Development and Tailoring of Low‐Density Cellulose‐Based Structures for Water Treatment

Abstract: The challenges posed by our limited clean water sources and the well-known global water pollution demand more efficient water purification technologies. Additionally, the increasing environmental awareness has inspired a shift towards eco-friendly and renewable materials and technologies. This thesis is focused on developing effective adsorbent materials from renewable resources to eliminate organic solvents, dyes, and metal ions from water. Cellulose, the most abundant biopolymer in nature, is the main component used to develop new materials in the present study. Its distinctive physical and colloidal properties, in the form of nanocellulose, along with tunable surface chemistry, play key roles in enhancing the effectiveness of the developed materials.The primary focus of the first part of the thesis was to develop a molecular layer-by-layer modification technique to customize the surface functionality of cellulose aerogels in a uniform and controlled manner. Through the sequential deposition of diamine and triacid monomers, exceeding lythin polyamide coatings were formed on the cellulose aerogels, altering the surface properties from hydrophilic to hydrophobic. This transformation made them well-suited structures for oil-water separation.Following this, a biohybrid aerogel was developed based on cellulose nanofibrils (CNFs) and amyloid nanofibrils (ANFs), the latter derived by heat treatment of β-lactoglobulin proteins. The pH-tunable surface charge of the aerogel, controlled by the amphiphilicity of the protein, allowed for the adsorption of both cationic and anionic contaminants by adjusting the pH of the solutions. Furthermore, the aerogels exhibited remarkable selectivity for lead (II) ions and they could also be regenerated and reused after each adsorption cycle without a significant loss of their adsorption capacity. This was to a large extent possible due to the excellent wet stability of these aerogels, which was achieved by crosslinking the CNFs during freezing and ice templating, eliminating the need for freeze-drying. However, a solvent exchange to acetone after melting was still necessary to reduce the influence of the capillary forces during drying to avoid the collapse of the aerogels. In a consecutive study, the foaming characteristics of the heat-treated β-lactoglobulin system were exploited to create highly stable Pickering foams with the aid of using CNFs as stabilizers and to physically lock the system through a controlled pH reduction. Interestingly, these Pickering foams could be directly oven-dried without collapsing, yielding low-density foams. Furthermore, it was demonstrated that the foams can be chemically crosslinked by incorporating chemical crosslinkers in the formulation or by pre-functionalizing the CNFs with dialdehydes. This crosslinking naturally also provided wet stability to the oven-dried foams.Finally, an innovative and environmentally friendly method was introduced to increase the charge of cellulose fibers by radical polymerization of acrylic acid from the fibers, enabling the preparation of fibers with an exceptionally high charge of 6.7 mmol/g. The introduction of these charged groups significantly enhanced the interaction of the fibers with methylene blue as a model dye and lead (II), Copper (II), and Zinc (II) ions as model metal ions, showing the huge potential of these fibers as building blocks for a wide range of adsorbent applications. Overall, this thesis demonstrates the development and characterization of several bio-based adsorbents for water remediation.