The global environmental concerns drive scientists all over the world to develop eco-friendly and sustainable alternatives to techniques and materials commonly used until now for water treatment applications. The relatively novel Additive manufacturing (AM) technology allows to process materials in a custom optimized, cost and time effective manner, while use of biobased materials minimizes the secondary pollution issue. Combining three-dimensional (3D) printing technology and biopolymer-based materials refines the water treatment industry, as it provides tailored water filtration systems easily available in the disadvantaged areas at low environmental impact and cost due to the raw materials' bio-origin and abundance. This review highlights the combination of various 3D printing techniques such as Fused deposition modelling (FDM), Direct ink wetting (DIW) and Stereolitography (SLA) with nature-derived biopolymers and biopolymerbased materials including chitosan, Polylactic acid (PLA), alginate and Cellulose acetate (CA) for their potential application within the water treatment industry with emphasis on oil separation and metal removal. Moreover, the environmental impact of the revised biopolymers is briefly discussed.

Considering the current trend of finding sustainable alternatives to the existing fossil-based plastics, in this review we describe what makes a bioelastomer “bio” and what this implies in terms of materials design. We analyze the current state of development of bioelastomers, including the most important types, their current and upcoming use, and their synthetic pathways. Moreover, we provide a general landscape of the hybridization or composite preparation of elastomers to acquire specific functionalities and their implementation in advanced applications, focusing mainly on electronics and biomedicine. Furthermore, we show how through the use of bioelastomers, one can, besides helping the environment, achieve materials with exceptional performances (e.g., very high mechanical properties and/or self-healing properties), which can be processed via novel techniques such as 3/4D-(bio)printing.

In this thesis, materials from renewable resources were used to develop functionalized surfaces for water treatment. The work is thus inspired by, and contributes to, the United Nations sustainable goals of: (i) clean water and sanitation, (ii) climate action, (iii) responsible consumption and production, (iv) life below water, and (v) partnerships for the goals.

Nanopolysaccharides, most specifically nanocellulose and nanochitin, are great candidates for functional and renewable materials for multiple applications, including the treatment of water and wastewater. This thesis focused on the formulation of different types of nanopolysaccharide-based coatings to enhance the performance of commercially available membranes and cellulose fabrics. We developed a simple waterborne layer-by-layer cellulose nanocrystals (CNC) and TEMPO-oxidized cellulose nanofibrils (T-CNF) coating for commercially available membranes. By changing the surface and pore structure of the membrane, the coating tuned which substrates could pass through the membrane, improved antifouling performanced, and when derived from T-CNF, it was harmful to bacterial colonization. Considering the observed T-CNF’s effect on bacteria, we developed a chemically crosslinked T-CNF/Poly(vinyl) alcohol (PVA) coating with outstanding antibiofouling performance, ion adsorption/rejection combined with size exclusion, and with dimensional and pH stability. Furthermore, we used a surface-impregnation approach based on bio-based nanotechnology which resulted in highly efficient, with improved mechanical properties, and fully bio-based high-flux water filtration membranes using commercially available nonwoven fabrics. Membranes with coatings prepared from CNC, chitin nanocrystals (ChNC) and T-CNF separated particles in the size range of bacteria and viruses, and those prepared from also T-CNF showed high microplastic filtration efficiency. Moreover, membrane coating based on ChNC and T-CNF had outstanding antibacterial properties.

Overall, we demonstrated that nanopolysaccharide coatings on membranes could provide a significant reduction in organic fouling and biofilm formation while enabling the adsorption of ions and separation of microplastics. In the case of biofilm formation, the functional group and surface charge of the different nanopolysaccharides determined the effect over bacteria, indicating that surfaces could be tailored against microbes. In addition, we directly compared the effect of the different nanopolysaccharides of interest (CNC, T-CNF, ligno-celullose nanocrystals (L-CNC), and ChNC) on bacterial viability and biofilm formation, and found a great difference between the different types of nanocellulose and a different mechanism for nanochitin. Thorough, none of the nanopolysaccharides displayed cytotoxic effects while in indirect contact with the bacterial cells. Nevertheless, T-CNF, ChNC and L-CNC showed a cytostatic effect on bacterial proliferation. Furthermore, the nanomechanical properties of the bacterial cells and interacting forces between the nanopolysaccharides and Escherichia coli (E. coli) were affected when in direct contact with the nanopolysaccharide surfaces.

