Tuning of Ag Nanoparticle Properties in Cellulose Nanocrystals/Ag Nanoparticle Hybrid Suspensions by H₂O₂ Redox Post-Treatment: The Role of the H₂O₂/AgNP Ratio

Abstract

Hybrid nanoparticles involving 10-nm silver nanoparticles (AgNPs) nucleated on unmodified rod-like cellulose nanocrystals (CNCs) were prepared by chemical reduction. H2O2 used as a post-treatment induced a size-shape transition following a redox mechanism, passing from 10-nm spherical AgNPs to 300-nm triangular or prismatic NPs (AgNPrisms), where CNCs are the only stabilizers for AgNPs and AgNPrisms. We investigated the role of the H2O2/AgNP mass ratio (α) on AgNPs. At α values above 0.20, the large amount of H2O2 led to extensive oxidation that produced numerous nucleation points for AgNPrisms on CNCs. On the contrary, for α below 0.20, primary AgNPs are only partially oxidized, releasing a reduced amount of Ag+ ions and thus preventing the formation of AgNPrisms and reforming spherical AgNPs. While XRD and EXAFS reveal that the AgNP fcc crystal structure is unaffected by the H2O2 treatment, the XANES spectra proved that the AgNP–AgNPrism transition is always associated with an increase in the metallic Ag fraction (Ag0). In contrast, the formation of new 15-nm spherical AgNPs keeps the initial Ag0/Ag+ ratio unmodified. For the first time, we introduce a complete guide map for the fully-controlled preparation of aqueous dispersed AgNPs using CNC as a template.

Keywords

• CNC/AgNP hybrids
• H₂O₂ redox post-treatment
• H₂O₂/AgNP mass ratio
• oxidation state
• XANES-EXAFS