Electrochemistry Communications 11 (2009) 18111814

Contents lists available at ScienceDirect

Electrochemistry Communications
journal homepage: www.elsevier.com/locate/elecom

Electrospun palladium (IV)-doped copper oxide composite nanobers for non-enzymatic glucose sensors
Wei Wang, Zhenyu Li, Wei Zheng, Jie Yang, Hongnan Zhang, Ce Wang *
Alan G. MacDiarmid Institute, College of Chemistry, Jilin University, Qianjin Street 2699#, Changchun 130012, PR China

a r t i c l e

i n f o

a b s t r a c t
Pd (IV)-doped CuO oxide composite nanobers (PCNFs) have been successfully fabricated via electrospinning and then employed to construct an amperometric non-enzymatic glucose sensor. The PCNFs based glucose sensors display distinctly enhanced electrocatalytic activity towards the oxidation of glucose, showing signicantly lower overvoltage (0.32 V) and ultrafast (1 s) and ultrasensitive current (1061.4 lA mM1 cm2) response with a lower detection limit of 1.9 108 M (S/N = 3). Additionally, excellent selectivity, reproducibility and stability have also been obtained. These results indicate that PCNFs are promising candidates for amperometric non-enzymatic glucose detection. 2009 Elsevier B.V. All rights reserved.

Article history: Received 16 June 2009 Received in revised form 9 July 2009 Accepted 24 July 2009 Available online 30 July 2009 Keywords: Electrospinning Copper oxide Doped Non-enzymatic Glucose sensor

1. Introduction The past several decades have witnessed the big progress on fabricating sensitive devices for fast and reliable monitoring glucose and carbohydrates driven by their practical applications in treating and controlling diabetes [1,2]. Among those devices, amperometric glucose biosensors with glucose oxidase (GOx) [3] and without GOx [4] have been the subject of considerable interest because a low detection limit can be achieved easily. Especially, the enzymeless glucose sensors have gained special focus taking the advantages of good stability, simplicity, reproducibility and so on [5]. Recently, bimetallic materials are of particular interest for non-enzymatic glucose detection owing to the improved electrocatalytic ability of pure metal anodes occurs as a consequence of the introduction of the other elements [68]. However, at nano-scale, these metallic nanomaterials based electrodes usually suffer from the stable problems (easy oxidization or poisoning) or high cost, which hinders their practical applications [9,10]. On the other hand, oxides based glucose sensors have been widely investigated for non-enzymatic detecting owing to their good stability [11,12]. Prompted by the high electrocatalytic ability of pure metallic nanomaterials and the good stability of oxides, in this communication, we demonstrate a novel type of ultrasensitive and stable enzymeless glucose sensor based on bimetal oxides of palladium-doped copper oxide composite nano-

bers (PCNFs) via electrospinning [13]. Ultrafast response with a lower detection limit at a lower applied potential can be obtained based on our sensor.

2. Experimental
D-Glucose, cupric acetate, palladium chloride, polyvinyl alcohol (PVA, Mw = 70,00075,000), NaOH and ethylene glycol were purchased from Beijing Chemical Co. (China). Uric acid (UA), L-ascorbic acid (AA), dopamine (DA), Triton-X100 and Naon (Nf) (v/v, 5%) were obtained from SigmaAldrich. All chemicals were used as received without any further purication. Distilled water was used in all experiments. PCNFs were fabricated through electrospinning and followed by calcination. In a typical procedure [14], 0.4 g of cupric acetate and 0.02 g palladium chloride were added slowly into 7.6 g of a PVA solution (7.9 wt.%) with 0.01 g of Triton-X100. Then, the solution was kept under vigorous magnetic stirring for 12 h, and a viscous gel was obtained. Finally, the as-prepared gel was loaded into a syringe and connected to a high-voltage power supply for electrospinning. An electric potential of 15 kV was applied between the orice and the ground at a distance of 20 cm. Then, calcination (500 C in air for 5 h) was used to treat the as-spun composite bers to remove the organic constituents of PVA and to convert the precursor into PCNFs. The modied electrode was prepared as follows: glassy carbon (GC) electrodes (3 mm diameter) were carefully polished with a diamond pad/3 lm polishing suspension, rinsed with distilled

