The non-trivial role of native xylans on the preparation of TEMPO-oxidized cellulose nanofibrils

Cellulose nanofibrils have become increasingly prized as a raw material toward the preparation of composites due to their specific surface character and biocompatibility. TEMPO-mediated oxidation with post-mechanical treatment has been proposed as a promising method for the preparation of cellulose nanofibrils from cellulosic raw materials. In the current study it was found that the native hemicellulosic components in the raw material played a pivotal chemical role on the kinetics of generation of TEMPO-oxidized cellulose nanofibrils (TOCNs), as well as on thermal stability, and transmittance. The removal of xylans from the original feedstock facilitated not only an increase in both the carboxylate content and water retention value of the TEMPO-oxidized fibers, but also improved the transmittance of subsequently obtained TOCNs suspensions. It was also determined that the presence of xylans in the cellulosic feedstock hindered chemical accessibility through a barrier mechanism in which the TEMPO-mediated oxidation reaction rate was reduced.