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Correlated Optical Spectroscopy and Electron Microscopy Studies of the Slow Ostwald-Ripening Growth of Silver Nanoparticles under Controlled Reducing Conditions

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Abstract

Metallic nanoparticles display distinct localized surface plasmon resonance (LSPR) properties that depend on their size, shape, and composition and that can be monitored to characterize their growth. Utilizing LSPR properties, we report the first investigation of ambient temperature formation of trioctylamine (TOA)-stabilized spherical silver nanoparticles (AgNPs) of ∼3.0-nm diameter by mild reduction of AgClO4 with the weak reducing agent heptamethyltrisiloxane in organic solvent. The appropriate choice of experimental conditions caused slow reduction, which allowed the study of the nanoparticle growth process by time-resolved UV–visible spectroscopy and transmission electron microscopy (TEM). The linear nanoparticle growth kinetics from 50 min to end of the reaction derived from LSPR changes, the absence of a bimodal size distribution during the initial stage of the reduction process from TEM analysis, and the single crystallinity of the resulting AgNPs suggested a diffusion-controlled Ostwald-ripening growth process. It was also found that in addition to its stabilizing ability, TOA acted as a catalyst and facilitated Ag+ reduction. Furthermore, a modest increase in reaction temperature caused a substantial enhancement in the AgNP formation rate, and low concentration of stabilizing ligand yielded an increase in size and dispersity.

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Acknowledgments

This work was supported by start-up funds provided by IUPUI. N.W. D. and J. C. N. acknowledge MURI fellowship from Center for Research and Learning, IUPUI. Authors would also like to acknowledge Dr. Carrie Donley (CHANL) for helping with XPS analysis.

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Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, Indiana University Purdue University Indianapolis, Indianapolis, IN, 46202, USA

    Nathan W. Dennis, Barry B. Muhoberac, John C. Newton & Rajesh Sardar

  2. University of North Carolina, Chapel Hill, NC, 27599, USA

    Amar Kumbhar

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Correspondence to Rajesh Sardar.

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Histogram for particle size analysis at early stages, XPS data, and UV–visible spectra. (DOCX 907 kb)

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Dennis, N.W., Muhoberac, B.B., Newton, J.C. et al. Correlated Optical Spectroscopy and Electron Microscopy Studies of the Slow Ostwald-Ripening Growth of Silver Nanoparticles under Controlled Reducing Conditions. Plasmonics 9, 111–120 (2014). https://doi.org/10.1007/s11468-013-9603-1

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