Bamboo‐Inspired Ultra‐Strong, Recyclable, and 3D Printable Supramolecular Eutectogels for Impact Protection and Stimuli‐Responsive Actuation

ABSTRACT Polymerizable deep eutectic solvent (PDES) gels, as sustainable alternatives to hydrogels, exhibit broad environmental tolerance and eco‐benefits. However, their mechanical fragility, complex synthesis, and limited fabrication methods restrict their applications in flexible devices. Here, drawing inspiration from the hierarchical architecture and multi‐component synergy of bamboo, we create a supramolecular eutectogel with a hierarchical architecture by dynamically integrating rigid frameworks and dissipative phases through multiple cross‐scale non‐covalent interactions. Microcrystalline cellulose (rigid framework), lignin (energy‐dissipative phase), and trehalose‐reinforced hydrogen‐bonding networks are dynamically interconnected by long‐chain PDES polymer networks (hemicellulose analogue), forming an isotropic biomimetic architecture that recapitulates the multi‐component composition and hierarchical organization of natural lignocellulosic structures. The one‐step 3D‐printable supramolecular eutectogel features ultra‐high tensile strength (17 MPa), exceptional toughness (64.5 MJ/m 3 ), and excellent adhesion (480 kPa). This design overcomes the strength‐toughness trade‐off in eutectogels while conferring anti‐freezing, self‐healing, and recyclability, and exhibits efficient dynamic energy dissipation, reliable shape memory, and ion‐tunable water resistance. Demonstrated in anti‐impact structures, artificial muscles, and intelligent logic switches, this material shows potential for aerospace shock‐absorption and next‐generation intelligent devices. Our work establishes a new paradigm for high‐performance eutectogels through nature‐inspired supramolecular design and simplified manufacturing.