Electrospun three-dimensional porous CuO/TiO2 hierarchical nanocomposites electrode for nonenzymatic glucose biosensing

https://doi.org/10.1016/j.elecom.2012.01.032Get rights and content

Abstract

Hierarchical nanocomposites of single-crystalline CuO nanoplates attached on the surface of polycrystalline TiO2 nanotubes were first prepared by electrospinning. In application to nonenzymatic glucose determination, the precusor was electrospun onto fluorine-doped tin oxide (FTO) glass directly. After hot press and calcination, a three-dimensional porous CuO/TiO2 modified electrode was fabricated. Because of the combination of hierarchical composite and three-dimensional structure, it exhibits a high sensitivity of 1321 μA mM 1 cm 2 in the range from 10 μM to 2 mM, a detection limit of 390 nM (S/N = 3) and a good stability.

Highlights

► CuO/TiO2 hierarchical heterojunction was prepared by electrospinning. ► Three-dimensional porous CuO/TiO2 electrode was fabricated on conductive glass. ► The electrode holds promising application in nonenzymatic glucose biosensing.

Introduction

For glucose oxidase (GOD) biosensor, due to the intrinsic nature of the enzymes and the tedious fabrication procedures of the enzyme electrodes, the stability and the reproducibility would be a problem. To overcome these drawbacks, nonenzymatic glucose biosensor has been proposed [1], [2], [3], [4], [5], [6], and reviewed by K. Toghill et al. recently [7], especially for CuO based one [8], [9], [10], [11]. Recent studies on glucose biosensor have been focused on the composites formed by metal or metal oxide nanoparticles and carbon nanotubes [12], [13], [14], [15], [16], [17], [18], [19]. However, seldom research has concerned with the hierarchical heterojunction formation between two oxide semiconductors, which has attracted great interests on the fields of photocatalysis, solar cells and gas sensing [20], [21], [22], [23]. It is expected that hierarchical heterojunction could improve the performance of the biosensors through the synergistic effect.

Among various methods to prepare hierarchical oxide nanostructures [24], [25], [26], electrospinning is a cost-effective and flexible platform for preparing one-dimensional nanowires/tubes. The electrospinning oxide semiconductors usually yield porous structure due to the remove of organic components in the annealing [27]. The sensors with porous structure usually exhibit good biosensing performance because of their higher active surface area and easier substrate penetration.

In this work, we first prepared a hierarchical heterojunction of single-crystalline CuO nanoplates on polycrystalline TiO2 nanotubes by electrospinning and electrospun it onto FTO glass directly to form three-dimensionally porous hierarchical composite modified electrode. The fabricated electrode represents a promising application in glucose detection due to its hierarchical components and porous structure.

Section snippets

Preparation of the samples

All chemicals used were analytical grade and without further purification. In a typical synthesis of CuO/TiO2 composites, 0.2 mL tetrabutyl titanate (Ti(OBu)4) was dissolved into 6 mL N,N-dimethylformamide (DMF), absolute ethanol and glacial acetic acid mixture (V:V:V = 1) with magnetic stirring at room temperature, 0.075 g citric acid (C6H8O7) was added after 10 min and stirred for 2 h, then cupric acetate (Cu(Ac)2) (0.2 g, 0.3 g and 0.4 g for samples A, B and C, respectively) was added. 12 h later, 0.8 g

Characterization of the samples

Fig. 1(a)–(c) shows the SEM images of the samples. It can be seen that samples A, B and C are all nanocomposites, in which there are some small nanoplates (NPs) (several ten to one hundred nanometers in diameter) attached randomly on the surface of the NTs, whose outer diameters are ~ 200 nm. Sample C was further examined by TEM (Fig. 1(d)) and HRTEM (Fig. 1(e)) images. The TEM image further indicates the tube-like trunk structure with well-dispersed NPs on the surface of them. From the HRTEM

Conclusions

In conclusion, CuO/TiO2 hierarchical nanostructure was first prepared by electrospinning method, and a three-dimensional modified electrode was fabricated using to detect glucose. Amperometric glucose sensing experiments ranging from 0.01 to 2 mM revealed that the CuO/TiO2 electrode exhibited a high sensitivity (1321 μA mM 1 cm 2) and low detection limit (390 nM) and good stability. It holds the promise for the development of nonenzymatic glucose sensor.

Acknowledgements

The authors are thankful for the financial support of the National Science Fund for Distinguished Young Scholars of China (Grant No. 60925018), the National Natural Science Foundation of China (Grant Nos. 51002062 and 20971051) and the Opened Fund of State Key Laboratory on Integrated Optoelectronics.

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