Silver Ions Drive Ordered Self-Assembly Mechanisms and Inherent Properties of Lignin Nanoflowers.

Abstract

Designing anisotropic lignin-based particles and promoting the high-value utilization of lignin have nowadays drawn much attention from scientists. However, systematic studies addressing the self-assembly mechanisms of anisotropic lignin-based particles are scarce. In this work, an interaction including the electrostatic forces and chelating forces between lignin and Ag+ was regulated via carboxymethylation modification. Subsequently, the aggregation morphology of carboxymethylated lignin in a Ag+ solution was observed via SEM. The result showed that a large number of Ag+ intercalated into the lignin molecules when the grafting degree of the carboxyl groups increased from 0.17 mmol/g to 0.53 mmol/g, which caused the lignin molecules to gradually transform from disordered blocks to ordered layers. Dynamics research indicated that the adsorption process of Ag+ in carboxymethylated lignin conforms to the Pseudo-first-order kinetic model. The saturated adsorption amount of Ag+ in the carboxymethylated lignin reached 1981.7 mg/g when the grafting rate of carboxyl groups increased to 0.53 mmol/g, which then fully intercalated into lignin molecules and formed a layered structure. The thermodynamic parameters showed that the thermal adsorption process conforms to the Langmuir model, which indicates that Ag+ is monolayer-adsorbed and intercalated into lignin molecules. Meanwhile, the ΔH values are more than 0, which suggests that this adsorption process is a endothermic reaction and that a higher temperature is conducive to an adsorption reaction. Therefore, self-assembly of lignin in a Ag+ solution under 70 °C is more conducive to the formation of a nanoflower structure, which is consistent with our experimental result. Finally, pH-responsive Pickering emulsions were successfully prepared using a lignin-based nanoflowers, which demonstrated their potential as a catalytic platform in the interface catalysis field. This work offers a deeper understanding into the formation mechanism of anisotropic lignin-based nanoflowers and hopes to be helpful for designing and preparing anisotropic lignin-based particles.