In situ growth of Zr-based metal-organic frameworks on cellulose sponges for Hg2+ and methylene blue removal.

Metal-organic frameworks (MOFs) are characterised by high porosity levels and controllable structures, making them ideal adsorbents for wastewater. However, obtaining substrate materials with mechanical stability, excellent pore accessibility, and good processability for compositing MOF crystal powders to adsorb multiple pollutants in complex aqueous environments is challenging. In this study, porous MOFs@ modified cellulose sponge (MCS) composites were fabricated using MCS as a scaffold to provide anchoring sites for the coordination of Zr4+ ions and further in situ synthesis of MOFs, namely UiO-66@MCS and UiO-66-NH2@MCS, which effectively removed heavy metal ions and organic dyes. MOFs@MCS composites exhibit excellent water and dimensional stability, maintaining the pore structure by ambient drying during reuse. Compared with UiO-66@MCS composite, UiO-66-NH2@MCS composite exhibited a higher adsorption capacity of 224.5 mg·g-1 for Hg2+ and 400.9 mg·g-1 for methylene blue (MB). The adsorption of Hg2+ onto the MOFs@MCS composites followed the Langmuir and pseudo-second-order models, whereas the Freundlich and pseudo-second-order models were more suitable for MB adsorption. Moreover, the MOFs@MCS composites exhibited excellent reusability and were selective for the removal of Hg2+. Overall, this approach effectively combines Zr-based MOFs with mechanically and dimensionally stable porous cellulose sponges, rendering the approach suitable for purifying complex wastewater.

Cellulose nanocrystal thermal smart molecular brushes with upper critical aggregation temperature.

Grafting thermo-responsive polymers onto cellulose nanocrystals (CNCs) and achieving critical temperature regulation has drawn significant research interest. The thermal transition behavior of CNCs can be controlled by adjusting the polymer molecular brushes on the CNCs surface. We synthesized poly((2-dimethylamino) ethyl methacrylate) (PDMAEMA) grafted CNCs via surface-initiated reversible addition-fragmentation chain transfer, followed by modifying PDMAEMA brushes into poly-3-dimethyl(methacryloyloxyethyl) ammonium propane sulfonate (PDMAPS) brushes via quaternization. The critical temperature was regulated by modifying and grafting of poly (ethylene glycol) methacrylate. Found the thermal stimulus-responsive type and transition point of CNCs can be controlled by adjusting the surface molecular brushes. Ultraviolet-visible spectroscopy and dynamic light scattering analyses indicated that CNC-PDMAEMA aggregated above 70 °C, whereas CNC-PDMAPS aggregated below 31 °C. The thermo-responsive materials based on CNCs exhibited a conversion from a lower critical aggregation temperature to an upper critical aggregation temperature (UCAT) type. CNC-PDMAPS-mPEG was obtained by modifying and grafting for UCAT to be regulated to approximately 37 °C, which is close to the human body temperature. CNC-PDMAPS and CNC-PDMAPS-mPEG exhibited only microscopic alterations and could encapsulate and release substances. Therefore, they demonstrate considerable potential for biomedical applications.

Co-assembly of stearoylated cellulose nanocrystals and GO (or CNTs) for the construction of superhydrophobic hierarchical structure with enhanced photothermal conversion.

The development of photothermal materials with high photothermal-conversion efficiencies is important in a range of applications, such as power generation, sterilization, desalination, and energy-production. To date, a few reports have been published related to improving the photothermal conversion performances of photothermal materials based on self-assembled nanolamellae. Herein, hybrid films of co-assembled stearoylated cellulose nanocrystals (SCNCs) and polymer-grafted graphene oxide (pGO)/polymer-grafted carbon nanotubes (pCNTs) were prepared. The chemical compositions, microstructures, and morphologies of these products were characterized, and it was found that the self-assembled SCNC structures exhibited numerous surface nanolamellae due to crystallization of the long alkyl chains. The hybrid films (i.e., SCNC/pGO and SCNC/pCNTs films) consisted of ordered nanoflake structures, confirming the co-assembly behavior of the SCNCs with pGO or pCNTs. The melting temperature (~65 °C) and latent heat of melting (87.87 J/g) of SCNC1.07 indicate its potential to induce the formation of nanolamellar pGO or pCNTs. Under light irradiation (50-200 mW/cm2), the pCNTs exhibited a higher light absorption capacity than pGO, and as a result, the SCNC/pCNTs film exhibited the best photothermal performance and electrical conversion, ultimately demonstrating its potential for use as a solar thermal device in practical applications.

Aliphatic chains grafted cellulose nanocrystals with core-corona structures for efficient toughening of PLA composites.

To promote the replacement of nondegradable petrochemical-based polymers with green polylactic acid (PLA) materials, aliphatic chains-grafted cellulose nanocrystals (ECNCs) were prepared and used as nanofillers to overcome the disadvantage of poor toughness of PLA. ECNCs with core-corona structures were obtained by modifying cellulose nanocrystals (CNC) with valeryl chloride, octanoyl chloride, dodecanoyl chloride, and stearoyl chloride. ECNCs consists of a cellulose crystalline core and a soft esterified corona layer with aliphatic chains. Among the diverse ECNCs, the obtained EOCNC by esterification of octanoyl chloride exhibited most efficient enhancement of the toughness of PLA. Specifically, PLA/EOCNC-1% film displayed the best elongation at breakage of 108%, which was 6.4 times that of pure PLA. The esterified outer layer of ECNCs, which improves the interfacial compatibility, is one of the key factors contributing to toughening of PLA. These ECNCs with core-corona structure open up new directions for the application of PLA advanced composites.

