Structure–Property Relationships and Surface Engineering of Natural Biopolymers for Triboelectric Applications: The Role of Additive Manufacturing

This comprehensive review aims to cover the surface tribology and triboelectric properties of additively manufactured (AM) natural biopolymers, including cellulose, chitosan (CS) and silk fibroin (SF), in biomedical interface engineering. While these sustainable materials exhibit innate biocompatibility and tribopositivity, their baseline triboelectric performance demands targeted surface engineering. We synthesize key physical mechanisms governing charge generation, emphasizing how controlled surface roughness, hierarchical porosity and nanoscale architectures maximize contact electrification. Furthermore, distinct dielectric and polarity modulation strategies are evaluated across the biopolymer families: cellulose relies heavily on chemical functionalization to overcome weak native polarity; chitosan utilizes ionic coordination and fillers to elevate its relatively low charge density; and silk fibroin achieves exceptional power outputs via highly porous three-dimensional nanocomposite aerogels. AM technologies afford unprecedented spatial control over these biointerfaces but introduce severe processing constraints. Techniques such as those based on extrusion impose strict shear-thinning rheology and rapid crosslinking for cellulose and chitosan, while SF frequently suffers from crystallization-induced nozzle clogging, necessitating photocurable derivatives.