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An approach to core–shell nanostructured materials with high colloidal and chemical stability: synthesis, characterization and mechanistic evaluation

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Abstract

Silver–polypyrrole (PPy) core–shell nanoparticles have been fabricated by a facile one-step “green” synthesis using silver nitrate as an oxidant and soluble starch as an environmentally benign stabilizer and co-reducing agent. The morphology and optical properties of the particles were significantly affected by the reaction temperature, soluble starch concentration, and ratio of pyrrole monomer to AgNO3 oxidant. The core–shell nanoparticles exhibited outstanding dispersive properties in deionized water due to residual starch, as compared with PPy nanoparticles in which starch was absent. The mechanism of core–shell nanoparticle formation was elucidated through TEM imaging vs. reaction time. The colloidal and chemical stability of the nanoparticles was demonstrated in a variety of solvents, including acids, bases, and ionic and organic solvents, through monitoring the localized surface plasmon resonance of the nanoparticles. Furthermore, the catalytic properties of these silver–PPy core–shell nanoparticles were also demonstrated.

Schematic illustration of silver-PPy core-shell nanoparticle formation and methylene blue (MB) reduction using the core-shell nanoparticles as a catalyst.

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Acknowledgments

This work was supported by the Georgia Institute of Technology. The authors thank Hyung Ju Kim for his help with the X-ray diffractometry experiments and Wun-Gwi Kim for his help with the SEM measurements.

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Authors and Affiliations

  1. School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW, Atlanta, GA, 30332-0100, USA

    Mincheol Chang & Elsa Reichmanis

  2. School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA, 30332-0100, USA

    Elsa Reichmanis

  3. School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA, 30332-0100, USA

    Elsa Reichmanis

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  1. Mincheol Chang
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  2. Elsa Reichmanis
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Correspondence to Elsa Reichmanis.

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Fig. S1

Effect of [pyrrole]/[AgNO3] molar ratio on silver–PPy core–shell nanoparticle size. Average change in size of the nanoparticles as a function of [pyrrole]/[AgNO3] molar ratios of 6, 12, 18, and 24. Synthetic conditions: AgNO3 0.25 mM, 4 wt.% soluble starch, reaction time 24 h, reaction temperature 95 °C. The average particle size was determined by SEM (100 particles counted) (DOC 231 kb)

Fig. S2

Effect of [pyrrole]/[AgNO3] molar ratio on the silver core and PPy shell size in the core–shell nanoparticles. Average change in core and shell size as a function of [pyrrole]/[AgNO3] molar ratios of 6, 12, 18, and 24. Synthetic conditions: AgNO3 0.25 mM, 4 wt.% soluble starch, reaction time 24 h, reaction temperature 95 °C. The average core and shell size were determined by TEM (100 particles counted) (DOC 260 kb)

Fig. S3

Effect of soluble starch concentration on silver–PPy core–shell nanoparticle size. Average change in size of the nanoparticles as a function of soluble starch concentrations of (a) 1 wt.%, (b) 2 wt.%, (c) 3 wt.%, and (d) 4 wt.%. Synthetic conditions: pyrrole 4.5 mM, AgNO3 0.25 mM, reaction time 24 h, reaction temperature 95 °C. The average particle size was determined by SEM (100 particles counted) (DOC 105 kb)

Fig. S4

UV–vis spectra of silver–PPy core–shell nanoparticles synthesized with different reaction times: 20, 30, 80, 330, 720, and 1,440 min from bottom to top. Synthetic conditions: pyrrole 4.5 mM, AgNO3 0.25 mM, 4 wt.% soluble starch, reaction temperature 95 °C. The spectra were normalized and shifted for comparison (DOC 155 kb)

Fig. S5

FT-IR spectra of (a) starch, (b) silver–PPy core–shell nanoparticles, and (c) PPy nanoparticles. The synthetic conditions for the silver–PPy core–shell nanoparticles: pyrrole 3.0 mM, AgNO3 1.2 mM, 4 wt.% soluble starch, reaction temperature 80 °C, reaction time 24 h. PPy nanoparticles were prepared through polymerization of pyrrole with FeCl3 as an oxidant in aqueous medium (DOC 343 kb)

Fig. S6

XPS spectrum of the silver–PPy core–shell nanoparticles. Synthetic conditions: pyrrole 4.5 mM, AgNO3 0.25 mM, 4 wt.% soluble starch, reaction time 24 h, reaction temperature 95 °C (DOC 237 kb)

Fig. S7

Photo images of pure PPy nanoparticles (left) and the silver–PPy core–shell nanoparticles (right) (a) immediately after dispersion and (b) at 40 h after initial dispersion. The pure PPy nanoparticles were prepared using FeCl3 as an oxidant in the presence of DTAB, and the silver–PPy core–shell nanoparticles were prepared using AgNO3 as an oxidant in the presence of soluble starch. Synthetic conditions for the silver–PPy core–shell nanoparticles: pyrrole 4.5 mM, AgNO3 0.25 mM, reaction time 24 h, reaction temperature 95 °C (DOC 89 kb)

Fig. S8

XRD pattern obtained for the silver–PPy core–shell nanoparticles. Synthetic conditions: pyrrole 4.5 mM, AgNO3 0.25 mM, 4 wt.% soluble starch, reaction time 24 h, reaction temperature 95 °C. The inset shows the electron diffraction pattern of the corresponding nanoparticles obtained by TEM (DOC 106 kb)

Table S1

Synthetic conditions used to investigate the effect of reaction temperature, molar ratio of pyrrole monomer to AgNO3, and concentration of aqueous starch solution on the composition, morphology, and optical properties of the silver–PPy core–shell nanostructured materials (DOC 350 kb)

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Chang, M., Reichmanis, E. An approach to core–shell nanostructured materials with high colloidal and chemical stability: synthesis, characterization and mechanistic evaluation. Colloid Polym Sci 290, 1913–1926 (2012). https://doi.org/10.1007/s00396-012-2731-x

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  • DOI: https://doi.org/10.1007/s00396-012-2731-x

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