The inherent colloidal dispersity (due to length, aspect ratio, surface charge heterogeneity) of CNCs, when produced using the typical traditional sulfuric acid hydrolysis route, presents a great challenge when interpreting colloidal properties and linking the CNC film nanostructure to the helicoidal self-assembly mechanism during drying. Indeed, further improvement of this CNC preparation route is required to yield films with better control over the CNC pitch and optical properties. Here we present a modified CNC-preparation protocol, by fractionating and harvesting CNCs with different average surface charges, rod lengths, aspect ratios, already during the centrifugation steps after hydrolysis. This enables faster CNC fractionation, because it is performed in a high ionic strength aqueous medium. By comparing dry films from the three CNC fractions, discrepancies in the CNC self-assembly and structural colors were clearly observed. Conclusively, we demonstrate a fast protocol to harvest different populations of CNCs, that enable tailored refinement of structural colors in CNC films.

Photonic films based on cellulose nanocrystals (CNCs) are sustainable candidates for sensors, structurally colored radiative cooling, and iridescent coatings. Such CNC-based films possess a helicoidal nanoarchitecture, which gives selective reflection with the polarization of the incident light. However, due to the hygroscopic nature of CNCs, the structural colored material changes and may be irreversibly damaged at high relative humidity. Thus, moisture protection is essential in such settings. In this work, hygroscopic CNC-based films are protected with a bioinspired synthetic plant cuticle; a strategy already adopted by real plants. The protective cuticle layers altered the reflected colors to some extent, but more importantly, they significantly reduced the water vapor permeance by more than two orders of magnitude, from 2.1 × 107 (pristine CNC/GLU film) to 12.3 × 104 g µm m−2 day−1 atm−1 (protected CNC/GLU film). This expands significantly the time window of operation for CNC/GLU films at high relative humidity.

Radiative cooling forms an emerging direction in which objects are passively cooled via thermal radiation to cold space. Cooling materials should provide high thermal emissivity (infrared absorptance) and low solar absorptance, making cellulose an ideal and sustainable candidate. Broadband solar-reflective or transparent coolers are not the only systems of interest, but also more pleasingly looking colored systems. However, solutions based on wavelength-selective absorption generate not only color but also heat and thereby counteract the cooling function. Intended as coatings for solar cells, we demonstrate a transreflective cellulose material with minimal solar absorption that generates color by wavelength-selective reflection, while it transmits other parts of the solar spectrum. Our solution takes advantage of the ability of cellulose nanocrystals to self-assemble into helical periodic structures, providing nonabsorptive films with structurally colored reflection. Application of violet-blue, green, and red cellulose films on silicon substrates reduced the temperature by up to 9 °C under solar illumination, as result of a combination of radiative cooling and reduced solar absorption due to the wavelength-selective reflection by the colored coating. The present work establishes self-assembled cellulose nanocrystal photonic films as a scalable photonic platform for colored radiative cooling. 

Cellulose nanocrystals (CNCs) possess the ability to form helical periodic structures that generate structural colors. Due to the helicity, such self-assembled cellulose structures preferentially reflect left-handed circularly polarized light of certain colors, while they remain transparent to right-handed circularly polarized light. This study shows that combination with a liquid crystal enables modulation of the optical response to obtain light reflection of both handedness but with reversed spectral profiles. As a result, the nanophotonic systems provide vibrant structural colors that are tunable via the incident light polarization. The results are attributed to the liquid crystal aligning on the CNC/glucose film, to form a birefringent layer that twists the incident light polarization before interaction with the chiral cellulose nanocomposite. Using a photoresponsive liquid crystal, this effect can further be turned off by exposure to UV light, which switches the nematic liquid crystal into a nonbirefringent isotropic phase. The study highlights the potential of hybrid cellulose systems to create self-assembled yet advanced photoresponsive and polarization-tunable nanophotonics.

Heterogeneous photocatalysis exhibits the potential for the complete degradation of pollutants present in water or gas phase. The effective realization of heterogeneous photocatalysis, at both large-scale industrial setups for water treatment and in situ application for solar remediation of ecological units, can be achieved by the concurrent development of photocatalytic supports along with solid semiconductor materials targeted for implementation as photocatalysts. This chapter provides an update of such developments in the field of photocatalytic supports, very specifically, on cellular solid-based carriers (foams). In the first part, a brief introduction to the fundamentals of cellular solids is presented. Subsequently, the role of cellular solids, as structured photocatalytic supports, for implementation in large-scale, continuously processed photoreactors for high-throughput water treatment, are discussed. The second part of this chapter reports all the materials used, up-to-date, in the fabrication of cellular solid-based photocatalyst carriers for the real-time solar remediation of the natural system. Finally, this chapter ends up in the discussion of novel cellulose nanofiber-based nanofoams as buoyant photocatalytic supports for the realization of bio-based, nonmetallic, nontoxic floating photocatalysts.

Lignin is a valuable bio-resource in the manufacturing of carbon-based functional materials, because of its large carbon content (~60%), various phenolic structural units, abundancy and sustainability. Here, we explored its use in photocatalytic and self-propelling applications. First, hydroxyl-abundant lignin-based carbon precursor particles, HCLSs, were produced by hydrothermal carbonization of lignin-based microcapsules (LCs). Then, by heating urea coated HCLSs, carbon spheres with a layer of graphitic carbon nitride (g-C3N4) were produced. The presence of surface available -OH groups on the HCLSs, were critical in the formation mechanism. Under visible-light irradiation, the photocatalytic spheres exhibited enhanced activity (49% of the model pollutant remained after 60 min, at 100 mW cm−2) and possessed a three times higher average removal rate constant compared to that of g-C3N4 powder. The g-C3N4 powder was obtained when heating urea only. Additionally, by introducing a Pt/Pd coating on only one side of the composite spheres, the spheres were made self-propelling in the presence of a fuel (H2O2). This work provides new insights into the preparation principles of lignin-based photocatalytic spheres for effective solar photocatalysis applications.

The transfer of heterogeneous photocatalysis applications from the laboratory to real-life aqueous systems is challenging due to the higher density of photocatalysts compared to water, light attenuation effects in water, complicated recovery protocols, and metal pollution from metal-based photocatalysts. In this work, we overcome these obstacles by developing a buoyant Pickering photocatalyst carrier based on green cellulose nanofibers (CNFs) derived from wood. The air bubbles in the carrier were stable because the particle surfactants provided thermodynamic stability and the derived photocatalytic foams floated on water throughout the test period (4 weeks). A metal-free semiconductor photocatalyst, g-C3N4, was facilely embedded inside the foam by mixing the photocatalyst with the air-bubble suspension followed by casting and drying to produce solid foams. When tested under mild irradiation conditions (visible light, low energy LEDs) and no agitation, almost three times more dye was removed after 6 h for the floating g-C3N4-CNF nanocomposite foam, compared to the pure g-C3N4 powder residing on the bottom of a ca. 2 cm-high water pillar. The buoyancy and physicochemical properties of the carrier material were imperative to render escalated oxygenation, high photon utilization, and faster dye degradation. The reported assembly protocol is facile, general, and provides a new strategy for assembling green floating foams that can potentially carry a number of different photocatalysts.