* Corresponding author. Tel.: +86 431 85168292. E-mail address: cwang@jlu.edu.cn (C. Wang). 1388-2481/$ - see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.elecom.2009.07.025

1812

W. Wang et al. / Electrochemistry Communications 11 (2009) 18111814

water and ethanol, and then dried under ambient nitrogen gas. The as-prepared nanobers (1 mg) were dissolved in 200 lL ethylene glycol. After ultrasonication (2 min), uniformly dispersed PCNFs were obtained. After dipping 5 lL PCNFs solution onto the electrode surface, the electrode was dried at 80 C. Subsequently, 5 lL Naon (Nf) (v/v, 1%) solution was dropped onto the modied electrode to form a lm. The crystal structures of the products were determined by X-ray powder diffraction (XRD) using an X-ray diffractometer (Siemens D5005, Munich, Germany). Analysis of the X-ray photoelectron spectra (XPS) was performed on an ESCLABMKII using Mg as excitation source. The morphologies of the electrospun nanobers were viewed by scanning electron microscopy (SEM, SHIMADZU SSX-550, Japan). Transmission electron microscopy observations (TEM, Model JEM-2000EX, JEOL) were performed with an accelerating voltage of 200 kV. All electrochemical measurements were performed on a CHI 660C electrochemical workstation (Shanghai, China) with a conventional three-electrode system composed of a platinum auxiliary, a saturated calomel electrode reference (SCE), and modied glassy carbon working electrodes. All electrochemical experiments were performed in 0.1 M NaOH solutions (5 mL) under nitrogen atmosphere at room temperature. Glucose concen-

tration was controlled by adding desired concentration of glucose into the NaOH solution. 3. Results and discussion SEM has been used to characterize the morphologies of pure CuO nanobers and PCNFs as shown in Fig. 1a and b. From the SEM images, it can be seen that the diameters of the as-prepared nanobers are ranging from 90 to 140 nm. Fig. 1c and d show the TEM images of the CuO nanobers and PCNFs, indicating that those bers have a rough surface and consist of the agglomeration of oxides nanoparticles with average size of about 40 nm. Fig. 1e shows XRD patterns of the pure CuO nanobers and PCNFs. The apparent monoclinic structure CuO (JCPDS 5-0661) can be detected in both samples [15]. And there is no indication of the presence of any dopants-related phases for the Pd-doped sample, attributing to the high dispersion or the poor crystallinity of dopants-related nanoparticles. In order to prove the existence of Pd component in the PCNFs, XPS has been used to investigate the bonding characteristics and oxidation states of Pd in the composite nanobers. As shown in Fig. 1f, the Pd 3d spectrum shows two

Fig. 1. SEM images of (a) pure CuO nanobers and (b) PCNFs. TEM images of (c) pure CuO nanobers and (d) PCNFs. (e) XRD patterns of the products and (f) XPS spectra of Pd 3d for PCNFs.

W. Wang et al. / Electrochemistry Communications 11 (2009) 18111814

1813

Fig. 2. Cyclic voltammograms (CVs) of 0.6 mM glucose in 0.1 M NaOH at the (a) pure CuO nanobers modied and (b) PCNFs modied electrodes. Solid and dashed curves represent the CVs without and with glucose, respectively. The scan rate is 50 mV s1. (c) Plots of signal-to-background ratio to the applied potential on PCNFs modied electrode. (d) Calibration curve of glucose on PCNFs modied electrode. Inset shows currenttime response on PCNFs modied electrode with consecutive ve injection of 20 lM glucose into 0.1 M NaOH at +0.35 V.

