Elsevier

Electrochimica Acta

Volume 229, 1 March 2017, Pages 129-140
Electrochimica Acta

CuO nanoparticles decorated nano-dendrite-structured CuBi2O4 for highly sensitive and selective electrochemical detection of glucose

https://doi.org/10.1016/j.electacta.2017.01.130Get rights and content

Abstract

In this study, a chemically modified electrode, consisting of CuO nanoparticles decorated nano-dendrite-structured CuBi2O4 (nanoCuBi2O4|CuO), was fabricated and its application as an electrocatalyst in catalyzing the oxidation of glucose was investigated. nanoCuBi2O4|CuO was fabricated by firstly electrodepositing BiOI nanosheet array (nanoBiOI) on the flourine-doped tin oxide coated glass substrate, followed by its conversion into nanoCuBi2O4|CuO via drop-casting an ethanolic Cu2+ solution and follow-up thermal treatment. The degree of conversion of nanoBiOI into nanoCuBi2O4|CuO and electrocatalytic activites of resultant nanoCuBi2O4|CuO were controlled by adjusting the dosage of the ethanolic Cu2+ precursor solution. Surface morphology, structure, crystal phase, chemical composition, and electrocatalytic properties of the nanoCuBi2O4|CuO were characterized using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, cyclic voltammetry, linear sweep voltammetry, and chronoamperometry. It was found that both CuO and CuBi2O4 are active in electrocatalyzing the oxidation of glucose, but the porous structure of nanoCuBi2O4|CuO along with the synergistic catalytic enhancement, exerted by CuBi2O4 and CuO, renders nanoCuBi2O4|CuO superior electrocatalytic activity than CuO or CuBi2O4 alone. The mechanism of electrocatalytic oxidation of glucose on nanoCuBi2O4|CuO is proposed. Finally, the sensing characteristics of nanoCuBi2O4|CuO was evaluated, and the results indicate nanoCuBi2O4|CuO is a promising sensing material for the electrochemical detection of glucose.

Introduction

Diabetes mellitus has become a worldwide health problem and its associated complications are a leading cause of death in the world [1]. As monitoring the glucose level in the blood is the first step for the diagnosis of diabetes mellitus and routine monitoring of blood glucose is required further management of diabetes mellitus, development of a rapid and reliable sensing platform for the detection of blood glucose is urgently required. The first generation of glucose biosensor was proposed by Clark and Lyons in 1962 [2]; the sensing principle of the proposed devices is based on the measurement of oxygen consumption by the platinum electrode with immobilized glucose oxidase (GOD) during the reaction of glucose with glucose oxidase (GOD) in presence of the dissolved oxygen (Eqs. 1-2) [3]:glucose+O2GODglucono-δ-lactone+H2O2O2+4H++4e2H2O

Since then, significant progress has been made to improve the sensing characteristics, such as sensitivity and selectivity, of this type of glucose sensors. Nevertheless, due to the drawbacks inherent to the enzyme based sensors, including complicated immobilization procedure, high cost, and instability, many efforts have been directed to develop the enzyme-free glucose sensor recently [4], [5], [6]. To this end, many materials, including noble metals [7], [8], [9], [10], [11], [12], transition metals [13], [14], [15], [16], [17], transition metal oxides and hydroxides [18], [19], [20], [21], [22], [23], [24], [25], have been explored and investigated. Noble metals offer high sensitivity, but their scarcity, low selectivity, and tendency to be poisoned by chloride ions and intermediates generated during the oxidation of glucose limit their practical applications [26]. Among the transition metals and their oxides explored so far, copper based nano-materials (nanoCu), including metallic copper [27], [28], [29], [30], copper hydroxide [31], and copper oxides (CuO [25], [32], [33], [34], [35] and Cu2O [36], [37], [38], [39]) have received much attention as they are earth-abundant, low-cost, easily synthesized, high activity, and most importantly, immune to poisoning species [27], [31], [35]. Though the mechanism for electrocatalytic oxidation of glucose by nanoCu is still under debate, the most accepted mechanism has been ascribed to the interaction between glucose and the high-valent Cu3+ species, in the form of oxides or hydroxides, generated under highly anodic condition in the alkaline electrolyte [40]. In addition, in order to further enhance the sensing performance, some efforts have been directed to synthesize a composite with other materials by preparing alloy-metals [41], [42], [43], [44], [45], [46] or directly depositing nano-sized copper materials (nanoCu) onto the nanostructured matrix [41], [47], [48], [49], [50], [51], [52], [53], [54], [55], [56], [57], [58], [59], [60]. In case of alloy-metals, the enhancement in the sensing performance can be attributed to the synergistic effects of multi-composition interface, whereas in the case of nanoCu modified nanostructured matrix material, the enhancement in the sensing performance can attributed not only to the fact that the synergistic effects through the interaction of nanoCu with the matrix material can be induced, but also to the fact that the minimal aggregation of nanoCu along with the high loading amount of nanoCu can be achieved by the virtue of the high surface area of the matrix material. Nevertheless, the preparation of these copper based nanocomposites often involves the tedious synthetic procedure [47], [48], [49], [50], [51], [52], [53], [54], [55], [56], [58], and instead of direct deposition onto the electrode surface, some of these nanocomposites were synthesized in powder form [47], [48], [49], [50], [51], which would not only cause the irreproducibility due to the un-controllable aggregation of these nanocomposites, but also require additional immobilization procedure and thus complicate the electrode preparation procedure.

