Chemiluminescence of CsPbBr3 perovskite nanocrystal on the

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Chemiluminescence of CsPbBr3 perovskite nanocrystal on the hexane/water interface Yongchao Fan, Huanhuan Xing, Qingfeng Zhai, Daoqing Fan, Jing Li, and Erkang Wang Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.analchem.8b03249 • Publication Date (Web): 04 Sep 2018 Downloaded from http://pubs.acs.org on September 4, 2018

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Analytical Chemistry

Chemiluminescence of CsPbBr3 perovskite nanocrystal on the hexane/water interface

Yongchao Fan,a,b Huanhuan Xing,a,b Qingfeng Zhai,a,c Daoqing Fan,a,c Jing Li,a,* Erkang Wang a,*

[a] State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin, 130022, P. R. China. [b] University of Science and Technology of China, Hefei, Anhui, 230026, P. R. China [c] University of the Chinese Academy of Sciences, Beijing, 100039, P. R. China. *Corresponding author: Assoc. Prof. Jing Li* and Prof. Erkang Wang*, Tel: +86-431-85262003, Email: [email protected] and [email protected]

ABSTRACT All-inorganic halide perovskite CsPbBr3 nanocrystals (NCs) have attracted more attention in recent years due to the unique optical feature. Up to date, most of research was mainly focused on the photoluminescence (PL) and electrochemiluminescence (ECL) of the perovskite NCs. In this work, the strong chemiluminescence (CL) emission of CsPbBr3 NCs was observed for the first time on the hexane/water interface with the assistance of ammonium persulfate-(NH4)2S2O8 as co-reactant. Different co-reactants were investigated to demonstrate the effect on the CL behavior 1

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and it was found that CL intensity achieved the maximum in the presence of (NH4)2S2O8. In this system, electron transfer took place on the surface of the CsPbBr3 NCs and the excited CsPbBr3 NCs was originated from the direct chemical oxidation of (NH4)2S2O8. The CL spectrum of CsPbBr3 NCs was also collected and was consistent with their PL and ECL spectra, indicating that CsPbBr3 NCs played a role of luminophor during the CL process. The discovery of monochromatic CL of highly crystallized CsPbBr3 NCs not only extends the applications of halide perovskite materials in the analytical field but also provides a new route for the exploration of the physical chemistry properties. INTRODUCTION Halide perovskite nanocrystals (NCs) are promising materials due to their high photoluminescence quantum yield (QY up to 90%), narrow full width at half-maximum (fwhm), and tunable wavelength covering the entire spectrum of visible light.1,2 Compared with traditional NC3 and organic dyes, halide perovskite NCs-MPbX3 NCs (M=CH3NH3 or Cs; X=Cl, Br, I) have been widely used in various fields including solar cell, laser, electroluminescence (EL), electrochemiluminescence (ECL), and light emitting diode (LED) owing to their excellent photophysical properties.4-14 In the above-mentioned work, the halide perovskite NCs were often initiated via external energy such as excitation light source and applied voltage. Moreover, the poor stability of MPbX3 NCs against water restricted their possible applications in the analysis field.15,16 Therefore, studying the application of MPbX3 NCs in aqueous solution still faces great challenges. 2


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Chemiluminescence (CL) is an optical radiation phenomenon via a redox chemical reaction without assistance of the external excitation energy. Owing to the lower (absence of) background signal than fluorescence sensors17 and simpler set-up than ECL sensors,18 CL based sensing platforms have been widely used in DNA, nucleic acid and protein detection in recent decades.19 Especially, CL from the semiconductor nanomaterials due to the unique optical and catalytical feature, such as carbon dots,20 CdTe NCs21 and carbon nitride quantum dots (g-CNQDs)22 have attracted more attention in recent years. Although the good CL performance has been obtained using different semiconductor nanomaterials as functionalized units, the CL from the monochromatic MPbX3 NCs has so far not been reported, which may be attributed to the poor stability due to the intrinsic affinity of MPbX3 for moisture.15,23 Given the excellent optical properties, the CL response of the CsPbBr3 NCs was reported for the first time in this work. To our surprise, by simply mixing CsPbBr3 NCs (dispersed in the hexane) and (NH4)2S2O8 (dissolved in aqueous solution), strong CL emission was observed on the hexane/water interface without the aid of the excited light and an external voltage. All experimental conditions influencing the CL intensity have been simply optimized. The CL mechanism was explored in details and inferred that the CL emission was from the direct chemical oxidation of CsPbBr3 NCs by collecting corresponding UV-visible absorption, PL spectra, CL spectra, and transmission electron microscopy (TEM). The discovery of monochromatic CL of highly crystallized CsPbBr3 NCs may shed new light on the applications of halide perovskite materials, especially as a novel CL emitter for the analytical field. 3



