic redox couples of PB. The modified electrode exhibited electrocatalytic activity towards reduction of H2O2.

Introduction

Prussian blue (PB), Fe4(III)[Fe(II)(CN)6]3, has received a lot of attention with well-known electrochromic [1], [2], electrochemical [3], photophysical [4], and potential analytical applications [5], [6]. PB is the simplest representative of which the metal ion centers are both iron. This unique structural arrangement and compositional variation via metal substitution lead to a combination of properties that is not readily found in other inorganic materials. In recent years, there have been extensive studies on PB for its applications in magnetic materials [7], [8], [9], molecular sieves [10], catalysis [11], solid-state batteries [12], electrochromic devices [13], biosensors [14], and molecular magnets [15]. Among the wide applications, nano-sized PB for device applications is particularly attractive. In addition, due to its excellent electrocatalysis, PB has been widely used as an electron-transfer mediator in the amperometric biosensors [16], [17]. For example, the PB modifier strongly catalyzes the reduction of hydrogen peroxide in a negative operating potential range, offering the most sensitive and interference-free detection [18]. The electrodeposition of PB and its analogues on various conductive substrates has been reported [19] to date, which requires the simultaneous presence of metal ions and the corresponding metal–cyanide ions in solution with an excess of supporting cations. Recently, Zhang et al. reported a potentiostatic electrochemical approach to format a PB nanocluster layer from an acidic solution of single ferricyanide at negative potential [20]. This effective and simple method has attracted most of researchers [21], [22], [23].

Modification of electrode surface through electrospinning technique is an interesting and potential research domain. Yang et al. first reported indium tin oxide (ITO) electrode modified with P2Mo18/polyvinyl alcohol (PVA) nanofiber-mats via layer-by-layer self-assembly technique [24]. P2Mo18 ions were successfully loaded on the PVA nanofibers because the electrospun nanofibers had higher surface area approximately 1–2 orders of the magnitude and larger surface energy than the corresponding flat substrate. However, the peak currents of P2Mo18 deposited on the PVA nanofibers were very small due to the poor electrical conductivity of PVA nanofibers, which limited the application of the modified electrode. In addition, the amount of P2Mo18 ions deposited on the outer layer decreased with increasing the layer numbers [25]. Obviously, the layer-by-layer technique was tedious and difficult to control the amount of the deposited P2Mo18 ions. In our experiments, electrospun chitosan (CS) nanofibers were selected to replace PVA nanofibers for modifying the ITO electrode. According to the literature [26], [27], pure CS nanofibers were obtained by the electrospinning of chitosan solution in a cosolvent system of trifluoroacetic acid (TFA) and dichoromethane (DCM). The electrospun CS nanofibers could overcome the poor electrical conductivity of PVA nanofibers because of comparatively high positive charge density of CS nanofibers. PB nanoparticles were directly electrodeposited on the CS nanofibers by potentiostatic technique in an acidic solution (pH 1.6) containing single ferricyanide. The large surface-to-volume ratio of CS nanofibers made the PB nanoparticles have larger contact surface with medium. Thus, the electrode modified with CS nanofibers had larger working area that provided more effective catalytic effect [28].

Taking advantages of nano-sized effect of nanofibers and nanoparticles, the ITO electrode modified with CS nanofibers containing PB nanoparticles showed electrocatalysis towards the reduction of hydrogen peroxide. The modified electrode can become potential candidate for the monitoring of hydrogen peroxide in medicine, environmental control, and industry because of its large reduction current and nontoxicity [29].

Section snippets

Chemicals

Chitosan (degree of deacetylation 78%, MW 400 000) was purchased from Sichuan Biochem-Zx Research Co. Ltd. (Sichuan, China). Trifluoroacetic acid (TFA) and Dichloromethane (DCM) were obtained from Sinopharm Chemical Reagent Co. Ltd. (Shanghai, China) and Tiantai chemical Reagent Co. Ltd. (Tianjin, China), respectively. K3Fe(CN)6, K2SO4, Na2CO3, were all analytical reagent grade, and were used as received. Phosphatic buffer solution (PBS) and H2O2 solution were all freshly prepared before used.

XRD spectra

XRD pattern of the ITO electrode modified with CS nanofibers/PB nanoparticles is shown in Fig. 1. The pattern shows a broad peak centered at 2θ = 25° which may be ascribed to the periodicity parallel to the polymer chain [31]. Obviously, CS still presents long-range disorder after electrospinning. The peaks corresponding to 2θ = 17.4°, 2θ = 24.6°, 2θ = 35.2°, 2θ = 39.4°, and 2θ = 43.4° are in agreement with those reported for Fe4[Fe(CN)6]3 particles [32]. The peaks at 2θ = 30.8°, 2θ = 42.1°, 2θ = 51.2°, and 2θ = 

Conclusion

In summary, we had successfully synthesized PB nanoparticles on the ITO/CS nanofibers electrode by potentiostatic technique in an acidic solution containing single ferricyanide. The electrocatalytic currents were higher than that of the traditional electrode modified with PB films by tedious layer-by-layer technique, which attributed to the effective working surface of PB nanoparticles, the high charge density, and the high surface-to-volume ratio of CS nanofibers. This article provided a

Acknowledgments

This work was supported by the Program for Changjiang Scholars and Innovative Research Team in University and the Science Foundation of Jilin Province (20070505).

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