Chemically stable polypyrrole-modified liquid metal nanoparticles with the promising photothermal conversion capability

doi:10.1016/j.jmst.2022.02.053

Abstract

Abstract:

The gallium-based eutectic alloy has gained particular attention in various fields due to its natural features of metallic fluids at room temperature. However, these alloy nanoparticles are extremely susceptible to be oxidized accompanied by de-alloying during the preparation, storage, and application. Here, with the assistance of the macromolecular stabilizer and dopant, sodium dodecylbenzene sulfonate (SDBS), we demonstrate a stable polypyrrole (PPy) layer acts as a protected “armor” on the surface of liquid metal (i.e., gallium-tin, EGaSn). SDBS enables the EGaSn to keep well dispersion and protects dispersed EGaSn from being durative oxidized before PPy coating. Furthermore, PPy greatly inhibits the oxidation of EGaSn owing to the strong interface interaction between the lone pair electrons around the N atoms of Py rings and the Ga³⁺ orbit of EGaSn. Consequently, the fabricated EGaSn nanoparticles possess the features of smaller particle size, superior uniform distribution, and stronger antioxidant capacity. The prepared EGaSn@PPy composite exhibits superior stability even after storing in an aqueous solution for up to 100 days. As a proof-of-concept application, the EGaSn@PPy composite displays remarkable photothermal performance with an enhanced photothermal conversion efficiency. This work provides a novel surface engineering strategy to ameliorate liquid metal for photothermal therapy applications.

Key words: Liquid metal, Polypyrrole, Polymeric architecture, Stability, Photothermal

Yaqin Qi, Ting Jin, Kai Yuan, Jingyuan You, Chao Shen, Keyu Xie. Chemically stable polypyrrole-modified liquid metal nanoparticles with the promising photothermal conversion capability[J]. J. Mater. Sci. Technol., 2022, 127: 144-152.

Figures/Tables 5

Fig 1. The schematic illustration of two different synthesis routes of EGaSn@PPy composite shows the nanostructure difference between without stabilizer of (a) EGaSn@C-PPy and with the SDBS adding of (b) EGaSn@W-PPy.

Fig 2. Microstructure characterization of EGaSn@C-PPy and EGaSn@W-PPy composite during the overall synthetic process. The TEM images of (a-i) EGaSn and (a-ii) EGaSn@C-PPy, and (b-i) S-EGaSn and (b-ii) EGaSn@W-PPy. The particle size distribution of (c) EGaSn and EGaSn@C-PPy, and (d) S-EGaSn and EGaSn@W-PPy. (e) The average diameter and PDI values of corresponding nanoparticles dispersion.

Fig 3. Detailed chemical composition and structure characterization of EGaSn@PPy composite. (a) XRD spectra of EGaSn, PPy, EGaSn@W-PPy, and EGaSn@C-PPy. (b) FT-IR spectra of pure PPy, EGaSn@W-PPy, and EGaSn@C-PPy. (c) XPS survey spectra of EGaSn, PPy, EGaSn@W-PPy, and EGaSn@C-PPy. High-resolution XPS spectra of (d) Ga 3d and (e) Ga 2p in EGaSn, EGaSn@W-PPy, and EGaSn@C-PPy. (f) High-resolution XPS spectra of N 1 s in PPy, EGaSn@W-PPy, and EGaSn@C-PPy.

Fig 4. Chemical stability test of EGaSn@C-PPy and EGaSn@W-PPy after storage in the aqueous solution. TEM images and EDS maps of (a) EGaSn@C-PPy and (b) EGaSn@W-PPy after storage 100 days. The XRD patterns of (c) EGaSn@C-PPy and (d) EGaSn@W-PPy after several different storage times. (e) The hydrodynamic size distribution of EGaSn@C-PPy and EGaSn@W-PPy after storage 100 days.

Fig 5. Photothermal performance and photothermal stability analysis of EGaSn@C-PPy and EGaSn@W-PPy. (a) Thermal images of EGaSn@C-PPy and EGaSn@W-PPy. (b) Temperature elevation and natural cooling curves of DI water, EGaSn, PPy, EGaSn@C-PPy, and EGaSn@W-PPy in the aqueous solution. (c) PCE values of EGaSn, PPy, EGaSn@C-PPy, and EGaSn@W-PPy. The TEM images and EDS maps (d) EGaSn@C-PPy and (e) EGaSn@W-PPy after NIR irradiation. (f) Schematic illustration of the photothermal stability of EGaSn@C-PPy and EGaSn@W-PPy composite. The gray sphere refers to the EGaSn nanoparticles. The blue circle is the oxide layer. The watermelon red layer and pink layer refer to the C-PPy and W-PPy, respectively.

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