Cellulose nanofibril (CNF) aerogels have attracted great interests in recent years due to the low cost, sustainability and biocompatibility of raw CNF. However, the poor thermal stability and flammable feature of CNF aerogels have limited their wider applications. In this paper, polydopamine/CNF composite aerogels with good comprehensive properties are fabricated by modification of CNF with polydopamine and metal coordination bonds crosslinking. The microstructure and properties of composite aerogels are thoroughly characterized by a variety of tests. It is found that the microstructure of aerogels are more regular and the compressive strength of aerogels are enhanced by the incorporation of polydopamine and Fe3+ crosslinking. Importantly, the thermal stability and flame resistance of aerogels are significantly improved, which permit the application of composite aerogels in high-temperature thermal insulation. In addition, the reversible characteristic of metal coordination bonds allows the water induced healing of fractured composite aerogels. This study is expected to provide information for future development of green and high-performance aerogels.
Graphic abstractIn this study, the effect of pectin extraction method on the properties of cellulose nanofibers (CNFs) isolated from sugar beet pulp (SBP) was studied. Pectin was extracted by the industrially practiced method by sulfuric acid hydrolysis or by enzymatic hydrolysis using a cellulase/xylanase enzymes mixture. The CNFs were then isolated by high-pressure homogenization and investigated in terms of their chemical composition, crystallinity, size, degree of polymerization, and re-dispersion in water after freeze-drying. The mechanical properties and surface characteristics of CNF films were also studied. The results showed that fibrillation of the de-pectinated SBP was more efficient for the acid hydrolyzed SBP. CNFs from the acid-hydrolyzed SBP had a slightly wider diameter, higher crystallinity, viscosity, and α-cellulose content but a lower degree of polymerization than CNFs from the enzyme-hydrolyzed SBP. Owing to the presence of more residual hemicelluloses in the CNFs from the enzyme-hydrolyzed SBP, the CNFs had higher re-dispersion ability in water. CNF films from enzyme-hydrolyzed SBP displayed slightly better mechanical properties and higher water contact angle than acid-hydrolyzed CNF films.
Graphic abstractThis study prepared a waterproof cellulose nanofibril (CNF) sheet via the deposition of an alkyl ketene dimer (AKD) on the sheet’s controlled porous structure. The porosity of the CNF sheet was controlled by drying under different conditions, which included hot-press drying (HD) and solvent-exchange drying (SD), and the effect on the hydrophobization and water-related barrier performance of the sheet were investigated. When the SD sheet was immersed in an AKD wax solution, the sheet exhibited super-hydrophobicity and a lower water vapor transmission rate, compared with the HD sheet. This indicated that the porous structure of the SD sheet enabled AKD to be adsorbed on both the surface and the inner surface and it filled in the pores of the sheet, thereby giving rise to excellent waterproofing properties. The performance of a hydrophobized SD sheet as a water barrier material was comparable to a linear low-density polyethylene film. This study confirms the possibility for AKD wax to be immersed in a porous CNF sheet and used as a potential barrier material in hydrogel packaging.
Graphical abstractIn this paper, we developed a microbial route to fabricate wood-inspired biomimetic composites comparable to natural wood. Focusing on the chemical composition of woody biomass, we performed in situ bioprocessing of bacterial cellulose (BC) imbibed in modified cationic lignin (Catlig), which exhibited significant bioactivity in improving the microbial growth dynamics. The structural and morphological characteristics were enhanced by the formation of hydrophobic and electrostatic interactions between BC and Catlig during biosynthesis. Microbially derived BC/Catlig composites exhibited enhanced thermal stability and crystallinity, with oriented cellulose fibers. The tensile properties, toughness, and specific strength of BC/Catlig composites were comparable to those of a heavy wood species (Zelkova serrata) under hydrated conditions and synthetic soft materials.
Graphic abstractThe development of a simple surface barrier discharge plasma device is presented to enable more widespread access to and utilization of plasma technology. The application of the plasma device was demonstrated for pretreatment of wood prior to application of protective coatings for outdoor usage. The coatings' overall performance was increased, showing a reduction or absence of cracking due to weathering on plasma-pretreated specimens. Moreover, after ten months of outdoor weathering, the plasma-pretreated specimens showed fewer infections with biotic factors and improved adhesion performance in cross-cut tests, while the surface gloss performed independently from plasma pretreatment. In contrast to that, plasma-pretreated specimens were slightly more prone to discoloration due to outdoor weathering, whereas the plasma pretreatment did not impact the initial color after coating application.
