In-Situ Growth of Metal Oxide Nanoparticles on Cellulose Nanofibrils for Dye Removal and Antimicrobial Applications

Nanocellulose is known to act as a platform for the in-situ formation of metal oxide nanoparticles, where the multiple components of the resultant hybrids act synergistically toward specific applications. However, typical mineralization reactions require hydrothermal conditions or addition of further reducing agents. Herein, we demonstrate that carboxylated cellulose nanofibril-based films can spontaneously grow functional metal oxide nanoparticles during the adsorption of heavy metal ions from water, without the need of any further chemicals or temperature. Despite the apparent universality of this behavior with different metal ions, this work focuses on studying the in-situ formation of copper oxide nanoparticles on TOCNF films as well as the resultant hybrid films with improved functionality toward dye removal from water and antimicrobial activity. Using a combination of cutting-edge techniques (e.g., in-situ SAXS and QCMD) to systematically follow the nanoparticle formation on the nanocellulosic films in real time, we suggest a plausible mechanism of assembly. Our results confirm that carboxylated cellulose nanofibril films act as universal substrate for the formation of metal oxide nanoparticles, and thus hybrid nanomaterials, during metal ion adsorption processes. This phenomenon enables the upcycling of nanocellulosic materials through multistage applications, thus increasing its sustainability and efficiency in terms of an optimal use of resources.