EXPERIMENTAL SECTION

Chemicals and Reagents. Cesium carbonate (Cs2CO3, 99.99%), lead bromide (PbBr2, 99.9%), lead iodide (PbI2, 99.9%), oleic acid (OA, 85%), oleylamine (OAm, 80-90%), octadecene (ODE,＞90%) were purchased from Aladdin (Shanghai, China). (NH4)2S2O8 (AR), N-hexane (AR) were obtained from Beijing Chemical Reagent Company (Beijing, China). Poly (ethylene-glycol) diacrylate (PEGD), and 2-hydroxy-2-methylpropiophenone (initiator) were obtained from Sigma-Aldrich. All chemicals were received without any further purification. The water used in this experiment was deionized water (18 MΩ·cm−1) purified by a Milli-Q system (Millipore, Bedford, MA). Instrumentation. Absorption curves were recorded on a Cary 500 Scan UV-vis-NIR spectrometer (Varian). The fluorescence (FL) spectrum was collected on a Fluoromax-4 spectrofluorometer (Horiba Jobin Yvon Inc., France) with excitation and emission slit widths of 5 and 5 nm, respectively. Fluorescence visual photos of CsPbBr3 NCs were acquired under a hand-held UV lamp (365 nm, 8.0 W). The morphology of CsPbBr3 NCs was characterized by the JEOL 2100F TEM with an accelerating voltage of 200 kV. X-ray diffraction (XRD) spectra were obtained using a Bruker D8 ADVANCE instrument with Cu Kα radiation (40 kV, 40 mA). The CL experiments were carried out on the MPI-A capillary electrophoresis ECL analytical system (Xi’an Remax Electronics Science & Technology Co. Ltd.). Preparation of CsPbBr3 NCs 4


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Sample of CsPbBr3 NCs was obtained according to the method in the literature.2,10 As shown in the Scheme 1, the precursors of Cs-Oleate and Pb-precursor need to be prepared before the synthesis of the CsPbBr3 NCs. For the generation of Cs-Oleate solution, 0.203 g Cs2CO3, 625 µL OA and 10 mL ODE were loaded into a 3-neck flask, and then heated to 100 °C under N2 to remove water and oxygen. Subsequently, the above mixture was further heated to 150 °C under N2 and stored for the synthesis of CsPbBr3 NCs. For the preparation of the Pb-precursor, the experimental condition was similar to that of the Cs-Oleate solution. Briefly, 0.138 g PbBr2, 1 mL OA, 1 mL OAm and 10 mL ODE were mixed a 3-neck flask and heated to 100 °C under N2 to remove water and oxygen. The above mixture was then heated to 120 °C under N2 to dissolve PbBr2. When PbBr2 were completely dissolved, the obtained solution was heated to 150 °C and 0.8 mL Cs-Oleate was added into the 3-neck flash quickly. After reaction for 5 s, the above mixture was transferred to the ice-water bath for further 10 min. The crude solution of CsPbBr3 NCs was achieved and the samples were cleaned by acetone for twice. After centrifugation (8000 rpm, 10 min), the supernatant was discarded and precipitates were ultrasonically re-dispersed in hexane and stored under dark conditions. Preparation of Paper chips For collecting of the CL signal easily, paper chips were employed in this work. Photolithography was used to pattern the chromatography paper using the method reported previously.24 The prepolymer solution was obtained by mixing PEGD and its initiator (the volume ratio is 10 :1). We poured the prepolymer solution onto a piece 5



of paper and spread over the paper to make it be impregnated with prepolymer. The prepolymer-impregnated paper was then covered with photomask and placed on a piece of black construction paper; the black paper served as an optical filter to minimize the reflected UV light. Then, the three components were exposed to the UV light (365 nm, 15 mJ/cm2, 3 s) which was provided by an ABM mask aligner. After exposure, the polymerized paper was immersed in methanol for 5 min to remove the unpolymerized prepolymer from the paper. And then, the paper was dried under ambient conditions before use. RESULT AND DISCUSSION

Characterization of Prepared CsPbBr3 NCs.

