Hydrovoltaic energy harvesting offers the potential to utilize enormous water energy for sustainable energy systems. Here, we report the utilization and tailoring of an intrinsic anisotropic 3D continuous microchannel structure from native wood for efficient hydrovoltaic energy harvesting by Fe3O4 nanoparticle insertion. Acetone-assisted precursor infiltration ensures the homogenous distribution of Fe ions for gradience-free Fe3O4 nanoparticle formation in wood. The Fe3O4/wood nanocomposites result in an open-circuit voltage of 63 mV and a power density of ∼52 μW/m2 (∼165 times higher than the original wood) under ambient conditions. The output voltage and power density are further increased to 1 V and ∼743 μW/m2 under 3 suns solar irradiation. The enhancement could be attributed to the increase of surface charge, nanoporosity, and photothermal effect from Fe3O4. The device exhibits a stable voltage of ∼1 V for 30 h (3 cycles of 10 h) showing good long-term stability. The methodology offers the potential for hierarchical organic-inorganic nanocomposite design for scalable and efficient ambient energy harvesting.

Nacre-mimicking nanocomposites based on colloidal cellulose nanofibrils (CNFs) and clay nanoparticles show excellent mechanical properties, yet processing typically involves preparation of two colloids followed by a mixing step, which is time- and energy-consuming. In this study, a facile preparation method using low energy kitchen blenders is reported in which CNF disintegration, clay exfoliation and mixing carried out in one step. Compared to composites made from the conventional method, the energy demand is reduced by about 97 %; the composites also show higher strength and work to fracture. Colloidal stability, CNF/clay nanostructure, and CNF/clay orientation are well characterized. The results suggest favorable effects from hemicellulose-rich, negatively charged pulp fibers and corresponding CNFs. CNF disintegration and colloidal stability are facilitated with substantial CNF/clay interfacial interaction. The results show a more sustainable and industrially relevant processing concept for strong CNF/clay nanocomposites.

Dense polymeric films based on network-forming cellulose nanofibrils (CNFs) have excellent mechanical properties but are limited by moisture sensitivity. Here, interfibrillar effects from CNF surface properties are investigated. TEMPO-oxidized CNFs and two native CNFs are prepared with a similar length and width, to exclude geometrical effects. The CNFs have different surface properties in terms of sorbed hemicellulose content, hemicellulose molar mass, and surface charge. Moisture sorption, structural changes, and mechanical properties at different relative humidities are characterized. The presence of sorbed hemicelluloses in the interfibrillar interphase has favorable effects on the mechanical tensile properties. Surface-charged carboxyls increased moisture sorption and film thickness swelling and reduced the mechanical properties. A comparison with biaxially oriented polyethylene terephthalate films provides a perspective into the structure and properties of CNF films. The present study shows the importance of the interfibrillar interface and interphase region for mechanical film properties, including moisture effects.

Holocellulose fibers produced by mild delignification form strong fiber networks, without beating or dry-strength agents. Recently, sequential batch delignification using peracetic acid (PAA) on finely cut wood sticks resulted in high-quality holocellulose fibers. Here, single step PAA delignification is developed for wood chips, which is simpler and can be used for larger fiber batches (400 g) with similar, high yield (60%). Such fibers have 1.4% lignin, 25% hemicelluloses content and well-preserved cellulose and hemicellulose molar mass. The corresponding paper sheet materials with a porosity of ~ 50%, have a Young’s modulus of 9 GPa and a strength of 90 MPa. Holocellulose fibers can now be readily investigated for use in larger scale paper, molded fiber and polymer biocomposite materials applications, or for cellulose nanofibril preparation.

Mildly delignified wood holocellulose fibers show well-preserved cellulose nanofibril (CNF) structure in the fiber cell wall. Fibers, paper, biocomposites, and compression-molded fiber materials demonstrate excellent mechanical properties. Here, wood holocellulose fibers and corresponding CNFs are discussed with respect to nanostructure, mechanical performance, and advanced materials potential. Functionalization routes are discussed, as well as materials selection, nanoscience of recycling, and the embodied energy in cellulosic candidates for multifunctional structural materials. 

