Electrochemically switchable electrochemiluminescent sensor constructed based on inorganic perovskite quantum dots synthesized with microwave irradiation

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Highlights

  • Inorganic perovskite quantum dots (IPQDs) were synthesized by microwave irradiation.

  • The IPQDs exhibited electrochemically switchable electrochemiluminescence (ECL).

  • The IPQDs gave promise for constructing ECL sensors for H2O2 and dopamine detection.

Abstract

Microwave irradiation was employed to synthesize inorganic perovskite quantum dots (IPQDs) which were demonstrated to be monoclinic phase and behaved tunable photoluminescent emissions across the entire visible light spectrum. The microwave-based synthetic method was proved to be easy-operation, high-throughput and low-cost. These microwave-synthesized IPQDs exhibited electrochemically switchable electrochemiluminescence (ECL). Obvious ECL was obtained when holes were injected into the electron-injected IPQDs while almost no ECL was observed in the reverse process. ECL of IPQDs gave promise for constructing electrochemiluminescent sensors for hydrogen peroxide (H2O2) and dopamine (DA) detection. Linear relationships between ECL intensities and H2O2/DA concentrations were detected and satisfactory correlation coefficients were obtained. Our results shed the light on the ECL sensing application of the high-throughput microwave-synthesized IPQDs.

Graphical abstract

Microwave irradiation was employed to synthesize inorganic perovskite quantum dots which exhibited excellent electroluminescence and gave promise for constructing electroluminescent sensors.

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Introduction

Colloidal semiconductor nanocrystals (NCs) which also are known as quantum dots (QDs) have drawn intensive attentions as future optoelectronic materials [[1], [2], [3], [4]]. QD materials feature a very favorable combination of quantum-size effect, versatile surface chemistry and a “free” colloidal state which render them enhanced optical properties compared to their bulk counterparts [[5], [6], [7]]. Furthermore, the QDs with excellent and stable dispersion in a variety of solvents and matrices give promise of being incorporated into various devices [[8], [9], [10], [11]]. To date, the well-developed optoelectronic NCs in terms of size, shape, and composition are binary and multinary metal chalcogenide NCs. In contrast, the potential of semiconducting metal halides in the form of colloidal NCs remains rather unexplored. Recently, CsPbX3 (X = Cl, Br, I, mixed Cl/Br and Br/I systems) as one kind of inorganic perovskite quantum dots (IPQDs) are widely investigated due to their high photoluminescence (PL) quantum yields [12,13]. These ternary compounds give tunable emissions across the entire visible light spectrum through component, morphology or size regulation [14]. However, there are limited methods available to synthesize IPQDs. The most widely used method is the high-temperature hot injection which needs to quench reaction during a very short time (5 s) causing thermal and concentration gradients of the bulk solution [[15], [16], [17]]. Size distribution of the obtained IPQDs is broad due to the fast and uncontrollable nucleation process [14]. In addition, the procedure of the hot injection method is complex and the yield is low. Various IPQDs need to be synthesized one by one. It is urgent to develop a facile, controllable and high-throughput method for IPQD synthesis.

Electrochemiluminescence (ECL) is an electrochemically triggered light emission process caused by energy relaxation of ionized materials. This technique essentially reveals the relationship between electrochemistry and spectroscopy [18]. IPQDs not only exhibited excellent PL properties but also demonstrated superior electroluminescence (EL) performance [19]. It is anticipated to explore the ECL performance of IPQDs. ECL of various NCs has been reported, such as Si NCs [20], CdTe [21], CdSe [22] QDs and nanoclusters [23,24]. However, ECL performance of IPQDs is scarcely investigated. The possible reasons are the instability of IPQDs in polar solvents and the insolubility in nonpolar solvents used in ECL characterization. Recently, CsPbBr3 NCs have been explored as one kind of novel ECL emitter [[25], [26], [27]]. Nevertheless, most of the researches are focused on samples with cubic or orthorhombic phase which are synthesized by hot-injection method [[28], [29], [30], [31]].

Here, microwave irradiation was employed to conveniently synthesize IPQDs in a heterogeneous solid-liquid reaction system without precursor preparations (Fig. 1). The synthetic method is one-step, efficient and high-throughput. Multiple kinds of IPQDs with different sizes and emissions could be achieved in minutes. A large quantity of IPQDs was obtained through once operation. The resulted CsPbBr3 IPQDs are demonstrated to be monoclinic and further proved to display efficient ECL with electrochemically switchable features. Effective ECL sensors for H2O2 and dopamine (DA) detection were successfully constructed based on the CsPbBr3 IPQDs.

Section snippets

Material and reagents

Cesium carbonate (Cs2CO3, 99%), lead bromide (PbBr2, 99%), lead chloride (PbCl2, 99%), lead iodide (PbI2, 99%) 1-octadecene (ODE, 90%), oleic acid (OA, 90%), and oleylamine (OAm, 70%) were all brought from Sigma-Aldrich Chemical Reagent Co., Ltd. (Shanghai, China). Tri-n-propylamine (TPrA, 99%), cyclohexane (C6H12, 90%), tetrabutylammonium hexafluorophosphate (TBAPF6, 99%), dichloromethane (CH2Cl2, HPLC), DA (99.9%) and hydrogen peroxide (H2O2, 30 wt%) were all purchased from Aladin Co., Ltd.

Microwave synthesis of IPQDs

As shown in Fig. 1, a household microwave oven was utilized to synthesize a series of IPQDs through a one-step operation. High quality IPQDs were obtained by virtue of heating effect generated through the interaction of the dipole moment of the liquid molecules with the high frequency electromagnetic radiation [[32], [33], [34], [35]]. The growth mechanism of IPQDs was systematically studied. At first, corner-sharing PbBr6 octahedra formed a scaffold which was further filled with Cs ions and

Conclusions

In summary, monoclinic IPQDs were successfully synthesized through microwave irradiation. This synthetic method was simple, controllable and high-throughput. A series of IPQDs with tunable properties and morphologies were obtained through once operation in a heterogeneous reaction system. The obtained IPQDs were demonstrated to be ECL emitter candidates. Strong ECL was observed by turning electron injecting process to hole injecting process while almost no ECL was given in the reverse way. This

CRediT authorship contribution statement

Yufei Wang:Investigation, Writing - original draft.Tianyou Chen:Investigation.Chunxia Huang:Investigation.Yanran Wang:Investigation.Jing Wu:Investigation, Writing - review & editing.Bing Sun:Writing - review & editing.

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 supported by the National Natural Science Foundation of China (No. 21874120) and the Fundamental Research Funds for the Central Universities (No. 2652018004).

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