Protonation of Surface Carboxyls on Rice Straw Cellulose Nanofibrils: Effect on the Aerogel Structure, Modulus, Strength, and Wet Resiliency

Abstract

Rice straw cellulose nanofibrils from the optimal 2,2,6,6-tetramethylpiperidine-1-oxyl oxidation/blending process carrying 1.17 mmol/g surface carboxyls were protonated to varying charged (COO-Na+) and uncharged (COOH) surfaces. Reducing the electrostatic repulsion of surface charges by protonation with hydrochloric acid from 11 to 45 and 100% surface carboxylic acid most prominently reduced the aerogel densities from 8.0 to 6.6 and 5.2 mg/cm3 while increasing the mostly open cell pore volumes from 125 to 152 and 196 mL/g. Irrespective of charge levels, all aerogels were amphiphilic, super-absorptive, stable at pH 2 for up to 30 days, and resilient for up to 10 repetitive squeezing-absorption cycles. While these aerogels exhibited density-dependent dry [11.3 to 1.5 kPa/(mg/cm3)] and reduced wet [3.3 to 1.4 kPa/(mg/cm3)] moduli, the absorption of organic liquids stiffened the saturated aerogels. These data support protonation as a critical yet simple approach toward precise control of aerogels’ dry and wet properties.