Endowing Thio-Dynamic Network into Bacterial Cellulose for Fabricating Self-Healing Bio-Leather

Bioleather based on bacterial cellulose (BC) offers a sustainable and eco-friendly alternative to traditional animal and synthetic leathers, eliminating toxic chemicals and reducing environmental impact. However, the inherent stiffness and brittleness of BC upon drying, along with limited water resistance and scalability challenges, hinder its practical adoption in high-performance applications. To overcome these challenges, a dual-network structure that leverages both dynamic covalent bonds and noncovalent interactions was designed to achieve simultaneous mechanical robustness and autonomous self-healing. Herein, we fabricated self-healing cellulose-based bioleather using an impregnation technique by incorporating poly(thioctic acid) (PTA) and poly(vinyl alcohol) (PVA) into the BC matrix. The thermally polymerized PTA introduced reversible disulfide exchange reactions, while PVA enhanced interfacial compatibility and flexibility within the BC network. The prepared composite BC–PVA–PTA exhibited tensile stress of 22 ± 0.4 MPa and an elongation at break of 25 ± 0.1%, indicating excellent flexibility and toughness upon drying. Further, this material achieved high self-healing efficiency of 96% at room temperature, along with antibacterial activity and biodegradability confirmed through soil burial testing. Furthermore, this composite was successfully applied in the fabrication of breathable bioleather, highlighting its potential for wearable and textile applications where comfort, durability, and sustainability are essential. This study presents a scalable and cost-effective strategy for developing dynamic, self-healing bio-based materials, addressing the long-standing trade-off between mechanical strength and healability, and advancing next-generation sustainable leather substitutes.