MnO2/multi-walled carbon nanotubes based nanocomposite with enhanced electrocatalytic activity for sensitive amperometric glucose biosensing

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Abstract

Functional nanostructured transition metal oxides hold great promise in catalysis based sensors due to their superb catalytic activity, good stability, ease of preparation and cost-effectiveness. In this work, MnO2 nanowires and MnO2/multi-walled carbon nanotubes (MWCNTs) nanocomposite were prepared via a simple hydrothermal method. The MnO2/MWCNTs nanocomposite was developed by deposition of MnO2 on MWCNTs surface, which have abundant hydrophilic groups facilitating ion-adsorption and nucleation process. The MWCNTs/MnO2 exhibited higher catalytic activity upon hydrogen peroxide (H2O2) electrooxidation, with reduced overpotential by 100 mV and 220 mV in contrast to those values of MWCNTs and MnO2 nanowires, respectively. Thus the MnO2/MWCNTs nanocomposite modified glass carbon electrode (GCE) enabled to detect H2O2 sensitively. Moreover, by incorporation of glucose oxidase (GOx), a glucose biosensor GOx/MnO2/MWCNTs/GCE was prepared. The as-proposed biosensor had wide linear range (5–200 μM and 0.2–1 mM) and a low detection limit of 2 μM (S/N = 3), which could be applicable to detect real sample with satisfying accuracy and reproducibility. Due to the superb electrochemical properties, the as-developed MnO2/MWCNTs nanocomposite is prospected in electrochemical sensor, electrocatalysis and supercapacitor.

Introduction

Glucose sensing plays a vital role in various fields including clinical diagnostics, chemical, biological, fermentational and bioenergy industries [1]. Compared to spectroscopic and chromatographic methods, electrochemical based glucose sensors have been widely studied due to their cost-effectiveness, simple steps and easy operation [2]. Among them, glucose oxidase (GOx) based glucose sensing has attracted increasing attention thanks to their high selectivity and good biocompatibility, unfortunately, they are affected by pH, interferences, applicability and repeatability [3]. To address these issues, noble metal nanoparticles and metal oxide nanoparticles with good peroxidase-like activity, have received extensive attention and explored for glucose sensing [[4], [5], [6]].

Until now, transition metal oxides (e.g. MoO3, MnO2, Mn3O4, Co3O4, V2O5, Cu2O and NiO) based nanostructures have been reported to demonstrate low-cost and good catalytic activity, which have been applied in biosensing, oxygen reduction, hydrogen revolution, Li-O2 battery and supercapacitors [[7], [8], [9], [10], [11], [12], [13], [14]]. Especially, manganese dioxide (MnO2) has received extensive attention owing to its low cost, low pollution and high catalytic activity [15,16]. Nevertheless, manganese dioxide suffers from poor electrical conductivity, and therefore its utilization rate is relatively low. By the fabrication of nanocomposites incorprating conducting polymers or carbon materials as supporting matrix, both of the utilization and conductivity of manganese dioxide can be improved. Unfortunately, when combined with conducting polymers [17,18], the chemical and mechanical stability of the corresponding composite materials are relatively poor. To overcome the above problems, nanocomposites containing carbon materials become popular, which can not only prevent manganese dioxide agglomerating, but also promote electron transfer during the redox process [19,20]. Particularly, carbon nanotubes (CNTs) exhibit many outstanding features, such as good electrical conductivity, superb mechanical strength, high surface area and high electrochemical stability [21,22], which may show great potential in constructing transition-metal-oxide/CNTs nanocomposites with remarkable performance.

Herein we report a simple hydrothermal method for the synthesis of MnO2 nanowires and MnO2/multi-walled carbon nanotubes (MWCNTs) nanocomposite. Using KMnO4 and MnSO4 as manganese source, the MnO2/MWCNTs nanocomposite is developed by deposition of MnO2 on the MWCNTs surface, which have abundant hydrophilic functional groups to facilitate ion-adsorption and nucleation. The combination of MnO2 and MWCNTs makes the nanocomposite capable of taking full advantages of superb electrical conductivity, good electrochemical stability, and high surface area. The MnO2/MWCNTs nanocomposite exhibits superb electrocatalytic activity upon H2O2 oxidation with much lower overpotential, compared with their counterparts of MWCNTs and MnO2 nanowires. The as-prepared MnO2/MWCNTs nanocomposite modified electrode is capable of detecting H2O2 with the detection limit of 0.8 μM. By combining with GOx, an amperometric glucose biosensor is developed with excellent performance, and applicable to glucose detection in human serum samples accurately and reproducibly.

Section snippets

Chemicals and materials

KMnO4, MnSO4, H2O2 (30%), K3[Fe(CN)6], NaCl, KCl, Na2HPO4, KH2PO4, maltose, ascorbic acid (AA) and glucose were purchased from Sinopharm Chemical Reagent Co. Ltd. (Shanghai, China). MWCNTs with a diameter of 60–100 nm were obtained from Nanotech Port Co. Ltd. (Shenzhen, China). Dopamine (DA), uric acid (UA), Nafion (5%), polyacrylic acid (PAA) and GOx were purchased from Aladdin Chemical Co. Ltd. (Shanghai, China).

Preparation of MnO2 and MnO2/MWCNTs nanostructures

For the synthesis of MnO2, KMnO4 (38.4 mg) and MnSO4 (61.6 mg) in a molar ratio

Synthesis and characterization of MnO2 nanowires and MnO2/MWCNTs nanocomposite

We developed a simple hydrothermal method to prepare MnO2 nanowires and MnO2/MWCNTs nanocomposite. As displayed in Fig. 1A–C, MnO2 nanoparticles are well deposited on MWCNTs surface with an average size of 112 nm (Fig. 1D), which is different from bare MWCNTs and MnO2 nanowires (Fig. S1, Supplementary material). Furthermore, EDS mapping analyses show that the elements of C, O and Mn are uniformly distributed on the whole images (Fig. 1E–H), and the composition proportions of C, O and Mn (Fig. 1

Conclusion

In summary, we prepared MnO2 nanowires and MnO2/MWCNTs nanocomposite via a simple hydrothermal method. In the presence of KMnO4 and MnSO4, MnO2/MWCNTs nanocomposite was developed by deposition of MnO2 on the MWCNTs surface, which have abundant hydrophilic groups for ion-adsorption and nucleation process. The overpotential upon H2O2 electrooxidation by MnO2/MWCNTs nanocomposite was 100 mV and 220 mV lower than those values by MWCNTs and MnO2 nanowires, respectively, indicating that MnO2/MWCNTs

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

This work was financially supported partially by National Natural Science Foundation of China (No. 81673172), Major Program of Shandong Province Natural Science Foundation (ZR2018ZC0125), and State Key Laboratory of Analytical Chemistry for Life Science (SKLACLS1906).

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