Lastly, we upscaled one of our coating processes, demonstrating that the method could be easily implemented at an industrial level. The impact of this thesis relies on the effectiveness of the coatings, the different types of functionalities observed, the demonstrated fast implementation at an industrial scale, and the potential to extrapolate this technology to other applications.

The utilisation of plant-derived nanoscale cellulosic materials (cellulose nanofibrils, CNF) in tailoring water purification membranes is constantly gaining interest in the context of green-functionalised membrane solutions. However, most of the existing approaches based on renewable and biobased materials suffer from the lack of efficient and scalable processing strategies. Here, we introduce a roll-to-roll membrane modification approach based on thin submicron nanocellulose coatings (400–800 nm) to manufacture anti-biofouling membranes with size and charge dependent selectivity using unit operations compatible with existing industrial lines. We turned a commercial polymeric polyethersulfone (PES) microfiltration membrane into highly hydrophilic and tight membrane structure by applying thin and water-durable cellulose nanofibril layers using cast or spray coating methods. Nanocellulose coated membranes exhibited water permeance values of 80 – 100 LMH/MPa with the highest rejection levels of > 90% for Cytochrome C. Furthermore, the nanocellulose layers were able to withstand relatively high filtration pressure levels of 1 MPa, indicating that the selected procedures to improve mechanical integrity i.e. polyethylene imine-based anchoring and acid induced CNF cross-linking were successful. The coated membranes with the thinnest nanocellulose layer exhibited a molecular weight cut-off (MWCO) of 2 kDa for negatively charged polystyrene sulfonate and 14 kDa for neutral dextrane indicating charge selective behaviour. It can be concluded that our nanocellulose coated PES membranes represent nanofiltration membranes and lower boundary of ultrafiltration membranes with clear anti-biofouling performance directly evidenced via systematic bovine serum albumin (BSA) adsorption investigations. Our approach paves the way towards tunable and sustainable water treatment technologies simultaneously opening space for novel biobased solutions in membrane sector.

This study reports the potential of TEMPO-oxidized cellulose nanofibrils (T-CNF)/poly(vinyl alcohol) (PVA) coatings to develop functionalized membranes in the ultrafiltration regime with outstanding antifouling performance and dimensional/pH stability. PVA acts as an anchoring phase interacting with the polyethersulfone (PES) substrate and stabilizing for the hygroscopic T-CNF via crosslinking. The T-CNF/PVA coated PES membranes showed a nano-textured surface, a change in the surface charge, and improved mechanical properties compared to the original PES substrate. A low reduction (4%) in permeance was observed for the coated membranes, attributable to the nanometric coating thickness, surface charge, and hydrophilic nature of the coated layer. The coated membranes exhibited charge specific adsorption driven by electrostatic interaction combined with rejection due to size exclusion (MWCO 530 kDa that correspond to a size of similar to 35-40 nm). Furthermore, a significant reduction in organic fouling and biofouling was found for T-CNF/PVA coated membranes when exposed to BSA and E. coli. The results demonstrate the potential of simple modifications using nanocellulose to manipulate the pore structure and surface chemistry of commercially available membranes without compromising on permeability and mechanical stability.

This article presents a comparative study of the surface characteristics and water purification performance of commercially available cellulose nonwoven fabrics modified, via cast coating, with different nano-dimensioned bio-based carbohydrate polymers, viz. cellulose nanocrystals (CNC), TEMPO-oxidized cellulose nanofibers (T-CNF), and chitin nanocrystals (ChNC). The surface-modified nonwoven fabrics showed an improvement in wettability, surface charge modification, and a slight decrease of maximum pore size. The modification improved the water permeance in most of the cases, enhanced the particle separation performance in a wide range of sizes, upgraded the mechanical properties in dry conditions, and showed abiotic antifouling capability against proteins. In addition, T-CNF and ChNC coatings proved to be harmful to the bacteria colonizing on the membranes. This simple surface impregnation approach based on green nanotechnology resulted in highly efficient and fully bio-based high-flux water filtration membranes based on commercially available nonwoven fabrics, with distinct performance for particle rejection, antifouling and antibacterial properties.

