Self‐Assembly of Organic–Inorganic Copolymers Toward Bio‐Inspired Cementitious Composites

ABSTRACT

Refined by millions of years of rigorous evolution, highly mineralized biological materials have perfected organic–inorganic self‐assembly to break the traditional trade‐off between strength and damage tolerance. Their rigid‐flexible precursor architectures motivate an organic–inorganic copolymerization strategy for the bottom‐up design of cementitious materials, the most pervasive and resource‐intensive engineered products. Herein, as the primary binding phase in cement, calcium silicate hydrate (CSH) is copolymerized with thioctic acid (TA) into a hybrid precursor through a thermodynamically spontaneous process driven by Lewis acid‐base coordination (Ca ²⁺ ‐COO ⁻ ). Hot pressing promotes the synergistic evolution of amorphous CSH into a denser and structurally reorganized framework together with TA crosslinking, resulting in a self‐organized organic–inorganic nanocomposite that resembles the disordered collagen‐mineral architecture in trabecular bone. Notably, the poly(CSH‐TA) composite features a microphase‐homogeneous architecture that delivers an exceptional compressive strength of over 300 MPa at 10% strain. Even more impressively, we demonstrated the intrinsic physical reprocessibility of cementitious materials, allowing retention of over 80% of strength and energy absorption capacity through five consecutive powder‐to‐bulk cycles. The organic–inorganic copolymerization route opens a bioinspired pathway for next‐generation cementitious materials toward achieving multifunctional performance breakthroughs.