Cellulose Nanowhisker/Silver Nanoparticle Hybrids Sterically Stabilized by Surface Poly(ethylene glycol) Grafting

Sterically stabilized hybrids of cellulose nanowhiskers (CNWs) and silver nanoparticles (AgNPs) were prepared via poly(ethylene glycol) (PEG) grafting and subsequent reduction of Ag⁺ counterions by sodium borohydride (NaBH₄) for improved dispersion stability after hybridization. The preparation scheme includes surface carboxylation of CNWs using a 2,2,6,6-tetramethyl-1-pyperidinyloxy radical (TEMPO), grafting of monomethoxy PEG (mPEG) via amidation mediated by 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride or 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride, exchange of countercation of residual carboxyls to Ag⁺, and deposition of AgNPs via reduction with NaBH₄. UV-vis spectroscopy and electron microscopy analyses confirmed the successful deposition of AgNPs. Most of the mPEG-grafted hybrids were stable under the presence of an electrolyte, although some of them were precipitated by the addition of 0.1 M CaCl₂. The addition of CaCl₂ was also found to trigger discoloration of the hybrids, suggesting the partial dissolution of AgNPs and the formation of water-insoluble AgCl.