Elsevier

Sensors and Actuators B: Chemical

Volume 193, 31 March 2014, Pages 492-500
Sensors and Actuators B: Chemical

Electrochemical determination of ascorbic acid, dopamine and uric acid based on an exfoliated graphite paper electrode: A high performance flexible sensor

https://doi.org/10.1016/j.snb.2013.12.004Get rights and content

Highlights

  • A flexible electrochemical sensor is successfully constructed by using a consumer-grade flexible graphite paper.

  • The exfoliated flexible graphite paper electrode with rough edges possesses high electrocatalytic activity toward the oxidation of ascorbic acid, dopamine and uric acid.

  • The flexible sensor with merits of high selectivity and low detection limits has great potential applications in flexible electronics.

Abstract

An exfoliated flexible graphite paper (e-FGP) with rough edges is proposed as a high performance working electrode for the electrochemical determination of ascorbic acid (AA), dopamine (DA), and uric acid (UA). Scanning electron microscopy (SEM), cyclic voltammetry (CV), different pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) were applied to investigate the unique properties of the high performance electrode. The results demonstrate its excellent electrocatalytic activity toward the oxidation of AA, DA and UA with well-separated voltammetric peaks. The calibration curves in the range of 20–400 μM, 0.5–35 μM, 0.5–35 μM, and the detection limits (S/N = 3) of 2.0 μM, 0.01 μM, 0.02 μM were obtained for AA, DA and UA in neutral phosphate buffer solutions (PBS), respectively. This mechanically flexible sensor with good selectivity and remarkable sensitivity could be used to determine DA and UA in real human urine samples.

Introduction

Sensors, acting important roles in smart sensor networks, are important components in the multifunctional integrated electrical device. With the rapid development of flexible electronics devices, flexible sensors with the merits of robust mechanical properties and space savings reveal attractive perspectives in various applications [1]. For instance, flexible electrochemical sensors have been widely explored for the determination or monitor of toxic or dangerous gases molecules such as hydrogen [2] and chlorine [3]. Carbon-based materials, from C60 and carbon nanotube (CNT) to graphene, provide plenty of opportunities for constructing different types of flexible sensors. Yamada et al. developed a stretchable carbon nanotube stain sensor for human motion detection [4]. Flexible biosensors fabricated on soft substrate with carbon nanotube were also reported by Juntae et al. [5]. It has also been proved that ultrasensitive and low-cost graphene-based cancer sensor could be constructed on a flexible PET substrate [6].

Dopamine (DA), as one of the most significant neurotransmitters in the brain, has been detected by using electrochemical methods since 1970 [7] because of necessity to monitor HIV infection, neurotransmission processes and diagnose Parkinson's disease [8], [9]. However, ascorbic acid (AA), dopamine and uric acid (UA) usually coexist in real systems and their electrochemical responses are severely overlapped on traditional electrodes. To addressed the problem, considerable efforts have been made to separate their signal potentials with enhanced intensity [10], [11], [12], [13]. Recently, many advanced materials including polymers [14], [15], [16], [17], metal complexes [18], [19], [20], metal oxide [21], multi-walled carbon nanotube [22] and graphene-based nanomaterials [23], [24] are reported effectively for the detection of AA, DA and UA. Though the previous studies have made profound progress, the fabrication of the electrodes is too complex and the reported modified glassy carbon electrodes are not suitable for flexible integrated devices, thus resulting in many limitations in practical applications. We recently reported a high performance microbial fuel cell by applying a flexible graphite electrode as an anodic material due to its good mechanical strength and excellent conductivity [25].

In this work, we have demonstrated a highly sensitive and selective flexible electrochemical sensor based on an exfoliated graphite paper electrode (e-FGPE) with plenty of rough edges and wrinkles for the determination of AA, DA and UA for the first time. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were used to study the electrochemical behaviors of these three analytes. Satisfactory results were obtained while applying standard addition method to real human urine samples.

Section snippets

Chemicals and materials

Flexible graphite papers were purchased from Beichuan Co. Ltd (China). AA was bought from Sinopharm Chemical Reagent Co. Ltd (China), DA and UA were obtained from Sigma–Aldrich. All other chemicals were from local chemical agent, and de-ionized water (>18.4  cm−1) was used throughout.

Apparatus

SEM images were recorded on NoVa™ NanoSEM 430 (FEI) with an accelerating voltage of 10.0 kV. Raman spectra were taken on LabRAM Aramis (HJY, France) with wavelength of 633 nm. All electrochemical measurements were

Characterization of the flexible graphite paper

A graphic illustration of the flexible sensor fabrication and the detection strategy is displayed in Scheme 1. A digital image of FGPE (a), e-FGPE (b) that was made by exfoliating FGPE with Kapton tape and e-FGPE in bending state is shown in Fig. 1A. The morphologies of the graphite papers were characterized by SEM (Fig. 1B–D). Rough edges and wrinkles on the surface of e-FGPE (Fig. 1C) provide more electrochemical active sites, as compared to the smooth surface of FGPE (Fig. 1B). Moreover, the

Conclusion

The present study demonstrates that an ordinary flexible graphite paper has been successfully fabricated to be a novel electrochemical sensor after easily exfoliated by Kapton tape. It is found that the flexible exfoliated graphite electrode with plenty of rough edges and wrinkles shows excellent electrocatalytic activity toward the oxidation of ascorbic acid, dopamine and uric acid. Additionally, our proposed sensor was successfully used for the determination of DA and UA in real human urine

Acknowledgment

The authors gratefully acknowledge the financial support by NSFC (81260639 and 21372088).

Weihua Cai is currently pursuing a Ph.D. at South China University of Technology (SCUT), Guangzhou, China. He received his Bachelor Degree from SCUT. His current interests are flexible electrochemical sensors and supercapacitors.

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    Weihua Cai is currently pursuing a Ph.D. at South China University of Technology (SCUT), Guangzhou, China. He received his Bachelor Degree from SCUT. His current interests are flexible electrochemical sensors and supercapacitors.

    Ting Lai is a graduate student in the College of Chemistry & Chemical Engineering SCUT, Guangzhou, China. Her current interests are electrochemical sensors.

    Haijun Du is currently a professor in College of Chemistry and Environment Science, Guizhou Minzu University, Guizhou, China. He received his Ph.D. in 2010 from SCUT. His current interests are graphene-based biosensors.

    Jianshan Ye is currently a professor at SCUT, Guangzhou, China. He received his Ph.D. from The Hong Kong University of Science & Technology, HK. He has already published more than 40 high-quality research papers and has mentored 5 Ph.D. students. His current interests are in the research fields of electrochemistry.

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