To demonstrate the formation of the CsPbBr3 NCs, the FL spectra, UV-visible absorption, XRD patterns and TEM were employed. As shown in the Figure 1A and B, the sharp emission spectrum for CsPbBr3 NCs was centered at 525 nm with a narrow fwhm of 25 nm when excited with 320 nm, which was consistent with the previous report.13 As shown in the Figure 1B, the CsPbBr3 NCs solution was yellow-green and emitted bright green light under UV irradiation. XRD patterns of the as-prepared CsPbBr3 NCs (Figure 1C) indicated that the well-defined diffraction peak of CsPbBr3 NCs was assigned to the orthorhombic phase of CsPbBr3 (ICSD#01-072-7929).25-27 The morphology of CsPbBr3 NCs was revealed by the TEM (Figure 1D), and highly monodisperse cubic structural CsPbBr3 NCs with an

6


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average size of 7 nm were observed.28,29 All these characterization results confirmed the successful preparation of the highly crystallized CsPbBr3 NCs.

Directly Oxidized CL.

The generation of CL was easily observed by mixing the prepared CsPbBr3 NCs (100 µL) with 50 mM (NH4)2S2O8 in the small quartz vial. A control experiment was also investigated to examine the influence of coexisting substances (Figure S1). Without the participation of the (NH4)2S2O8, there was no any emission observed, inferring that the emission might be from the electron-transfer reaction between (NH4)2S2O8 and CsPbBr3 NCs. Then, the common oxidant of CL system, H2O2 and NaClO were also introduced to this CsPbBr3 NCs system.30 As shown in the Figure 2B, the presence of H2O2 and NaClO can also generate the CL response under the same condition. However, the CL signals from H2O2 and NaClO were obviously weaker than that of CsPbBr3-(NH4)2S2O8 system. According to CL energy match theory,31 the results may be attributed to the energy matching degree, where the more the chemical energy generated between CsPbBr3 NCs and oxidants matches the excitation energy needed for CsPbBr3 NC, the stronger the CL intensity.21 Moreover, the redox reaction degree between CsPbBr3 NCs and different oxidants can also be recognized visually by observing the color change of the CsPbBr3 NCs and FL signals. As shown in the Figure 2C, the reaction between (NH4)2S2O8 and CsPbBr3 NCs led to the obvious color change from yellow-green to yellow and decreased FL performance. Based on the maximum CL emission, the consequent experiments 7



selected (NH4)2S2O8 as oxidant for the CL generation. As demonstrated in the previous work,22 the above color change may be induced by the structure change of CsPbBr3 NCs, therefore, the TEM image was recorded. As shown in the Figure 2D, nanocrystal lattice structure of CsPbBr3 NCs was destroyed and aggregated. Thus, nanostructure with the increased size (ca. 300 nm) was formed after reaction, which may be benefit for the energy acceptable by CsPbBr3 NCs based on the reduced distance between nanocrystals. This phenomenon was in good agreement with that reported in the system of CL between CdTe NCs and H2O2.21 In addition, the UV-vis absorption curves, FL and the FL lifetime of the CsPbBr3 NCs before and after the reaction were also collected to reveal the reaction between (NH4)2S2O8 and CsPbBr3 NCs (Figure 3). The introduction of the (NH4)2S2O8 led to an obvious decrease of adsorption and FL signals without the wavelength shift (Figure 3A and B), similar to that obtained using the other luminophore nanomaterials.22,32 Moreover, the incubation of CsPbBr3 NCs with (NH4)2S2O8 resulted in the shorter FL lifetime (Figure 3B, C), indicating the dynamic quenched mechanism through energy transfer. In addition, the poor stability in the aqueous solution was also the cause for the decreased FL.

