Effect of different copper sources on the morphology of cuprous oxide and its application as a non-enzymatic glucose sensor
Introduction
Diabetes is a chronic disease caused by long-term high blood glucose level, which can also trigger a series of complications such as heart disease, blindness, and kidney failure [1]. Continuous and effective monitoring of blood glucose levels is important for diabetic patients. However, currently commercially available blood glucose monitoring devices are enzyme sensors, which are usually strict with the conditions of use and storage [2]. In recent years, some non-enzymatic glucose sensors based on noble metal have been reported [[3], [4], [5]]. Due to the absence of biomolecules, the requirements for the use and storage environment have been solved, however, there are still problems of poor selectivity, high cost and being poisoned easily [6]. Transition metal oxides have been reported for non-enzymatic glucose detection due to their high reactivity, low price and susceptibility to poisoning [[7], [8], [9], [10]]. What’s more, the morphology of some metal oxides can be effectively controlled, which is of great significance in the field of glucose sensors [11], since different morphology of the same material usually exhibits different physicochemical properties. This interesting phenomenon has spurred researchers' interest in the morphology-dependent behavior of metal oxides. Some of metal oxides such as ZnO [12], TiO2 [13], Cu2O [[14], [15], [16]]/CuO [17] and Co3O4 [18] have been widely investigated. Among those, Cu2O has attracted a great deal of attention.
Cuprous oxide (Cu2O) as a typical direct bandgap (Eg = 2.17 eV) semiconductor has been widely used in many fields, such as photovoltaics [19], catalysis [20], gas sensors [21] and biosensor [22]. Moreover, Cu2O is environmentally friendly, inexpensive, and easy to prepare in various morphologies (such as cubes [[23], [24], [25]], spheres [26] and octahedrons [[27], [28], [29]]). X F Zhang et al [30] synthesized three Cu2O microcrystals (spheres, octahedrons, and truncated octahedrons) via a simple electrochemical route by successfully controlling the electrodeposition temperature. Y H Tsai et al [31] studied the effect of volume of hydrazine on Cu2O morphology, and obtained three morphologies of Cu2O (cubes, octahedrons, and octapods). D F Zhang et al [32] reported the effect of amount of surfactant (PVP) on the morphology of Cu2O, they insist that PVP is preferentially adsorbed on the (111) facets of Cu2O, so that the different facets formation speed which usually lead to different crystal morphology can be controlled by adjusting the amount of PVP.
Although many efforts have been paid to control the morphology of Cu2O, on the one hand, the samples they obtained are all independent structures with specific morphology (such as cubes, octahedrons, spheres and so on). Compared with traditional growth process, Cu2O formed by self-assembly usually has a special morphology, which may be a supplement to the study of Cu2O morphology. In addition, special morphology usually leads to different performance. On the other hand, most reports are generally concentrated on different surfactants or reducing agents. However, different copper sources usually carry different anions, and these anions usually have a certain influence on the morphology of Cu2O. Therefore, it is necessary to study the influence of different copper sources on the morphology of Cu2O.
In this work, we successfully synthesized Cu2O with different morphology by simply adjusting the copper sources. We first synthesized a stacked octahedron shape Cu2O that was stacked by the self-assembly of cubic Cu2O and studied its formation mechanism. As shown in Scheme 1, the Cu2O cubes and Cu2O stacked octahedrons exhibit electrocatalysis toward glucose oxidation. The S-Cu2O modified electrode showed relatively high sensitivity and the N-Cu2O modified electrode exhibited wide linear range, low detection limit, excellent selectivity and long-term stability due to its special stacked octahedral structure. In addition, the obtained sensor can be used in the human blood serum samples. Owing to these obvious advantages, the modified electrode has a promising prospect in practical applications.
Section snippets
Chemicals
Sodium hydroxide (NaOH), copper sulfate pentahydrate (CuSO4·5H2O), copper chloride dihydrate (CuCl2·2H2O), copper nitrate trihydrate (Cu(NO3)2·3H2O), copper acetate monohydrate (Cu(Ac)2·H2O), sodium dodecylbenzenseulfonate (SDBS), D-(+)-glucose, sodium ascorbate (SA), uric acid (UA), dopamine (DA), galactose, ascorbic acid (AA), sodium chloride (NaCl), fructose and potassium chloride (KCl) were purchased from Macklin Reagent. All chemicals were analytically grade and required no further
Structural and compositional characterizations
Fig. 1a shows the XRD patterns of all samples, three obvious diffraction peaks are observed at the 2θ values of 36.5°, 42.4° and 61.5° for all samples, which are respectively related to the diffractions of the (111), (200) and (220) crystalline planes of Cu2O powder (JCPDS, No. 65-3288). No other obvious diffraction peaks are detected in these prepared samples, which indicates the high purity of the as-synthesized samples. Fig. 1b shows the XPS survey spectrum of S-Cu2O, the XPS spectrum
Conclusion
In summary, Cu2O cubes and stacked octahedrons were successfully synthesized by simply adjusting the sources of copper via a seed-medium process. The morphology and formation mechanism of the obtained samples were investigated. Moreover, the obtained Cu2O were further fabricated as nonenzymatic glucose biosensor. All electrodes exhibited fast electrocatalytic response (<1 s) toward glucose oxidation. S-Cu2O modified electrode exhibited the highest sensitivity (2864 μA mM−1 cm-2), N-Cu2O
Credit author statement
All authors of this manuscript have directly participated in planning, execution, or analysis of this study.
The contents of this manuscript have not been copyrighted or published previously.
The contents of this manuscript are not now under consideration for publication elsewhere.
Declaration of Competing Interest
We declare that we have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper
Acknowledgments
This work is supported by the National Natural Science Foundation of China (61961116), China Postdoctoral Science Foundation (2018M631801), Fundamental Research Funds for the Central Universities (N170203007) and Postdoctoral Foundation of Northeastern University (20180301).
Wenbin Liu is pursuing his Ph.D. in the School of Materials Science and Engineering, Northeastern University. His research interests include glucose biosensor and electrochemistry sensor.
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2022, Journal of Alloys and CompoundsCitation Excerpt :The beverages were bought from local supermarket. Cu2O stacked octahedrons were synthesized via a simple seed-medium process, which has been reported in our previously work [27]. The glassy carbon electrodes (GCE, Ф = 3 mm) was selected as the initial electrode for modification of Cu2O.
Wenbin Liu is pursuing his Ph.D. in the School of Materials Science and Engineering, Northeastern University. His research interests include glucose biosensor and electrochemistry sensor.
Yuxiang Dai is working as lecturer in the School of Materials Science and Engineering, Northeastern University. He received his Ph.D. degree in 2017 in the College of Physics, Jilin University.
Yang Qi is working as Professor in the School of Materials Science and Engineering, Northeastern University. He received his Ph.D. degree in 2000 in the Department of Electrical Engineering, Faculty of Engineering, Osaka University.