Graphic abstractUniformly-sized porous cellulose beads functionalized with amidoxime groups were prepared for the first time using a microfluidic method with N-methylmorpholine N-oxide (NMMO) monohydrate as a cellulose solvent. The molten state cellulose dope in NMMO monohydrate (cell/NMMO dope) as a disperse phase and hot mineral oil as a continuous phase were used in a T-junction microfluidic chip to produce uniformly-sized cell/NMMO droplets. Coagulation of the molten state cell/NMMO droplet at high temperature and amidoxime functionalization could prepare the highly-porous spherical amidoxime-functionalized cellulose beads with a uniform fibrous open internal structure. The prepared amidoxime-functionalized cellulose beads showed excellent metal adsorption properties with a maximum adsorption capacity of?~?80 mg g?1 in the case of Cu2+/phthalate ions. The newly developed highly-porous cellulose beads can open many new applications with other proper functionalization at the reactive hydroxyl groups of the cellulose.
Graphic abstractThe development of a versatile platform that can separate oil/water mixture, remove dye from water, and purify wastewater is extremely desirable, yet still hard to realize. Herein, to address this challenge, a composite hydrogel was produced by freezing–thawing treatment using chitosan, polyvinyl alcohol, and carbon black as the raw materials. The obtained hydrogel displayed both slippery oil-repellency and water-affinity in air, underwater, when submerged in oil, and exploiting this special wettability, the hydrogel coated mesh can be used to separate oil/water mixtures efficiently. After 25 oil–water separation cycles, the hydrogel-coated filter still had a separation efficiency of over 98%. With its superhydrophilicity and active functional groups, the resulting hydrogel was able to absorb dye molecules dissolved in water effectively. Due to the photothermal effect of carbon black, the local temperature of the hydrogel was increasing quickly under sunlight illustration, which allowed it to be an advanced platform for daily wastewater purification through solar distillation.
Graphical abstractA versatile hydrogel platform for oil–water separation, dye adsorption, and domestic wastewater purification was developed.
Vulcanized fibers are all-cellulose materials made from cotton and/or wood cellulose after aqueous zinc chloride treatment. These materials were invented in the UK in the mid-nineteenth century and is widely used because of their excellent characteristics, such as impact resistance and electrical insulation. Recently the matured vulcanized fibers have been recognized as renewable and biodegradable materials and reevaluated with advanced cellulose technologies derived from cellulose nanofibers (CNFs) and all-cellulose composites. The microscopic analysis based on the improved freeze-drying method revealed that the strength of vulcanized fiber sheets can be attributed to the chemically defibrillated CNFs. The architecture is similar to all-cellulose composites made from the same raw materials in which the residual cellulose fibers serve as reinforcement, and the CNFs serve as adhesives or matrix components. In this report, we describe the history and structural characteristics of vulcanized fibers and introduce a new aspect in aqueous zinc chloride treatment of cellulose.
Graphical abstractCellulose nanocrystals (CNCs) with high crystallinity exhibit high mechanical stiffness and strength. However, the high dispersibility of CNCs results in limited spinnability and orientation. In this study, oxidized nanocellulose was selected to obtain regionally oxidized CNCs (RO-CNC) with carboxyl groups appended. For the formation of orientable and extensible RO-CNC filaments, chitosan was introduced as the sheath solution to induce orientation by electrostatic action. The chemical structures were analyzed by Fourier transform infrared spectroscopy. The morphology of the oriented CNCs filaments was characterized by scanning electron microscopy and wide-angle X-ray scattering. Analysis of the relationship between the mechanical strength and the CNCs directional arrangement revealed that the mechanical strength of the composite fibers increased with the injection speed ratio as a result of the orientation of the RO-CNC. The mechanical strength of the oriented reinforced composite filaments reached as high as 104 MPa with an orientation index of 0.73. The tensile strength and elastic modulus of the filaments increased by 33% and 20%, respectively, compared to the unmodified CNCs spun fiber.
