Hydroxyl groups on cellulose nanocrystal surfaces form nucleation points for silver nanoparticles of varying shapes and sizes

Abstract

In this study, we investigate the interactions between the cellulose surface and Ag nanoparticles (AgNPs) for the purpose of manufacturing hybrid nanomaterials using bacterial cellulose nanocrystals (BCNs) as a model substrate. We focus on the role of the BCN surface chemistry on the AgNP nucleation obtained by chemical reduction of Ag⁺ ions. Homogeneous hybrid suspensions of BCN/AgNP are produced, regardless of whether the BCNs are quasi-neutral, negatively (TBCNs) or positively charged (ABCNs). The characterization of BCN/AgNP hybrids identifies the -OH surface groups as nucleation points for AgNPs, of about 20 nm revealing that surface charges only improve the accessibility to OH groups. X-ray Absorption technics (XANES and EXAFS) revealed a high metallic Ag₀ content ranging from 88% to 97%. Moreover, the grafting of hydrophobic molecules on a BCN surface (HBCNs) does not prevent AgNP nucleation, illustrating the versatility of our method and the possibility to obtain bifunctional NPs. A H₂O₂ redox post-treatment on the hybrid induces an increase in AgNPs size, up to 90 nm as well as a shape variation (i.e., triangular). In contrast, H₂O₂ induces no size/shape variation for aggregated hybrids, emphasizing that the accessibility to -OH groups ensures the nucleation of bigger Ag nano-objects.

Keywords: AgNP size-shape variation; Bacterial cellulose nanocrystal (BCN); Hybrid nanomaterial; Hydrophobic BCN; Hydroxyl groups; Silver nanoparticles (AgNPs); Surface modification.