peaks centered at 337.4 (Pd 3d5/2) and 342.6 (Pd 3d3/2) eV, respectively, conrming the presence of Pd component and the bonding state of palladium is in the form of Pd4+ [16]. The electrocatalytic activity of the PCNFs modied electrode towards the oxidation of glucose in an alkaline solution is demonstrated rst of all. Fig. 2a and b displays the cyclic voltammograms (CVs) behaviors of the pure CuO nanobers modied and PCNFs modied GC electrodes, respectively, in the absence and presence of 0.6 mM glucose in 0.10 M NaOH solution recorded at 50 mV s1. Upon addition of 0.6 mM glucose, a single forward oxidative wave, corresponding to the irreversible glucose oxidation is observed for both electrodes. The pure CuO nanobers based electrode exhibits signicant oxidation of glucose starting at ca. +0.15 V (vs. SCE) with a shoulder peak at ca. +0.4 V. It is much lower than that of other pure Cu or CuO based electrodes [12,17,18]. For the PCNFs modied electrode, a further substantial negative shift of the anodic peak potential and dramatic increase of current signal are observed as depicted in Fig. 2b (dashed curve). The oxidation process starts at only 0.08 V vs. SCE, and the broad oxidative wave centers at as low as +0.32 V. The distinctly improved electrocatalytic activity of the PCNFs modied electrode towards glucose may be explained as follow. Pd sites in the PCNFs, with lower electron occupancy in their 3d orbitals in comparison to the Cu sites, can function as Lewis acid sites for adsorption of polar glucose molecules, which are Lewis bases, via their non-bonded electron pairs. Thus an increased residence time for the reactant species within the electried interface at the electrode surface will occur, with the result of increased electrocatalytic activity towards the oxidation of glucose [7,8]. The above CV measurements suggest that the PCNFs modied electrodes might be applied in the detection of glucose. In order to choose the optimal value of the applied potential for glucose

detecting, Fig. 2c shows signal-to-background ratio on the PCNFs modied electrode under different potentials measured in chronoamperometry system in 0.1 M NaOH with successive addition of 0.05 mM glucose. The signal-to-background ratio increases with the potential in range from +0.20 to +0.35 V, and then decays obviously after that potential. For a high sensitivity, a constant potential of +0.35 V is chosen and employed as the optimum potential for the determination of glucose. Fig. 2d displays a typical amperometric response curve of glucose in 0.1 M NaOH recorded at 50 mV s1 at the PCNFs modied electrode. A well-dened, stable and fast amperometric response can be observed at 0.35 V. With the successive addition of glucose the biosensor yields a step-like increase amperometric response (the inset of Fig. 2d). The time required to reach the stable response is less than 1 s. The calibration curve for the glucose sensor is worked out (Fig. 2d). The sensor displays a linear range from 0.2 lM to 2.5 mM glucose with a correlation coefcient of 0.99, a sensitivity of 1061.4 lA mM1 cm2, and a detection limit of 1.9 108 M (S/N = 3). Moreover, the excellent sensing properties of our glucose sensor are also much more attractive than former reports [1720] and can be explained as follow. The as-prepared electrospun nanobers are made up of nanoparticles as demonstrated in Fig. 1d, which have not only large surface for adsorption of the reactants but also more electron transfer passages, the electrochemical probe can arrive to the surface of the electrode more easily. Moreover, the larger length-to-diameter ratio will promote electron transfer in the oxidation of glucose [21,22]. The reproducibility and stability of the sensor is evaluated by comparing the response currents of six PCNFs modied electrodes prepared under the same conditions. The relative standard deviation (RSD) of response current is 1.9% for 1.0 mM glucose. Thirty successive measurements of 1.0 mM glucose on one PCNFs

1814

W. Wang et al. / Electrochemistry Communications 11 (2009) 18111814

modied electrode yield an error about 7%. When the sensor is stored in air at 4 C, it retains 94% of its initial response current after 50 days. It indicates that the sensor based on PCNFs has good reproductivity and stability. To evaluate the selectivity of the proposed biosensor, three possible interfering biomolecules, AA, UA and DA, which normally coexist with glucose in real samples (human blood) are examined. Considering that the concentration of glucose in the human blood is about 30 times of AA, UA or DA, the amperometric response of the PCNFs modied electrode towards the addition of 1 mM glucose, 0.05 mM AA, 0.1 mM UA and 0.1 mM DA is examined in 0.10 M NaOH solution. The current response produced by AA, UA and DA are 3.0, 1.9 and 2.4 lA, only 4.1%, 2.6% and 3.3% compared to that of glucose (72.7 lA), respectively. The other interference test for carbohydrate compounds is also carried out (data not shown), and negligible interference has been caused by these common interfering biomolecules. Electrodes based on metals or alloys towards the oxidation of glucose usually lose their activity due to the poisoning of chloride ions [11]. In order to understand whether chloride ions will poison the PCNFs modied electrode, the CV is measured in the solution with high concentration of chloride ions (i.e., replacing 0.10 M NaOH with 0.30 M KCl + 0.10 M NaOH as the electrolyte). The current response of PCNFs modied electrodes towards glucose oxidation remains unchanged (data not shown), implying that the PCNFs modied electrode is also highly resistant to poisoning by chloride ions and can be used as a glucose sensor even in the presence of high concentration of chloride ions. 4. Conclusion In summary, a novel amperometric non-enzymatic glucose sensor based on Pd (IV)-doped CuO nanobers (PCNFs) has been successfully fabricated via electrospinning. The PCNFs modied electrodes display distinctly enhanced electrocatalytic activity towards the oxidation of glucose, showing signicantly lower over-

