Highly stable aqueous phase black phosphorus quantum dots with enhanced fluorescence property

doi:10.1016/j.jmst.2021.11.039

Abstract

Abstract:

Black phosphorus quantum dots (BPQDs) are a kind of outstanding optical material due to the tunable band structure. However, their fluorescence property and stability are obviously weakened in the aqueous phase, which extremely restricts the development of BPQDs. Here, we propose a new method to prepare stable BPQDs in an aqueous solution directly with high absolute fluorescence quantum yield. Aqueous phase BPQDs are synthesized by liquid exfoliation and hydrothermal with NH₂-polyethylene glycol (PEG)-NH₂ as the modification agent to protect the BPQDs, which have high stability more than six months. In addition, NH₂-PEG-NH₂ is also a surface passivation agent to enhance the emission of BPQDs by forming P-N bonds, which is confirmed by an absolute fluorescent quantum yield of 11.5%. Moreover, BPQDs show excellent resistance to a strong acid environment and high ionic strengths except for Fe³⁺. Therefore, the BPQDs are a kind of highly selective and linear response fluorescence probe for Fe³⁺. Considering the good biocompatibility of BPQDs, they are employed as cell fluorescent label probes and show excellent fluorescence imaging contrast. Based on the unique structural stability and fluorescence performance in the aqueous phase, BPQDs are potential candidates for Fe³⁺ detection and optical bio-imaging.

Key words: Black phosphorus, Quantum dots, Fluorescence, Iron detection, Cell imaging

Yingli Ma, Xiaoguang Xu, Xiaoshuang Zhang, Mayifei Rong, Liying Lu, Yan Li, Wenhao Dai, Hongwu Du, Yong Jiang. Highly stable aqueous phase black phosphorus quantum dots with enhanced fluorescence property[J]. J. Mater. Sci. Technol., 2022, 116: 50-57.

Figures/Tables 8

Scheme 1. Schematic illustration of the design of PEG@BPQDs and their applications on Fe3+ detection and cell imaging.

Fig. 1. (a) TEM image of PEG@BPQDs. (b) HRTEM image of PEG@BPQDs. (c) AFM topographic image of PEG@BPQD. (d) Height profiles along the directions shown in the AFM image.

Fig. 2. (a) XRD pattern of PEG@BPQDs. (b) FT-IR spectrum of PEG@BPQDs. (c) P 2p spectrum of PEG@BPQDs. (d) N 1s spectrum of PEG@BPQDs.

Fig. 3. (a) UV-vis absorption, PL excitation, and emission spectra of PEG@BPQDs. The inset images show photographs of PEG@BPQDs in water under visible (left) and UV (right) light. (b) PL spectra of PEG@BPQDs under different excitation wavelengths. (c) PL spectra of BPQDs and PEG@BPQDs under the excitation of 320 nm. (d) Emission wavelength of L-PEG@BPQDs, PEG@BPQDs, and H-PEG@BPQDs under the excitation of 350 nm, 370 nm, and 400 nm. (e) PL intensity of L-PEG@BPQDs, PEG@BPQDs, and H-PEG@BPQDs under the excitation of 320 nm, 350 nm, 370 nm, and 400 nm. (f) PL spectra of PEG@BPQDs in ethanol or water under different excitation wavelengths.

Fig. 4. Time-resolved fluorescence-decay curves of PEG@BPQDs (a) with and (b) without Fe3+ in water.

Fig. 5. Stability of PEG@BPQDs. (a) The effect of storage time in the air on the PL intensity of PEG@BPQDs. (b) The effect of NaCl concentration on the PL intensity of PEG@BPQDs. (c) The effect of pH value on the PL intensity of PEG@BPQDs.

Fig. 6. (a) The effect of different ions on the PL intensity of PEG@BPQDs. The concentration of each kind of ion is set to 500 μM. (b) Fluorescence responses of PEG@BPQDs toward different concentrations of Fe3+ (from top to bottom: 0, 50, 70, 100, 120, 150, 170, 200, 250, 300, 350, and 400 μM). The inset shows the fluorescence intensities of PEG@BPQDs as a function of Fe3+ concentration, where F and F0 represent the fluorescence intensities in the presence and absence of ions, respectively.

Fig. 7. (a) The viability of the A549 cells after incubation with PEG@BPQDs for 24 h. (b) and (c) are confocal fluorescence images of A549 cells labeled with PEG@BPQDs in bright-field and excited by 405 nm. (d) Merged image of A549 cells.

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