Elsevier

Electrochimica Acta

Volume 65, 30 March 2012, Pages 288-293
Electrochimica Acta

Electrocatalytic reduction of H2O2 by Pt nanoparticles covalently bonded to thiolated carbon nanostructures

https://doi.org/10.1016/j.electacta.2012.01.070Get rights and content

Abstract

Glassy carbon electrodes were coated with thiolated carbon nanostructures – multi-walled carbon nanotubes and graphene oxide. The subsequent covalent addition of platinum nanoparticles and coating with poly(diallydimethylammonium chloride) resulted in biosensors that detected hydrogen peroxide through its electrocatalytic reduction. The sensors were easily and quickly prepared and showed improved sensitivity to the electrocatalytic reduction of H2O2. The Pt nanoparticles covalently bonded to the thiolated carbon nanostructures were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, and energy dispersive X-ray spectroscopy. Cyclic voltammetry and amperometry were used to characterize the biosensors’ performances. The sensors exhibited wide linear ranges and low detection limits, giving fast responses within 10 s, thus demonstrating their potential for use in H2O2 analysis.

Highlights

► Novel thiolated carbon nanostructuresplatinum nanoparticles [t-GO-C(O)-pt and t-MWCNT-C(O)-S-pt] have been synthesized, and [t-GO-C(O)-pt and t-MWCNT-C(O)-S-pt] denotes as t-GO-pt and t-MWCNT-Pt in manuscript, respectively. ► The modified electrode denoted as PDDA/t-GO-pt/GCE was used for the electrochemical determination of H2O2 for the first time. ► The results show that PDDA/t-GO-pt nanoparticles have the promising potential as the basic unit of the electrochemical biosensors for the detection of H2O2. ► The proposed H2O2 biosensors exhibited wide linear ranges and low detection limits, giving fast responses within 10 s.

Introduction

The determination of hydrogen peroxide is important in various fields [1], [2], [3], [4], [5] and has been achieved through methods such as titrimetry [6], chemiluminescence [7], fluorescence [8], and spectrophotometry [9]. However, such methods are costly, complex, time consuming, and involve various sources of interference. H2O2 can be reduced to water via aqueous two-electron transfer under effective catalysts in a process related to the reduction of O2 in physiological systems. The electrochemical determination of H2O2 has advantages of facile preparation, fast detection, low consumption of materials, and high selectivity and sensitivity [10]. However, direct electrochemical reduction of H2O2 at ordinary solid electrodes is slow and requires a large overpotential, a major drawback.

Nanoparticles of noble metals such as platinum exhibit electrocatalytic behavior towards hydrogen peroxide and have been widely used in sensors [11], [12], [13], [14]. Electrodes modified with such nanoparticles can show enhanced electron transfer and reduced overpotential. Modified electrodes containing composites of platinum nanoparticles with carbon nanotubes have been fabricated for the electrocatalytic determination of hydrogen peroxide [15], [16], [17], [18], [19]. Improved graphene production [20], by methods such as chemical exfoliation and reduction, has led to considerable investigation of graphene systems in a similar pattern to carbon nanotubes and graphene composites with Pt nanoparticles have also been studied for H2O2 detection [19], [21], [22], [23], [24]. Interactions between the metal and the carbon nanomaterial can enhance catalytic activity by inducing specific microstructures or modifying the electron density in the metal clusters.

Nanomaterials can possess good conductivity and high surface areas, which can aid electrocatalysis. A glassy carbon electrode (GCE) modified with Nafion®-coated, thiolated multi-walled carbon nanotubes with covalently bonded Pd nanoparticles (Nafion®/t-MWCNT-Pd/GCE) has been reported for the determination of H2O2 by electrocatalytic reduction. It showed a wide linear range, fast responses, and good selectivity due to the synergies between the t-MWCNT-Pd and the Nafion® [25]. Various polyelectrolytes, including poly-(diallyldimethylammonium chloride) (PDDA), have been used as interlinkers for depositing metal nanoparticles on CNTs [26], [27]. PDDA was selected as a typical polyelectrolyte in this work, as it has been used in the fabrication of several polyelectrolyte multilayers [28], [29], [30].

This work reports the synthesis of thiolated carbon nanomaterials (MWCNT and graphene oxide (GO)) with covalently bonded platinum nanoparticles (t-MWCNT-Pt, t-GO-Pt). They were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and energy dispersive X-ray spectroscopy (EDS). They were then used to modify GCEs. The thiolated carbon nanomaterials with covalently bonded Pt nanoparticles were dropped onto GCE surfaces, and then coated with PDDA, also by dropping. The resulting PDDA/t-MWCNT-Pt/GCE and PDDA/t-GO-Pt/GCE H2O2 biosensors were characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV), and chronoamperometry (CA). They were easily and quickly prepared and showed improved sensitivity to the electrocatalytic reduction of H2O2.

Section snippets

Chemicals

MWCNT (diameter, 20–30 nm; length, 1.0–2.0 μm) were from Carbon Nano Tech. Co., Ltd. (City, South Korea). Graphite power (∼325 mesh, 99.999%), hydrogen hexachloroplatinate (H2PtCl6), sodium borohydride (NaBH4), sodium hydrogensulfide (NaSH), and PDDA were from Aldrich. The membrane filter was from Tokyo Roshi Kaisha, Ltd. (pore size 0.45 μm; diameter 47 mm). All other reagents were of analytical grade and used without further purification. Phosphate buffer solution (PBS) was prepared using 0.1 M NaHPO

Characterization of Pt nanoparticles on thiolated carbon nanomaterials

TEM images of t-MWCNT-Pt and t-GO-Pt show highly dispersed nano-sized particles anchored to the surfaces to the thiolated carbon supports (Fig. 1(a) and (b)). Small, highly dispersed nanoparticles were much more abundant than larger aggregates. Their average size, measured from 200 particles, was ca. 3.0 nm. High-resolution TEM (HRTEM) images show that the graphitic sheets of the thiolated carbon supports maintained highly ordered crystalline structures. SEM showed that the t-MWCNT-Pt and

Conclusions

Modification of a support with single bondSH over carboxilic groups allowed the covalent bonding of Pt nanoparticles. Novel thiolated carbon nanostructures covalently bonded with Pt nanoparticles [MWCNT-C(O)-S-Pt] and [GO-C(O)-S-Pt] were synthesized. Pt nanoparticles were quickly and simply covalently bonded to the thiolated carbon nanostructures. Electrodes incorporating the thiolated carbon-supported Pt showed sensitive and selective determination of H2O2. The nanostructures had electrochemical and

Acknowledgments

This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2010-0007864).

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