Graphic abstractA novel 3D porous reduced graphene oxide/montmorillonite composite hydrogel (rGO–MMT) was prepared by solvent method, where the MMT nanosheets were homogenously dispersed in 3D rGO hydrogel. The porous 3D structure and the high dispersion of MMT nanosheets can promote the adsorption capacity. The effects of MMT content (wt%), the initial concentration of Cr(VI) solution (C0), pH value (pH0), the adsorption dose and temperatures on the adsorption capacity of rGO–MMT for Cr(VI) ions have been investigated. The optimum pH value for Cr(VI) adsorption is 2, and the adsorption capacity increases with MMT content and adsorption temperature. The rGO–MMT composite hydrogel displays the excellent adsorption property for both the heavy metal and organic pollutants. The adsorption capacity of rGO–MMT composite hydrogel is obviously higher than those of single rGO hydrogel and MMT due to the synergistic adsorption of rGO hydrogel and MMT. The adsorption of Cr(VI) ions on the rGO–MMT composite hydrogel follows linear pseudo-second-order kinetics, and the Langmuir model describes the adsorption process much better. Thermodynamic parameters indicate that adsorption is spontaneous, favorable and endothermic in nature.
Graphic abstractIn this work, visible light response CeO2/CdS decorated cotton fabrics as durable and facile recyclable composite photocatalysts were fabricated for photo-degradation of methylene blue (MB). First of all, amino-functionalized CeO2/CdS heterojunctions were synthesized through a fast, efficient and low-cost co-precipitation method. Subsequently, the as-prepared CeO2/CdS heterojunctions were immobilized on aldehyde-functionalized cotton fabric surfaces as composite photocatalysts via "amine-aldehyde" chemical reaction. The surface microstructure and chemical composition of the CeO2/CdS decorated cotton fabric (CeO2/CdS-CF) were characterized by SEM, FTIR and XPS, respectively. The results showed that CeO2/CdS heterojunctions were successfully anchored and uniformly distributed on the surface of cotton fabric. Since the CeO2/CdS heterostructure with efficient photo-generated charge transfer and separation, the as-prepared CeO2/CdS-CF exhibited excellent photocatalytic activity, degrading MB under simulated sunlight irradiation with a degradation efficiency of 93.8% within 90 min. In addition, the degradation efficiency remained above 90.3% even after five successive degradation cycles, indicating the outstanding stability and recyclability of the obtained CeO2/CdS-CF. This work opened up a facile preparation way for the fabrication of durable and recyclable composite photocatalysts, and has a promising application in treating dye contaminated wastewater.
Graphic abstractOceans and soils have been contaminated with traditional plastic due to its lack of degradability. Therefore, green biopolymer composites reinforced with cellulose nanocrystal-zinc oxide hybrids (ZnO hybrids) with good biodegradation ability provided a positive impact on reducing environmental challenges. In this work, the effect of various morphologies of ZnO hybrids on the biodegradation ability of poly(butylene adipate-co-terephthalate), PBAT) under seawater, soil burial, and UV aging conditions were investigated. Sheet-like ZnO hybrids (s-ZnO hybrid) efficiently enhanced the mechanical, UV-blocking properties and biodegradation ability of PBAT nanocomposite films. Compared to neat PBAT, the best tensile strength of PBAT nanocomposite with 2 wt% s-ZnO hybrid was increased by 15.1%, meanwhile this nanocomposite films showed the highest biodegradation rate after 80 days of soil degradation and 90 days of seawater degradation. Besides, three possible biodegradation mechanisms of green PBAT nanocomposite films were presented, hinting that such PBAT nanocomposite have great promising packaging applications.
