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Preparation and optical properties of colloidal Ag0 nanoclusters from reduction of solution ionomer Ag-carboxylate ionic aggregates activated by swelling of covalently attached chain segments

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Abstract

Small colloidal Ag0 nanoclusters successfully were prepared from solution reaction of CH3COOAg with a copolymer acid, poly(methyl methacrylate-ran-methacrylic acid) (MMA–MAA), in a methanol-containing solvent at room temperature in the dark in the absence of a typical chemical reductant. Tentatively mechanistically, slow PMMA-ionomerisation of the Ag+ ions produces intramolecular –COO−–Ag+ aggregate cross-links in the solution, which, upon swelling of the chain segments covalently bound to them, are activated by the resultant elastic forces to dissociate instantaneously at the O–Ag coordination bonds to give bare (i.e. uncoordinated), highly oxidative Ag+ ions, which are subject to reduction by the active α-H atoms of the solvent methanol to make Ag0 nanoclusters supported by the re-formed MMA–MAA; the MMA–MAA acid-copolymer, without itself undergoing any permanent chemical change, serves as a mechanical-activator or, say, catalyst for the mechanochemical reduction of CH3COOAg. This novel, facile approach may universally be extended to fabricate other transition-metal nanoclusters deposited in diverse polymeric matrices.

Ag+-ion solution ionomerisation introduces intramolecular Ag-carboxylate ionic aggregates that subsequently are broken by covalently attached, swollen chain segments and subject to room temperature, dark mechanochemical reduction.

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Acknowledgements

We acknowledge with gratitude that this work was supported by the Open Fund of the Hubei Provincial Key Laboratory of Green Materials for Light Industry, China (Contract no. [2013]2-key-3), as well as by the Overseas High-level Talents Scientific-research Starting Fund of Hubei University of Technology, China (Contract no. HBUT-science-[2005]2). We also very much thank Dr. Yan Xiong from MCE of HBUT for his helpful discussions.

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Authors and Affiliations

  1. Hubei Provincial Key Laboratory of Green Materials for Light Industry, Hubei University of Technology, Wuhan, Hubei, 430068, People’s Republic of China

    Bofeng Li, Tao Hu, Xinghou Gong & Chonggang Wu

  2. Collaborative Innovation Centre of Green Light-weight Materials and Processing, Hubei University of Technology, Wuhan, Hubei, 430068, People’s Republic of China

    Bofeng Li, Tao Hu, Xinghou Gong & Chonggang Wu

  3. School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, Hubei, 430068, People’s Republic of China

    Bofeng Li, Tao Hu, Nian Ma, Zhen Hu, Xinghou Gong & Chonggang Wu

  4. Department of Chemical and Biochemical Engineering, Rutgers University, Piscataway, NJ, 08854, USA

    Masanori Hara

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  1. Bofeng Li
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  2. Tao Hu
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Correspondence to Chonggang Wu or Masanori Hara.

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Li, B., Hu, T., Ma, N. et al. Preparation and optical properties of colloidal Ag0 nanoclusters from reduction of solution ionomer Ag-carboxylate ionic aggregates activated by swelling of covalently attached chain segments. Colloid Polym Sci 295, 583–599 (2017). https://doi.org/10.1007/s00396-017-4033-9

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