Possible CL mechanism: To verify the origin of the above CL, the CL spectrum was recorded in the presence of the (NH4)2S2O8 (Figure 3D). CL emission peak was also observed at 530 nm with narrow fwhm of 30 nm, which was similar to the ECL spectrum11 and FL spectrum. 8


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As a control, the CL response of other coexisting substrates including the protective agents in the CsPbBr3 NCs was also investigated. There was no any CL or FL response observed, indicating the CL was possible from the excited state of CsPbBr3 NCs (Figure S1). And we inferred that the mechanism of this reaction belonged to direct CL (See equation 1). During the interface reaction process, transfer of electron took place which resulted in the generation of electron and hole due to chemical reaction,33 and the electron could be injected into the conduction band of CsPbBr3 NCs and a hole could be injected into the valence band of CsPbBr3 NCs, which resulted in the CL emission. CsPbBr3 NCs + S2O8 2-

(CsPbBr3 NCs)*

hν (~530 nm)

(1)

Some reports on semiconductor nanocrystals indicated that dissolved oxygen played an important role in CL reactions.20-22,34,35 Therefore, the effect of dissolved oxygen on the CL signals was investigated (Figure S2). The results showed that when the dissolved oxygen was removed from the solution by nitrogen, the CL intensity would be significantly reduced, indicating that dissolved oxygen did influence the reaction. It could be noted that OA/OAm-capped CsPbBr3 NCs were used in our experiment, and that surface ligands OA/OAm containing double bond (C=C) and amidogen (-NH2) can be oxidized by dissolved oxygen. In this case, dissolved oxygen was reduced to produce reaction intermediate, e.g., superoxide ions (O2-), while OA/OAm was oxidized (See equation 2). OA/OAm (Red) + O2

O2- + OA/OAm (Ox)

The above generated O2- can easily donate one electron in the reaction (O29


(2) O2


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+ e-) and lead to the electron from O2- to be injected into CsPbBr3 NCs, meanwhile the hole can be injected into the valence band by S2O8

2-

as strong oxidant and

produce the oxidized-state CsPbBr3 (h+ injection)+. In addition, S2O8 2- can also react .

with O2- and produce reaction intermediate, e.g., (SO4 ).36 O2- + CsPbBr3

CsPbBr3(e- injection)- + O2

CsPbBr3+ S2O8 2-

CsPbBr3(h+ injection)+ + SO42. SO42- + SO4 + O2

O2- + S2O8 2CsPbBr3 + SO4

(3)

.

(5)

CsPbBr3(h+ injection)++SO42-

CsPbBr3(h+ injection)+ + CsPbBr3(e

-

injection)

(4)

(CsPbBr3 NCs)*

(6) hν (7)

Finally, CsPbBr3 NCs* were produced by recombination of electron and hole, accompanying CL emission (See equation 7). Optimization of condition. In the subsequent work, to obtain the high CL efficiency, the parameters which could influence the CL performance of CsPbBr3 NCs including the pH of the reaction, the concentration of the CL probe and (NH4)2S2O8 were then investigated. Since the organic phase of CsPbBr3 NCs and the aqueous solution of (NH4)2S2O8 were not miscibility, the reaction only occurred on the hexane/water interface, which made the accurate CL control difficult. Paper based chip, a widely used inexpensive platform that used small volumes of sample, was employed for solving the above problems.24 The CsPbBr3 NCs solution was dropped on the patterned paper chips to form a solid film of CsPbBr3 NCs and then the (NH4)2S2O8 solution was injected on the other side 10


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of the paper-chip. Using the above paper based chip, the effect of different parameters was carried out. As depicted in Figure 4A, the strongest CL signal was obtained when pH was 7 to 7.5. The CL response exhibited the concentration-dependent performance on the CsPbBr3 NCs and (NH4)2S2O8. As shown in the Figure 4B, with the increase of the amount of CsPbBr3 NCs, CL intensity increased because of the participation of more CL nanoprobes. In addition, the concentration of (NH4)2S2O8 played a crucial role for achieving high CL. In the presence of 5 mM (NH4)2S2O8, the CL reached the maximum. With the further increase of (NH4)2S2O8, the CL decreased sharply, which may be due to the quenching effect of (NH4)2S2O8 on the optical property of CsPbBr3 NCs. Figure 4D gave the CL image of CsPbBr3 NCs and bright light signal was observed in the presence of the (NH4)2S2O8 on paper based chip. Moreover, the CL from different perovskite nanocrystals was also studied using CsPb(Br/I)3 NCs and CsPbI3 NCs (Figure S3). Due to the lower stability than CsPbBr3 NCs in the aqueous solution,23 when the two perovskite solutions (CsPb(Br/I)3 NCs and CsPbI3 NCs) were dropped on the paper chips, there were very weak CL signals observed (Figure S4). So, the perovskite nanocrystal with good stability needs to be explored for the good CL performance. CONCLUSIONS

