Structure Selectivity of Alkaline Periodate Oxidation on Lignocellulose for Facile Isolation of Cellulose Nanocrystals

Reported here for the first time is the alkaline periodate oxidation of lignocelluloses for the selective isolation of cellulose nanocrystals (CNCs). With the high concentrations as a potassium salt at pH 10, periodate ions predominantly exist as dimeric orthoperiodate ions (H2I2O104−). With reduced oxidizing activity in alkaline solutions, dimeric orthoperiodate ions preferentially oxidized non‐ordered cellulose regions. The alkaline surroundings promoted the degradation of these oxidized cellulose chains by β‐alkoxy fragmentation and generated CNCs. The obtained CNCs were uniform in size and generally contained carboxy groups. Furthermore, the reaction solution could be reused after regeneration of the periodate with ozone gas. This method allows direct production of CNCs from diverse sources, in particular lignocellulosic raw materials including sawdust (European beech and Scots pine), flax, and kenaf, in addition to microcrystalline cellulose and pulp. Structure based: A novel method based on a recyclable and newly selective alkaline periodate oxidation at pH 10 provides a sustainable strategy for the efficient isolation of cellulose nanocrystals (CNCs) from various lignocellulosic materials. Isolation of the CNCs results from the structural differences between the ordered and non‐ordered regions of the lignocellulose.