A general cation-exchange strategy for constructing hierarchical TiO2/CuInS2/CuS hybrid nanofibers to boost their peroxidase-like activity toward sensitive detection of dopamine
Graphical abstract
Hierarchical TiO2/CuInS2/CuS hybrid nanofibers have been prepared as peroxidase-like catalyst for dopamine detection.
Introduction
Natural enzymes have been broadly applicable in a large variety of catalytic processes especially for molecular transformation in biological systems with an ultrahigh efficiency and selectivity [1]. However, they possess intrinsic disadvantages of high cost, poor environmental stability and difficulty in separation and storage [2]. To overcome these shortcomings, much work focuses on the fabrication of various types of artificial enzymes during the past period of time [3], [4]. Most interestingly, some functional nanomaterials, such as noble metals, carbon nanomaterials, metal oxides, and metal sulfides, etc., are demonstrated to present a certain enzyme-like property, which are named as nanozymes [5], [6], [7], [8], [9]. Among the developed nanozymes, metal sulfides have aroused strong interests in many fields due to their multiple active sites, desirable catalytic activity, and excellent environmental stability [10], [11]. Recently, a series of metal sulfide nanomaterials with different architectures have been developed to present favorable enzyme-like properties [12], [13], [14]. In comparison with single-component metal sulfides, bimetallic ones have attracted more attention for their enhanced enzyme-like performance resulting from a better electrical conductivity, larger active sites, and superior redox reversibility. Up to now, many studies on the fabrication of bimetallic sulfides for enzyme mimicking have been reported, including ZnxCo1-xS, (CoxM1-x)9S8 (M = Ni, Cu), NiFeS2, CoMoSx, Co8FeS8, (Co0.75Ni0.25)9S8, and CuInS2, etc. [15], [16], [17], [18], [19]. Another efficient route to enhance the enzyme-like efficiency of metal sulfides is to construct hybrid nanomaterials with multiple components to regulate their affinity with the enzyme substrates and the electronic structure from the generated interface among different components [20], [21], [22], [23], [24]. However, it is still a challenge to design and fabricate metal sulfides-based hybrids with a unique architecture to present a synergistic catalytic effect toward enhanced enzyme-like properties.
In this work, we have developed a general cation-exchange strategy to construct hierarchical ternary TiO2/CuInS2/CuS nanofibers. In this hybrid system, TiO2 nanofibers with a high aspect ratio act as the support to load In2S3 nanosheets, benefitting for the achievement of a cation-exchange reaction to form CuInS2/CuS nanosheets on their surface. Owing to the synergistic effect among TiO2, CuInS2 and CuS components, the prepared TiO2/CuInS2/CuS nanofibers exhibit a superior peroxidase (POD)-like activity compared with the control samples including bare TiO2 nanofibers, In2S3 nanosheets, TiO2/In2S3 nanofibers, and CuInS2/CuS nanosheets. Furthermore, the amount of the CuCl2 feeding source is also optimized to boost the POD-like activity. Based on the excellent catalytic performance, a facile and convenient route to determine dopamine (DA) with a detection limit of 1.2 μM has been developed. This study establishes an innovative synthetic way to prepare uniform ternary metal sulfides-based hybrids to boost the POD-like activity with a synergistic catalytic effect, providing a promising prospect toward highly sensitive biosensing application.
Section snippets
Preparation of TiO2/In2S3 nanofibers
Firstly, TiO2 nanofibers were fabricated through an electrospinning procedure based on the previous reports [24], [25]. Typically, a mixing solution containing 0.5 g of polyvinylpyrrolidone (PVP) (Aldrich, Mw = 1300 000 g mol−1) and 1.0 g of tetrabutyl titanate (Sinopharm Chemical Regent Co., ltd.) in 7 mL ethanol and 2 mL of acetic acid is prepared for electrospinning under 18 kV. After that, the resultant membrane was calcined in air at 470 °C for 2 h to obtain TiO2 nanofibers. In the
Results and discussion
The synthetic procedure of TiO2/CuInS2/CuS nanofiber is presented in Fig. 1a, which is mainly involved in three steps. First, TiO2 nanofibers are fabricated via an electrospinning and subsequent calcination process, which present uniform fiber-like morphology and smooth surface with diameters in the range of 130–240 nm (Fig. 1b and c). Second, a uniform growth of In2S3 nanosheets on the surface of TiO2 nanofibers is realized via a hydrothermal reaction, which enables to avoid the
Conclusions
In this work, a hierarchical TiO2/CuInS2/CuS hybrid nanofiber with a core-sheath morphology has been constructed via an electrospinning-calcination-hydrothermal reaction and cation-exchange process. The obtained TiO2/CuInS2/CuS hybrid nanofibers display excellent POD-like properties compared to the control samples due to their unique 1D nanofibrous structure and synergistic effect among the three components. Based on the desirable POD-like activity of the hierarchical TiO2/CuInS2/CuS hybrid
CRediT authorship contribution statement
Wendong Zhu: Conceptualization, Investigation, Data curation. Ya Cheng: Visualization. Su Yan: Formal analysis. Xiaojie Chen: Formal analysis. Ce Wang: Supervision. Xiaofeng Lu: 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.
Acknowledgement
This work was financially supported by the National Natural Science Foundation of China (51973079, 21875084).
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