Fabrication of the Ni-based composite wires for electrochemical detection of copper(Ⅱ) ions
Graphical abstract
Introduction
Cu2+ is an essential element in living organisms and plays an important role in body functions [1,2]. Nevertheless, excess Cu2+ intake can cause Wilson, Alzheimer’s and Menkes diseases [3,4]. The potential toxic effects of Cu2+ to human beings continue to be a global challenge as its pollution in rivers or sea. It is important for clinical research, food industry and environmental monitoring to develop an efficient method for the trace detection of Cu2+ [5,6].
Various techniques for detecting Cu2+ have been developed, including inductively coupled plasma atomic emission spectroscopy (ICP-AES) [7], flameless atomic absorption spectroscopy (FAAS) [8] and atomic absorption spectroscopy (AAS) [9]. Although they are sensitive and selective, they require relatively expensive instruments, complicated procedures and long time. Electrochemical analysis methods have attracted much attention because of its simple operation, fast response and high sensitivity. The current electrochemical method for detection of Cu2+ is adsorptive stripping voltammetry (ASV) [10], but it is an indirect and complex process involving enrichment and dissolution. Therefore, it is desired to develop a direct electrochemical method for online detection of Cu2+.
In recent years, the fabrication of semiconductor heterojunctions has become a focus of attention in improving the electronic performance in the applications of solar cells, sensors, catalytic reduction and so on [[11], [12], [13], [14]]. For example, the prepared Co3O4–ZnO core-shell nanofibers showed the improved gas sensing performance to formaldehyde [15]. The heavily doped Si p-n junction nanowires show a highly localized sensitive area at the interface, which can be used for intracellular recording [16]. Moreover, Wang’s research team reported that the use of Schottky contacts could obtain the highly sensitive and fast-responsive field-effect transistor devices [17]. All of these demonstrate that the formation of special semiconductor interfaces has a significant impact on the sensing function. Therefore, the rational design of semiconductor heterojunction may provide a new opportunity for heavy metals detection.
With the development of nanotechnology, the metal oxides nanostructures have become a kind of promising electrochemical sensing material due to their easy availability, excellent electronic properties and chemical stability. Among them, NiO, a wide band gap p-type semiconductor material (Eg = 3.55 eV), is widely studied in catalysts and sensors due to its well catalytic and sensing performance [18]. ZnO, a wide band gap n-type semiconductor (Eg = 3.37 eV), has been recognized as a good sensing material due to its high photosensitivity, excellent electronic transmission characteristics [19]. Since both NiO and ZnO have the wide band gap, the formed p-n junction has a large adjustable range of the electronic characteristics. In addition, Au nanoparticles decorated metal oxides can form Schottky junction and obtain the special electronic characteristics [[20], [21], [22]]. Chitosan (CS) is a polymer material with strong adhesion and film-forming ability. Because it is rich in hydroxyl and amino active functional groups, it opens up possibilities for various chemical modifications such as acylation, chelation, graft copolymerization, and crosslinking. And it shows excellent selective adsorption properties for Cu2+ in solution [23,24].
In this work, the Ni/NiO/ZnO/CS and Ni/NiO/Au/CS wires were successfully fabricated and used for the direct electrochemical detection of Cu2+. The electrochemical signal was produced by the adsorbed Cu2+ induced change of the barrier height and exhibited the excellent stability and recovery rate in the real water samples. It is promising to be applied in the direct detection of Cu2+ in the actual water environment by employing the interfacial barrier effects on electrochemistry.
Section snippets
Reagents and chemicals
All reagents stated below were of analytic grade and used without further purification. KCl, NaCl, AgCl, Hg(NO3)2, BaSO4, NiSO4·6H2O, ZnSO4·7H2O, CoSO4·7H2O, Pb(NO3)2 and Al2(SO4)3•18H2O were supplied by Aladdin Chemistry Co. Ltd. Nickel wire (diameter ∼ 0.8 mm) purchased from Hengxin research Metal Co., Ltd. CuSO4 was purchased from Bodi Chemical Co. Ltd. (Tianjin, China). Chitosan (viscosity 100–200 mPa s) was purchased from Aladdin Chemistry Co. Ltd. Deionized (DI) water with a resistivity
Characterization of the Ni/NiO/ZnO/CS wire and the Ni/NiO/Au/CS wire
The surface of the Ni wire is uniform after the high temperature oxidation (Fig. 1a), and the obtained NiO layer has a regular grain arrangement with the grain size about 1.5 μm (Fig. 1b). As shown in Fig. 1c, ZnO nanoflower clusters are fully loaded on the surface of the Ni/NiO wire after hydrothermal synthesis, which are composed of regular hexagonal nanorods with the length about 10 μm and the diameter about 0.1–1.5 μm. ZnO nanoflower clusters can also partially cover on the surface by
Conclusion
In summary, Ni-based composite wires were successfully fabricated and used for the direct electrochemical detection of Cu2+. The direct electrochemical response can be driven by the interfacial barriers of semiconductor heterojunctions, and different types of interfacial barriers can produce different detecting performance. This novel electrochemical sensing mechanism achieves the low detection limit (0.81 nM), the wide detection range (0–6000 nM) and the excellent anti-interference ability.
CRediT authorship contribution statement
Jiatuo Yu: Conceptualization, Methodology, Investigation, Data curation, Visualization, Writing - original draft. Xiaomin Zhang: Investigation, Data curation, Visualization. Minggang Zhao: Conceptualization, Supervision, Funding acquisition, Writing - review & editing. Yu Ding: Data curation, Visualization. Zhengming Li: Data curation, Visualization. Ye Ma: Supervision, Funding acquisition. Hui Li: Conceptualization, Supervision. Hongzhi Cui: Conceptualization, Supervision.
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 sponsored by Fundamental Research Funds for the Central University (202042009 and 201964011). National Natural Science Foundation of China (Grant No. 61804087), the Natural Science Foundation of Shandong Province (ZR2019QF015).
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Author Contributions: These authors contributed equally.