Tough Supramolecular Hydrogels Crafted via Lignin-Induced Self-Assembly

Supramolecular hydrogels are typically assembled through weak non-covalent interactions, posing a significant challenge in achieving ultra strength. Developing a higher strength based on molecular/nanoscale engineering concepts is a potential improvement strategy. Herein, a super-tough supramolecular hydrogel is assembled by gradually diffusing lignosulfonate sodium (LS) into a polyvinyl alcohol (PVA) solution. Both simulations and analytical results indicate that the assembly and subsequent enhancement of the crosslinked network are primarily attributed to LS-induced formation and gradual densification of strong crystalline domains within the hydrogel. The optimized hydrogel exhibits impressive mechanical properties with tensile strength of ≈20 MPa, Young's modulus of ≈14 MPa, and toughness of ≈50 MJ m⁻³, making it the strongest lignin-PVA/polymer hydrogel known so far. Moreover, LS provides the supramolecular hydrogel with excellent low-temperature stability (<-60 °C), antibacterial, and UV-blocking capability (≈100%). Interestingly, the diffusion ability of LS is demonstrated for self-restructuring damaged supramolecular hydrogel, achieving 3D patterning on hydrogel surfaces, and enhancing the local strength of the freeze-thaw PVA hydrogel. The goal is to foster a versatile hydrogel platform by combining eco-friendly LS with biocompatible PVA, paving the way for innovation and interdisciplinarity in biomedicine, engineering materials, and forestry science.