Spontaneous Co-Assembly of Cellulose Nanocrystals and TiO2 Nanorods Followed by Calcination to Form Cholesteric Inorganic Nanostructures

Chiral nanomaterials possess unique electronic, magnetic, and optical properties that are relevant to a wide range of applications including photocatalysis, chiral photonics, and biosensing. A simple, bottom-up method to create chiral, inorganic structures is introduced that involves the co-assembly of TiO₂ nanorods with cellulose nanocrystals (CNCs) in water. To guide experimental efforts, a phase diagram was constructed to describe how phase behavior depends on the CNCs/TiO₂/H₂O composition. A lyotropic cholesteric mesophase was observed to extend over a wide composition range as high as 50 wt % TiO₂ nanorods, far exceeding other examples of inorganic nanorods/CNCs co-assembly. Such a high loading enables the fabrication of inorganic, free-standing chiral films through removal of water and calcination. Distinct from the traditional templating method using CNCs, this new approach separates sol-gel synthesis from particle self-assembly using low-cost nanorods.