Click chemistry-induced modification of acrylated cellulose nanocrystals for application in PVA-based nanocomposites.

The surface functionalization of cellulose nanocrystals (CNC) is crucial for promoting their diverse applications, especially regarding their use as sustainable biobased polymer reinforcements. In this study, we develop poly (vinyl alcohol) (PVA)-CNC composites with improved tensile strength and gas-barrier performance using CNC-based nanofillers. Acrylated CNCs (ACNCs) were prepared from cellulose via one-pot acid hydrolysis/Fischer esterification; subsequently, surface modification was performed through a thiol-ene reaction to obtain surface-thiolated ACNCs, namely, DACNC, MACNC, and PACNC. The various functional groups on the surface-thiolated ACNCs not only affect the dispersion stability but also alter their interfacial interactions with the PVA matrix, thus realizing the PVA nanocomposites with tailored properties, including the thermal properties, mechanical properties, and gas barrier performance. This study demonstrates that surface-thiolated ACNCs with appropriate surface chemistry and loading levels can serve as excellent nanofillers for PVA, forming biobased composites with desired properties.

Multifunctional Reversible Self-Assembled Structures of Cellulose-Derived Phase-Change Nanocrystals.

Owing to advantageous properties attributed to well-organized structures, multifunctional materials with reversible hierarchical and highly ordered arrangement in solid-state assembled structures have drawn tremendous interest. However, such materials rarely exist. Based on the reversible phase transition of phase-change materials (PCMs), phase-change nanocrystals (C18-UCNCs) are presented herein, which are capable of self-assembling into well-ordered hierarchical structures. C18-UCNCs have a core-shell structure consisting of a cellulose crystalline core that retains the basic structure and a soft shell containing octadecyl chains that allow phase transition. The distinct core-shell structure and phase transition of octadecyl chains allow C18-UCNCs to self-assemble into flaky nano/microstructures. These self-assembled C18-UCNCs exhibit efficient thermal transport and light-to-thermal energy conversion, and thus are promising for thermosensitive imaging. Specifically, flaky self-assembled nano/microstructures with manipulable surface morphology, surface wetting, and optical properties are thermoreversible and show thermally induced self-healing properties. By using phase-change nanocrystals as a novel group of PCMs, reversible self-assembled multifunctional materials can be engineered. This study proposes a promising approach for constructing self-assembled hierarchical structures by using phase-change nanocrystals and thereby significantly expands the application of PCMs.

Cellulose-Based Superhydrophobic Surface Decorated with Functional Groups Showing Distinct Wetting Abilities to Manipulate Water Harvesting.

Inspired by the distinct functions of desert beetles with efficient droplet nucleation and lotus leaves with excellent droplet removal, an integrated method is presented for the design of a superhydrophobic surface decorated with hydrophilic groups that can efficiently nucleate and remove water droplets. We constructed a cellulose-based superhydrophobic surface containing numerous olefin terminal groups by solvent exchange and spray coating. This surface is different from most of the reported biomimicking water harvesting surfaces that rely on complicated lithography and micropatterning techniques requiring special instruments. The obtained superhydrophobic surface was further modified using various thiol compounds via a thiol-ene reaction to manipulate the water harvesting property. The modified surfaces containing hydrophobic groups (e.g., 1-octadecanethiol and 1H,1H,2H,2H-perfluorodecanethiol) or a strong hydrophilic group (e.g., 3-mercaptopropionic acid and 6-mercapto-1-hexanol) exhibited insufficient fog collecting abilities due to poor water droplet nucleation or strong water adhesion. By contrast, the modified surface decorated with moderately hydrophilic amino groups combines the advantages of biological surfaces with distinct wetting features (such as fog-harvesting beetles and water-repellent lotus leaves), resulting in accelerated water nucleation and less compromise of the water removal efficiency. Molecular dynamic simulations revealed that the efficient droplet nucleation is attributed to the hydrophilic amino groups whereas the rapid droplet removal is due to the maintained superhydrophobicity of the amino group-modified surface. This strategy of decorating a superhydrophobic surface with moderately hydrophilic functional groups provides insight into the manipulation of droplet nucleation and removal for water collection efficiency.

Thermal, antioxidant and swelling behaviour of transparent polyvinyl (alcohol) films in presence of hydrophobic citric acid-modified lignin nanoparticles.

Lignin nanoparticles (LNP) have been esterified and etherified by citric acid and then blended with poly (vinyl alcohol) (PVA) at various loading levels (up to 10 wt%). Poly(vinyl alcohol) nanocomposite films containing unmodified and modified lignin nanoparticles (LNP and MLNP) were prepared through solvent casting approach. Microscopic investigation of films fractured surfaces confirmed that MLNP could be evenly dispersed in PVA matrix, and no macroscopic phase separation was generated in the nanocomposite films. Water contact angle, swelling efficiency and moisture adsorption properties of LNP and MLNP based films were measured and compared, revealing an overall increase of dimensional stability and reduced moisture adsorption for MLNP nanocomposites. MLNP based nanocomposite films outperformed the films containing LNP in antioxidant property and transparency, slight sacrificing in UV-absorbing, confirming these materials as promising candidates for applications requiring high antioxidant potential and improved performance towards light absorbance.