Additive Manufacturing of Nanocellulose Aerogels with Structure-Oriented Thermal, Mechanical, and Biological Properties.

Additive manufacturing (AM) is widely recognized as a versatile tool for achieving complex geometries and customized functionalities in designed materials. However, the challenge lies in selecting an appropriate AM method that simultaneously realizes desired microstructures and macroscopic geometrical designs in a single sample. This study presents a direct ink writing method for 3D printing intricate, high-fidelity macroscopic cellulose aerogel forms. The resulting aerogels exhibit tunable anisotropic mechanical and thermal characteristics by incorporating fibers of different length scales into the hydrogel inks. The alignment of nanofibers significantly enhances mechanical strength and thermal resistance, leading to higher thermal conductivities in the longitudinal direction (65 mW m-1 K-1) compared to the transverse direction (24 mW m-1 K-1). Moreover, the rehydration of printed cellulose aerogels for biomedical applications preserves their high surface area (≈300 m2 g-1) while significantly improving mechanical properties in the transverse direction. These printed cellulose aerogels demonstrate excellent cellular viability (>90% for NIH/3T3 fibroblasts) and exhibit robust antibacterial activity through in situ-grown silver nanoparticles.

Aerosol-Assisted Deposition for TiO2 Immobilization on Photocatalytic Fibrous Filters for VOC Degradation.

Atomization and spraying are well-established methods for the production of submicrometer- and micrometer- sized powders. In addition, they could be of interest to the immobilization of photocatalytic nanoparticles onto supports because they enable the formation of microporous films with photocatalytic activity. Here, we provide a comparison of aerosol-assisted immobilization methods, such as spray-drying (SD), spray atomization (SA), and spray gun (SG), which were used for the deposition of TiO2 dispersions onto fibrous filter media. The morphology, microstructure, and electronic properties of the structures with deposited TiO2 were characterized by SEM and TEM, BET and USAXS, and UV-Vis spectrometry, respectively. The photocatalytic performances of the functionalized filters were evaluated and compared to the benchmark dip-coating method. Our results showed that the SG and SA immobilization methods led to the best photocatalytic and operational performance for the degradation of toluene, whereas the SD method showed the lowest degradation efficiency and poor stability of coating. We demonstrated that TiO2 sprays using the SG and SA methods with direct deposition onto filter media involving dispersed colloidal droplets revealed to be promising alternatives to the dip-coating method owing to the ability to uniformly cover the filter fibers. In addition, the SA method allowed for fast and simple control of the coating thickness as the dispersed particles were continuously directed onto the filter media without the need for repetitive coatings, which is common for the SG and dip-coating methods. Our study highlighted the importance of the proper immobilization method for the efficient photocatalytic degradation of VOCs.

Superinsulating nanocellulose aerogels: Effect of density and nanofiber alignment.

Cellulose aerogels are potential alternatives to silica aerogels with advantages in cost, sustainability and mechanical properties. However, the density dependence of thermal conductivity (λ) for cellulose aerogels remains controversial. Cellulose aerogels were produced by gas-phase pH induced gelation of TEMPO-oxidized cellulose nanofibers (CNF) and supercritical drying. Their properties are evaluated by varying the CNF concentration (5-33 mg·cm-3) and by uniaxial compression (9-115 mg·cm-3). The aerogels are transparent with specific surface areas of ~400 m2·g-1, mesopore volumes of ~2 cm3·g-1 and a power-law dependence of the E-modulus (α ~ 1.53, and the highest reported E of ~1 MPa). The dataset confirms that λ displays a traditional U-shaped density dependence with a minimum of 18 mW·m-1·K-1 at 0.065 g·cm-3. For a given density, λ is ~5 mW·m-1·K-1 lower for compressed aerogels due to the alignment of nanofibers, confirmed by small angle X-ray scattering (SAXS).

Biomimetic Light-Driven Aerogel Passive Pump for Volatile Organic Pollutant Removal.

Inspired by the solar-light-driven oxygen transportation in aquatic plants, a biomimetic sustainable light-driven aerogel pump with a surface layer containing black manganese oxide (MnO2 ) as an optical absorber is developed. The flow intensity of the pumped air is controlled by the pore structure of nanofilbrillated cellulose, urea-modified chitosan, or polymethylsilsesquioxane (PMSQ) aerogels. The MnO2 -induced photothermal conversion drives both the passive gas flow and the catalytic degradation of volatile organic pollutants. All investigated aerogels demonstrate superior pumping compared to benchmarked Knudsen pump systems, but the inorganic PMSQ aerogels provide the highest flexibility in terms of the input power and photothermal degradation activity. Aerogel light-driven multifunctional gas pumps offer a broad future application potential for gas-sensing devices, air-quality mapping, and air quality control systems.

Biohybrid Nanocellulose-Lysozyme Amyloid Aerogels via Electrostatic Complexation.