Graphic abstractA bio-adsorbent (DAWP-PEI-β-CD) was facilely prepared by introducing polyethylenimine (PEI) and β-cyclodextrin (β-CD) into dialdehyde waste paper (DAWP) via a facile two-step method. The structures, morphologies and compositions of the as-prepared adsorbents were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), solid state nuclear magnetic resonance spectrometry (NMR) and X-ray photoelectron spectroscopy (XPS) techniques. Results showed that the pH values, adsorption temperature and contact time played a vital role in uptake of Eu(III) and Au(III). Meanwhile, the adsorption behavior of Eu(III) and Au(III) could be fitted felicitously with the Langmuir and the pseudo-second-order models, and the maximum adsorption capacities of Eu(III) (pH = 6.0) and Au(III) (pH = 2.0) onto DAWP-PEI-β-CD were 424.2 and 241.3 mg/g, respectively. Further advanced spectroscopy analysis revealed that the elimination of Eu(III) was attributed to host-guest inclusion and surface complexation interaction, while adsorption of Au(III) might stem from a combination of electrostatic attraction, chelation, host-guest inclusion and redox interaction. This study demonstrated that DAWP-PEI-β-CD was a promising environmental functional material to separation and enrichment of Eu(III) and Au(III) from contaminated water.
Graphical abstractMultifunctional materials for water purification have attracted significant attention due to the increased water pollution problems. However, fabricating the low-cost, effective, and recyclable separation material for wastewater containing various hazardous substances is still a challenge. Herein, we developed an Ag/TiO2@PDMS coated cotton fabric with self-cleaning ability, high flux, superior visible-light photocatalytic ability, and recyclability via the “powder?+?glue” strategy. The composites are superhydrophobic (water contact angle 157°) and show high separation efficiency. After 20 times of repeated use, the separation efficiency remains 16,322 Lm?2 h?1, and methylene blue (MB) 's degradation rate remains almost unchanged. The high oil purification, catalytic property, excellent stability in harsh conditions, and recyclability enable the material as a satisfactory candidate for water purification.
Graphical abstractFabricating mechanically strong hydrogels that can withstand the conditions in internal tissues is a challenging task. We have designed hydrogels based on multicomponent systems by combining chitosan, starch/cellulose, PVA, and PEDOT:PSS via one-pot synthesis. The starch-based hydrogels were homogeneous, while the cellulose-based hydrogels showed the presence of cellulose micro- and nanofibers. The cellulose-based hydrogels demonstrated a swelling ratio between 121 and 156%, while the starch-based hydrogels showed higher values, from 234 to 280%. Tensile tests indicated that the presence of starch in the hydrogels provided high flexibility (strain at break?>?300%), while combination with cellulose led to the formation of stiffer hydrogels (elastic moduli 3.9–6.6 MPa). The ultimate tensile strength for both types of hydrogels was similar (2.8–3.9 MPa). The adhesion and growth of human osteoblast-like SAOS-2 cells was higher on hydrogels with cellulose than on hydrogels with starch, and was higher on hydrogels with PEDOT:PSS than on hydrogels without this polymer. The metabolic activity of cells cultivated for 3 days in the hydrogel infusions indicated that no acutely toxic compounds were released. This is promising for further possible applications of these hydrogels in tissue engineering or in wound dressings.
Graphical abstractThe complex anatomy of teeth limits the accessibility and efficacy of regenerative treatments. Therefore, the application of well-known inducers as injectable hydrogels for the regeneration of the dentin-pulp complex is considered a promising approach. In this regard, this study aimed to develop an injectable hydrogel containing mineral trioxide aggregate (MTA). The injectable chitosan/oxidized-nanocrystalline cellulose/MTA (CS/OCNC/MTA) hydrogels were prepared, and the physicochemical properties of these hydrogels were evaluated by TGA, FTIR, Rheological analysis, and SEM. Moreover, the effect of MTA on the swelling and degradability of scaffolds was assessed. The proliferative effects of synthesized hydrogels were also determined on human dental pulp stem cells (hDPSCs) by MTT assay. For induction of differentiation and biomineralization in these cells, the alkaline phosphatase activity and Alizarin Red S staining tests were performed in the presence of fabricated scaffolds. The proliferation of hDPSCs was significantly increased in the presence of these hydrogels. Moreover, the addition of MTA to hydrogel structure dramatically improved the differentiation of hDPSCs. These results suggested that this novel injectable hydrogel provides appropriate physiochemical properties and can be considered a promising scaffold for regenerative endodontic procedures.