voltage (0.32 V) and ultrafast (1 s) and sensitive current response with a lower detection limit. It is believed that our method will provide a desirable platform for large-scale design and construct effective biosensors and electrocatalyst. Acknowledgements This work has been supported in part by the National 863 Project (No. 2007AA03Z324), National 973 Project (No. 2007CB936203), and NSFC grants (Nos. 20674027 and 50873045). References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] J.D. Newman, A.P.F. Turner, Biosens. Bioelectron. 20 (2005) 2435. Y.J. Zou, C.L. Xiang, L.X. Sun, F. Xu, Biosens. Bioelectron. 23 (2008) 1010. M.E.G. Lyons, G.P. Keeley, Chem. Commun. 22 (2008) 2529. J.P. Wang, D.F. Thomas, A.C. Chen, Anal. Chem. 80 (2008) 997. R. Wilson, A.P.F. Turner, Biosens. Bioelectron. 7 (1992) 165. P.H. Hindle, S. Nigro, M. Asmussen, A.C. Chen, Electrochem. Commun. 10 (2008) 1438. S. Mho, D.C. Johnson, J. Electroanal. Chem. 500 (2001) 524. I.H. Yeo, D.C. Johnson, J. Electroanal. Chem. 484 (2000) 157. H. Liu, X. Su, X. Tian, Z. Huang, W. Song, J. Zhao, Electroanalysis 18 (2006) 2055. X. Kang, Z. Mai, X. Zou, P. Cai, J. Mo, Anal. Biochem. 363 (2007) 143. J. Chen, W.D. Zhang, J.S. Ye, Electrochem. Commun. 10 (2008) 1268. E. Reize, W.Z. Jia, M. Gentile, Y. Wang, Y. Lei, Electroanalysis 20 (2008) 2482. D. Li, Y.N. Xia, Adv. Mater. 16 (2004) 1151. W. Wang, H.M. Huang, Z.Y. Li, H.N. Zhang, Y. Wang, W. Zheng, C. Wang, J. Am. Ceram. Soc. 91 (2008) 3817. H.Y. Guan, C.L. Shao, B. Chen, J. Gong, X.H. Yang, Inorg. Chem. Commun. 6 (2003) 1409. J.M. Giraudon, A. Elhachimi, F. Wyrwalski, S. Siffert, A. Aboukais, J.F. Lamonier, G. Leclercq, Appl. Catal. B 75 (2007) 157. X. Li, Q.Y. Zhu, S.F. Tong, W. Wang, W.B. Song, Sens. Actuators, B 136 (2009) 444. C. Batchelor-McAuley, Y. Du, G.G. Wildgoose, R.G. Compton, Sens. Actuators, B 135 (2008) 230. X.J. Zhang, G.F. Wang, A.X. Gu, Y. Wei, B. Fang, Chem. Commun. 45 (2008) 5945. J.J. Yu, T. Zhao, B.Z. Zeng, Electrochem. Commun. 10 (2008) 1318. Z.Y. Li, H.N. Zhang, W. Zheng, W. Wang, H.M. Huang, C. Wang, A.G. MacDiarmid, Y. Wei, J. Am. Chem. Soc. 130 (2008) 5036. J.S. Huang, D.W. Wang, H.Q. Hou, T.Y. You, Adv. Funct. Mater. 18 (2008) 441.