Directed Assembly of Proteinaceous–Polysaccharide Nanofibrils to Fabricate Membranes for Emerging Contaminant Remediation

Emerging contaminants, including per- and polyfluoroalkyl substances and heavy metals, are threatening the health of humans and ecosystems. Their removal from the environment remains challenging. Here, we designed silk fibroin-cellulose nanocrystal (silk-CNC) nanofibrillar and nanoporous membranes for emerging contaminant remediation. The protein-polysaccharide nanofibrils were fabricated by templating the assembly of silk fibroin using CNCs. Silk fibroin polymorphic nature combined with surface charge modulation of CNCs produced cationic silk-CNC(+) and anionic silk-CNC(-) nanofibrils that can target a broad spectrum of contaminants. Silk-CNC(+) nanofibrils and membranes exhibited antimicrobial properties and captured both short-chain heptafluorobutyric acid, perfluorobutanesulfonic acid, and long-chain perfluorooctanoic acid by virtue of hydrophobic attraction from β-sheeted silk fibroin and electrostatic interactions with CNC(+). Silk-CNC(-) provided the opportunity to target cations such as heavy metal cocontaminants. The nanofabrication of biopolymer-based membranes combines high performance with environmentally benign and cost-effective removal of emerging contaminants for water purification, wastewater treatment, and remediation.