On the other hand, due to its favorable conduction band level, excellent optical and catalytic properties, CuBi2O4, a p-type semiconductor, has been identified as a promising material in the field of photoelectrochemical water splitting [61], [62], [63], [64], photocatalysis [65], and the activation of peroxymonosulfate/persulfate [66], [67]. However, to our best knowledge, the electrocatalytic properties of CuBi2O4 and its composite with CuO towards the oxidation of glucose have not been investigated yet.

In this report, we report the fabrication of a highly porous nanocomposite of CuBi2O4 and CuO (nanoCuBi2O4|CuO) and its application in electrocatalytic oxidation of glucose. nanoCuBi2O4|CuO, consisting of CuO nanoparticles decorated nanodendrite-structured CuBi2O4, was synthesized by firstly growth of bismuth oxyiodide nanosheet array (nanoBiOI) onto the fluorine-doped tin oxide coated glass substrate (FTO) using electrochemical deposition, followed by drop-casting a Cu2+ solution onto nanoBiOI and subsequent annealing process to convert nanoBiOI into nanoCuBi2O4|CuO. The effects of the dosage of Cu2+ solution on the conversion of nanoBiOI, and structure along with the electrocatalytic activity of the resultant electrode were thoroughly studied. It was found synergetic effects of CuO with CuBi2O4 along with the highly porous nanostructure of CuBi2O4 render nanoCuBi2O4|CuO significantly enhanced electrocatalytic activity, in terms of overpotential and catalytic current, towards the oxidation of glucose as compared with the CuO and CuBi2O4 thin film alone. Finally, the excellent sensing performances, evaluated from sensitivity test and the interference test, suggest the applicability of nanoCuBi2O4|CuO in amperometric detection of glucose.

Section snippets

General consideration

Starting materials for the synthetic part of the work were purchased from commercial suppliers and of the highest available purity for the analytical work. Flourine-doped tin oxide (FTO) coated glass (sheet resistance 7 ohm sq−1, TEC GlassTM 7) substrates (1.0 × 3.0 cm2) were cleaned with an ammonia-hydrogen peroxide-deionized water mixture (volume ratio: 1:1:5) at 70 °C for 30 min, after which the FTO substrates were dried at room temperature under nitrogen purge. Glucose stock solutions (0.5 M),

Physical characterization

Figs. S1a and 1 , respectively, show the X-ray diffraction patterns of nanoBiOI template and the resultant electrodes converted from the nanoBiOI template with various dosages (D) of Cu2+ solution. It can be found that without drop-casting the Cu2+ precursor solution, i.e., D = 0 μL cm−2, nanoBiOI (JCPDS No. 73-2062) was converted into Bi2O3 (JCPDS No. 65-3319) after the annealing process. However, with the increase in the dosage of Cu2+ solution for the conversion process, the decrease in the

Conclusion

A chemically modified electrode, consisting of CuO nanoparticles decorated nano-dendrite-structured CuBi2O4 (nanoCuBi2O4|CuO), were successfully fabricated by using BiOI nanosheets array as the template. The electrocatalytic properties along with the sensing characteristics of nanoCuBi2O4|CuO towards glucose was thoroughly examined for the first time. It was found that both CuO and CuBi2O4 thin films are active in electrocatalyzing the oxidation of glucose, but the porous structure of nanoCuBi2O

Acknowledgements

Financial support from the Ministry of Science and Technology of Taiwan (104-2221-E-006-235- and 104-ET-E-006-004-ET) and Research Center for Energy Technology and Strategy, National Cheng Kung University are gratefully acknowledged.

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