Sustainable Tailoring of Lignin Nanoparticles Assisted by Green Solvents

Abstract This work aimed at studying the self‐assembly of lignin macromolecules towards lignin nanoparticles (LNPs) with green solvents and shedding light on a tailor‐made production of LNPs through a meticulous study of different variables. The methodology (antisolvent to lignin solution – method A; or lignin solution to antisolvent – method B), the lignin solvent, the flow rate of solvent/antisolvent addition, the lignin solution loading and the washing step (centrifugation vs dialysis) were examined. Remarkably, method B enabled achieving desired LNPs (127.4–264.9 nm), while method A induced the formation of lignin microparticles (582.8–7820 nm). Among lignin solvents, ethanol allowed the preparation of LNPs with the lowest hydrodynamic diameter (method B=127.4 nm), while the largest particles (method A=7820 nm) were obtained with ethylene glycol. These latest particles were characterized as heterogeneous, irregular, and highly aggregated when compared for instance with γ‐valerolactone counterparts, which showed the most homogeneous (PDI=0.057–0.077) and spherical particles. Moreover, decreasing lignin solution loading enabled the reduction on LNP size and Zeta potential. Dialysed samples allowed the formation of LNPs with lower hydrodynamic size, reduced aggregation, and higher homogeneity. Furthermore, dialysis provided high stability to LNPs, avoiding particle coalescent phenomenon.