Graphical abstractCellulose-based triboelectric nanogenerators (TENGs) can provide power for various monitoring devices and are environmentally friendly and sustainable. Chemical functional modification is a common method to improve the electrical output performance of cellulose-based TENGs. In this work, an environmentally friendly high-performance triboelectric nanogenerator based on a polydopamine/cellulose nanofibril (PDA/CNF) composite membrane and fluorinated ethylene propylene was developed. Dopamine generates polydopamine nanoparticles through oxidative self-polymerization and adheres to the surface of nanofibers. The synergistic effect of amino group introduction and membrane surface microstructure effectively enhanced the output performance of TENGs to a certain extent. The effects of PDA content, CNF composite film thickness and different working conditions on the electrical output were systematically investigated. The optimized PDA/CNF-TENGs exhibited an enhanced electrical output performance with voltage, current, and power density values of ≈205 V, ≈20 µA, and ≈48.75 μW·cm?2, respectively. The PDA/CNF-TENGs exhibited stable and identifiable signals when used as a self-powered sensor for human motion monitoring, showing the potential prospects of cellulose materials for TENGS and other electronic applications.
Graphical abstractThere are growing research interests in flax fibers due to their renewable ‘green’ origin and high strength. However, these natural fibers easily absorb moisture and have poor adhesion with polymer matrix leading to low interfacial strength for the composites. A hybrid chemical treatment technique combining alkali (sodium hydroxide) and silane treatments is adopted in the current study to modify flax fibers for improved performances of flax/polypropylene composites. Changes in chemical composition, microstructure, wettability, surface morphology, crystallinity and tensile properties of single flax fiber before and after chemical treatments were comprehensively characterized using techniques including SEM, FTIR, AFM, XRD, micro-fiber tester, etc. It was found that hemicellulose and lignin at the fiber surface were removed due to alkali treatment, which helped to reduce moisture absorption of the composites. Alkali-treated flax fibers were later subjected to silane treatment, which helped to improve the compatibility between flax fiber and polypropylene matrix. After alkali-silane hybrid chemical treatment, moisture absorption of the composites was further decreased. At the same time, the interfacial bonding strength between flax and polypropylene is significantly enhanced. All these results validate the great advantage of the hybrid chemical treatment approach for flax/polypropylene composites, which has the potential to promote the application of chemical treatment techniques in the plant fiber composite industry.
Graphic abstractExploitation of cotton fabric as electromagnetic interference (EMI) shielding substrates have attracted a growing interest due to their desirable low carbon footprint, economic feasibility, and sustainability. Herein, a facile strategy was proposed for preparing a cellulose-based multifunctional PNIPAAm/PPy hydrogel/cotton (PPHC) EMI shielding composites with simultaneous high-efficient electro-photo-thermal conversion and comfort regulation functions. The PPHC was fabricated via in situ polymerization conductive PPy hydrogel on cotton substrate followed by deposition of PNIPAAm. Benefiting from the unique interconnected three-dimensional networked conductive structure of PPy hydrogel, the obtained PPHC composites exhibited high conductivity (15 mS/cm), and EMI shielding effectiveness (EMI SE?~?40 dB) in the frequency of 8.2–12.3 GHz. Moreover, the PNIPAAm coating endowed the composite fabrics with adjustable wettability performance in response to external temperature, leading to excellent comfort regulation performance. This work provided feasible avenue toward low cost and sustainability cotton-based EMI shielding composites with efficient EMI shielding and comfort regulation performance.
Graphical abstractArrowroot starch (AA)-based films incorporated with a carnauba wax nanoemulsion (CWN), cellulose nanocrystals (CNCs), and essential oils (EOs) from Mentha spicata (MEO) and Cymbopogon martinii (CEO) were produced using the casting technique and then characterized in terms of their water barrier, tensile, thermal, optical, and microstructural properties and in vitro antifungal activity against Rhizopus stolonifer and Botrytis cinerea. Whereas the incorporation of CNCs decreased the moisture content and water vapor permeability of the AA/CWN/CNC film, the additional incorporation of either EO decreased the transparency and affected the microstructure of the AA/CWN/CNC/EO nanocomposites. MEO and CEO incorporation improved the thermal stability of the films and provided excellent protection against fruit-spoiling fungi. Because of their excellent barrier properties against fungal growth, water vapor permeability, and ultraviolet and visible light, these AA/CWN/CNC/EO films have promising potential for application as active food packaging or coating materials.
Graphic abstract