The CL of CsPbBr3 NCs in aqueous medium was investigated for the first time through direct chemical oxidation. The CL response of CsPbBr3 NCs under different conditions was also investigated and a possible mechanism of the CL was put 11



forward. By adding oxidant to the CsPbBr3 NCs, the electron and hole were generated in-situ during the chemical reaction and resulted in CL emissions. CL spectra of CsPbBr3 NCs confirmed the emission species during the oxidized CL reaction was from CsPbBr3 NCs. The discovery of monochromatic CL of highly crystallized CsPbBr3 NCs not only extends the applications of halide perovskite materials in the analytical field but also provides a new route for the exploration of the physical chemistry properties. In the following work, more stable CL probes need to be prepared for the excellent CL response. ASSOCIATED CONTENT Supporting Information Detailed description of the preparation of CsPb(Br/I)3 NCs and CsPbI3 NCs, TEM images of CsPb(Br/I)3 NCs and CsPbI3 NCs, CL curves of the precursor of CsPbBr3 (Cs-Oleate and Pb-precursor), the influence of air, N2 and O2 on the CL of CsPbBr3-(NH4)2S2O8 system, the CL performance of CsPb(Br/I)3-(NH4)2S2O8 and CsPbI3 -(NH4)2S2O8.

ACKNOWLEDGMENT This work was supported by the MOST China (No.2016YFA0201300), National Natural Science Foundation of China (Grant No. 21427811), Youth Innovation Promotion Association CAS (No.2016208) and Jilin Province Science and Technology Development Plan Project 20170101194JC. 12


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Scheme 1. The schematic synthesis route for the CsPbBr3 NCs.

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Figure 1. (A) UV-vis absorption and FL spectra of monodispersed CsPbBr3 NCs in hexane; (B) Photographs of CsPbBr3 NCs under visible and UV light. (C) XRD patterns of synthetic CsPbBr3 (black line) and reference pattern of bulk CsPbBr3 NCs (red line). (D) TEM image of CsPbBr3 NCs. The inset shows HRTEM image of CsPbBr3 NCs.

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Figure 2. (A) CL curves of CsPbBr3 -(NH4)2S2O8 (red line) and individual CsPbBr3 (blue line). (B) Normalized CL curves of different oxidants: (NH4)2S2O8 system (red line); H2O2 system (blue line); NaClO system (black line). (C) The color change mixing different oxidants with perovskite. From left to right were CsPbBr3-H2O, NaClO, H2O2, (NH4)2S2O8 system: the top picture was obtained under visible light; the picture below was obtained under UV light. (D) HRTEM image of CsPbBr3 -(NH4)2S2O8 system.

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Figure 3. (A) The UV-vis absorption curve of the CsPbBr3 NCs before (red line) and after (black line) the reaction. (B) FL intensity images CsPbBr3 NCs before (red line) and after (black line) the reaction. (C) FL lifetime pictures before (red line) and after (blue line) the reaction. (D) The CL spectrum of CsPbBr3-(NH4)2S2O8 system. The inset shows photographs of actual CL in the instrument.

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Scheme 2. Schematic diagram of the CL mechanism of CsPbBr3-(NH4)2S2O8 system

Figure 4. (A) Influence of pH in this system. (B) Influence of the concentration of CsPbBr3 NCs in this system. (C) Influence of the concentration of (NH4)2S2O8 in this system. (D) CL curves of CsPbBr3 NCs under optimum conditions on paper-chip. The inset shows CL photograph of CsPbBr3 NCs in a dark room: (a) only CsPbBr3 NCs (b) 23



CsPbBr3 NCs and (NH4)2S2O8 solution.

for TOC only

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Chemiluminescence of CsPbBr3 perovskite nanocrystal on the

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