Novel Electrically Conductive Cellulose Nanocrystals with a Core-Shell Nanostructure Towards Biodegradable Electronics

Nanomaterials (Basel). 2023 Feb 20;13(4):782. doi: 10.3390/nano13040782.

Abstract

Electronic waste (e-waste) is the fastest growing waste stream and its negative impact on the environment and human health is major because of the toxicity and non-biodegradability of its constituents. For their biodegradability and nontoxicity, bio-based materials have been proposed as potential material candidates in the field of electronics. Among these, cellulose nanocrystals (CNCs) have many interesting properties including biodegradability, high mechanical strength, and possibility to functionalize. In terms of electrical properties, CNCs are electrically insulated, limiting their potential in electronics. This work aims to build up a poly(o-toluidine)-like shell around the CNCs to render them conductive. For this goal, the surface of the CNCs was carbamated using 2,4-toluene diisocyanate through the para-isocyanates and the ortho-isocyanates were later hydrolyzed to amine groups using HCl-acidified dimethylsulfoxide. The resultant o-toluidine-like molecules on the CNC surface were then polymerized using ammonium persulfate to form an electrically conductive shell around each CNC. The resultant CNCs were then characterized for their chemical, morphological, and electrical properties. Fourier-transform infrared analysis of the CNCs at each stage confirmed the expected chemical changes upon carbamation, hydrolysis, and polymerization and X-ray diffraction confirmed the permanence of the native crystalline structure of the CNCs. The atomic force microscopy images showed that the obtained CNCs were on average slightly thicker than the original ones, possibly due to the growth of the poly(o-toluidine) shell around them. Finally, using the four-point method, the obtained CNCs were electrically conductive with a conductivity of 0.46 S/cm. Such novel electrically conductive CNCs should have great potential in a wide range of applications including electronics, sensing, and medicine.

Keywords: cellulose; core-shell; e-waste; electrical conductivity; nanocrystals; toluene diisocyanate.