Modern science is increasingly turning to nature for inspiration to design sustainable biomaterials in a smart and effective way. Herein, we describe biohybrid aerogels based on electrostatic complexation between cellulose and proteins-two of the most abundant natural polymers on Earth. The effects of both particle surface charge and particle size are investigated with respect to aerogel properties including the morphology, surface area, stability, and mechanical strength. Specifically, negatively charged nanocellulose (cellulose nanocrystals and cellulose nanofibers) and positively charged lysozyme amyloid fibers (full-length and shortened via sonication) are investigated in the preparation of fibrillar aerogels, whereby the nanocellulose component was found to have the largest effect on the resulting aerogel properties. Although electrostatic interactions between these two classes of charged nanoparticles allow us to avoid the use of any cross-linking agents, the resulting aerogels demonstrate a simple additive performance as compared to their respective single-component aerogels. This lack of synergy indicates that although electrostatic complexation certainly leads to the formation of local aggregates, these interactions alone may not be strong enough to synergistically improve bulk aerogel properties. Nevertheless, the results reported herein represent a critical step toward a broader understanding of biohybrid materials based on cellulose and proteins.

Seaweed-Derived Alginate-Cellulose Nanofiber Aerogel for Insulation Applications.

The next generation of green insulation materials is being developed to provide safer and more sustainable alternatives to conventional materials. Bio-based cellulose nanofiber (CNF) aerogels offer excellent thermal insulation properties; however, their high flammability restricts their application. In this study, the design concept for the development of a multifunctional and non-toxic insulation material is inspired by the natural composition of seaweed, comprising both alginate and cellulose. The approach includes three steps: first, CNFs were separated from alginate-rich seaweed to obtain a resource-efficient, fully bio-based, and inherently flame-retardant material; second, ice-templating, followed by freeze-drying, was employed to form an anisotropic aerogel for effective insulation; and finally, a simple crosslinking approach was applied to improve the flame-retardant behavior and stability. At a density of 0.015 g cm-3, the lightweight anisotropic aerogels displayed favorable mechanical properties, including a compressive modulus of 370 kPa, high thermal stability, low thermal conductivity (31.5 mW m-1 K-1), considerable flame retardancy (0.053 mm s-1), and self-extinguishing behavior, where the inherent characteristics were considerably improved by crosslinking. Different concentrations of the crosslinker altered the mechanical properties, while the anisotropic structure influenced the mechanical properties, combustion velocity, and to some extent thermal conductivity. Seaweed-derived aerogels possess intrinsic characteristics that could serve as a template for the future development of sustainable high-performance insulation materials.

Solvents, CO2 and biopolymers: Structure formation in chitosan aerogel.

The functionality of biopolymer aerogels is inherently linked to its microstructure, which in turn depends on the synthesis protocol. Detailed investigations on the macroscopic size change and nanostructure formation during chitosan aerogel synthesis reveal a new aspect of biopolymer aerogels that increases process flexibility. Formaldehyde-cross-linked chitosan gels retain a significant fraction of their original volume after solvent exchange into methanol (50.3 %), ethanol (47.1 %) or isopropanol (26.7 %), but shrink dramatically during subsequent supercritical CO2 processing (down to 4.9 %, 3.5 % and 3.7 %, respectively). In contrast, chitosan gels shrink more strongly upon exchange into n-heptane (7.2 %), a low affinity solvent, and retain this volume during CO2 processing. Small-angle X-ray scattering confirms that the occurrence of the volumetric changes correlates with mesoporous network formation through physical coagulation in CO2 or n-heptane. The structure formation step can be controlled by solvent-polymer and polymer-drying interactions, which would be a new tool to tailor the aerogel structure.

Dual-porous cellulose nanofibril aerogels via modular drying and cross-linking.

Nanofibrillar foams and aerogels are traditionally either macroporous with low surface area and high mechanical strength, or mesoporous with high surface area and low mechanical strength. In this work, an anionic cellulose nanofibril (CNF)-based dual-porous aerogel with BET specific surface area up to 430 m2 g-1 was prepared via a modular process combining directional freeze-thawing (creating macro-pores, ca. 50-200 µm) and supercritical drying (creating meso-pores, ca. 2-50 nm). Furthermore, by optionally utilizing both physical and chemical cross-linking strategies, aerogels with a Young's modulus of up to 711 kPa and good stability in aqueous conditions were demonstrated. By altering cross-linking strategies, the properties of resulting aerogels, such as hydrophilicity, mechanical strength and stability in water, can be precisely controlled for different applications. As a result, cationic methylene blue (MB) and metal ions (Ag+) were chosen as model species to investigate the absorption properties of the physically cross-linked aerogels in water. The aerogels showed a maximum adsorption of MB up to 234 mg g-1 and of Ag+ up to 116 mg g-1 as a result of the high specific surface area of the aerogels and their strong electrostatic interaction with the model species. Importantly, the hierarchical dual porosity of the aerogels enabled fast adsorption kinetics combined with a considerable adsorption capacity overall. Finally, it was shown that the adsorbed Ag+ could be converted to metallic Ag, demonstrating the additional functionality of these dual porous hybrid aerogels for antibacterial or catalytic applications.