This article presents a waterborne nanocellulose coating process to change the surface characteristics and mitigate fouling of commercially available polyethersulfone (PES) microfiltration membranes. An extensive comparative study between nanoporous and nano-textured layers composed of cellulose nanocrystals (CNC) or TEMPO-oxidized cellulose nanofibrils (T-CNF), which were coated on the PES membrane by taking advantage of the electrostatic interactions between the PES substrate, a polyallylamine hydrochloride (PAHCl) anchoring layer, and the nanocellulose functional layer. Coated PES membranes exhibited decreased surface roughness and pore sizes as well as rejection of compounds with a M_w above 150 kDa, while the water permeability and mechanical properties of remained largely unaffected. The coatings improved the wettability as confirmed by a reduction of the contact angle by up to 52% and exhibited a higher negative surface charge compared to the uncoated membranes over a pH range of 4–8. A significant reduction in organic fouling was observed for the coated membranes demonstrated by bovine serum albumin (BSA) adsorption studies on T-CNF and CNC surfaces using Quartz Crystal Microbalance with Dissipation monitoring (QCM-D), UV–vis spectroscopy and FTIR mapping after exposing the membranes to dynamic adsorption of BSA. The T-CNF coating exhibited effective antibacterial action against Escherichia coli (E. coli) attributed to the pH reduction effect induced by the carboxyl groups; while CNC coatings did not show this property. This work demonstrates a simple, green, and easy-to-scale layer-by-layer coating process to tune the membrane rejection and to improve antifouling and antibacterial properties of commercially available membranes.

Microporous (<2 nm) crystalline aluminosilicates in the form of zeolites offer a great potential as efficient adsorbents for atmospheric CO2 in the eminent battle against global warming and climate change. The processability of conventional zeolite powders is, however, poor, which limits their implementation in many applications, such as in gas filtration industrial systems. In this work, we overcome this issue through the preparation of hybrid foams using mesoporous/macroporous supporting materials based on the strong network properties of gelatin/nanocellulose, which can support ultrahigh loadings of silicalite-1, used as a model sorbent nanomaterial. We achieved up to 90 wt % of zeolite content and a microporous/mesoporous/macroporous hybrid material. The application of hybrid foams for selective CO2 sorption exhibits a linear relationship between the zeolite content and CO2 adsorption capacity and high selectivity over N2, where the gelatin/nanocellulose foam efficiently supports the zeolite crystals without apparently blocking their pores.

Membrane technology is commonly used for filtration processes of industrial wastewater. Using membranes for water filtration is a safe and energy efficient solution. One of the main problems that arises during the usage of membranes is the fouling effects. Fouling increases the membrane separation resistance, reduces productivity due to a flux decline and affect membrane selectivity. These effects can be avoid by modifying the surface of the membranes using bio-based materials such as nano-cellulose. Nano-cellulose is a great example of a material obtained from renewable resources, which provides high reinforcement and antifouling properties to membranes.

The aim of this work was the development of coatings with cellulose nano-crystals (CNC) and Tempooxidized cellulose nano-fribrils (T-CNF) using polyvinyl-alcohol (PVOH), as binding phase to enhance mechanical and antifouling properties over pure commercial PES membranes. The coatings were chemically crosslinked to increase mechanical properties and to improve stability of the coating and avoid swelling. It is expected that by avoiding swelling, permeability remains stable through time. All coating formulations remained stable after 10 hours of crossflow filtration. Mechanical properties of the coated membranes were improved in both dry and wet conditions, showing higher values of tensile strenght and E modulus compared to the uncoated ones. In addition, coated membranes showed high hydrophilicity and low adherence of bovine serum albumin (BSA).

The coatings developed showed stability over PES membranes and provide them with a nanostructured surface which showed an extended durability in use. The modified surface membranes presented good mechanical properties in dry and wet conditions, high flux, high hydrophilicity, resistance to BSA fouling and to different pH environments. Moreover, these modified membranes showed promising results for fast upscaling at industrial level due to the simplicity of the coating process and the availability of the materials in the market.