Cellulose nanofibrils (CNFs) show high modulus and strength and are already used in industrial applications. Mechanical properties of neat CNF films or CNF-polymer matrix nanocomposites are usually much better than for polymer matrix composite films reinforced by clay, graphene, graphene oxide, or carbon nanotubes. In order to obtain small CNF diameter and colloidal stability, chemical modification has so far been necessary, but this increases cost and reduces eco-friendly attributes. In this study, an unmodified holocellulose CNF (Holo-CNF) with small diameter is obtained from mildly peracetic acid delignified wood fibers. CNF is readily defibrillated by low-energy kitchen blender processing. The hemicellulose coating on individual fibrils in the wood plant cell wall is largely preserved in Holo-CNF. This "native" CNF shows well-preserved native fibril structure in terms of length (similar to 2.1 mu m), diameter (<5 nm), high crystallinity, high cellulose molar mass, electronegative charge, and limited mechanical processing damage. The hemicellulose coating contributes mechanical properties and high optical transmittance for CNF nanopaper, which can otherwise only be achieved with chemically modified CNFs. The CNF nanopaper shows superior mechanical properties with a Young's modulus of 21 GPa and an ultimate strength of 320 MPa. Moreover, hemicellulose imparts recyclability from the dried state. Altogether, this native CNF represents a class of colloidally stable, eco-friendly, low-cost CNF of small diameter for large-scale applications of nanopaper and nanomaterials.

This study investigates the relationships between the composition, cell wall microstructure, and mechanical properties of the abaca fiber. Raw abaca fibers have undergone a series of sequential chemical treatments (acetone/methanol, boiling water, EDTA, HCl, NaClO2, and NaOH) to selectively remove certain non-cellulosic components (NCCs) in the fiber, such as waxes, water-soluble fragments, pectin, and lignin in a step-by-step manner. Changes in composition, morphology, and mechanical properties were observed using FTIR spectroscopy and ion chromatography, digital microscope and SEM, and tensile tests, respectively. The raw fiber was composed of 23% NCCs, 18% hemicellulose, and 58% cellulose, and exhibited a 17.4 GPa Young’s modulus and a 444 MPa tensile strength. Furthermore, the raw abaca fibers demonstrated a linear tensile graph without yielding, and a planar fracture surface without fiber pull-outs, thus suggesting a highly elastic but brittle nature. At the end of the alkali treatment, the fibrillated fiber was 83% cellulose, yet the stiffness and strength dropped to 7.3 GPa and 55 MPa, respectively, as more components were removed, and microfibril relaxation and realignment have occurred. Load-bearing cellulose and hemicellulose accounted for 42% and 36% of the stiffness, respectively, due to –OH groups capable of hydrogen bonding. 63% of the strength was due to thenative NCC matrices, which contribute a significant role within the cell wall’s load-transfer activities.

Cellulosic paper products based on sustainable resources are of interest as a replacement for petroleum-based plastics, for example, in packaging applications. Improvements are desired for mechanical performance, recyclability, and possibilities to shape fiber networks into complex geometries. Commercial bleached wood fibers from the kraft process have insufficient mechanical properties for many applications, even with beating and additives. In addition, mechanical properties of paper structures are significantly reduced after recycling. Here, recycling and 3D shaping performance of holocellulose fibers are compared with kraft fibers and investigated in the context of wood fiber tailoring for eco-friendly materials. Holocellulose fibers from wood are prepared by mild peracetic acid delignification for well-preserved nanostructures and hemicellulose content (28 wt %). Paper structures of about 50% porosity are prepared from both types of fibers by vacuum filtration and drying. Mechanical tensile tests are performed, and fracture surfaces are investigated. The effects of recycling on the fiber structure (chemical composition, morphology, and crystallite size in fibers) and mechanical paper properties are reported. 3D-shaping performance is studied using compression molding with a double-curved mold. Holocellulose paper structures showed much better mechanical properties than kraft fiber paper (Young's modulus 10 GPa, ultimate tensile strength 100 MPa), as well as better recycling performance (only 26% decrease in strength after 5 cycles) and 3D formability. The well-preserved cellulose and hemicellulose components are important, as well as the homogeneity of the fiber cell wall nanostructure. This preserves the intrinsic mechanical properties of fibers, reduces hornification effects, and provides strong interfiber adhesion. Furthermore, the water-soluble hemicelluloses present at the cellulose-cellulose interface are able to facilitate recycling and 3D forming.

In the native wood cell wall, cellulose microfibrils are highly aligned and organized in the secondary cell wall. A new preparation strategy is developed to achieve individualization of cellulose microfibrils within the wood cell wall structure without introducing mechanical disintegration. The resulting mesoporous wood structure has a high specific surface area of 197 m2 g−1 when prepared by freeze‐drying using liquid nitrogen, and 249 m2 g−1 by supercritical drying. These values are 5 to 7 times higher than conventional delignified wood (36 m2 g−1) dried by supercritical drying. Such highly mesoporous structure with individualized cellulose microfibrils maintaining their natural alignment and organization can be processed into aerogels with high porosity and high compressive strength. In addition, a strong film with a tensile strength of 449.1 ± 21.8 MPa and a Young's modulus of 51.1 ± 5.2 GPa along the fiber direction is obtained simply by air drying owing to the self‐densification of cellulose microfibrils driven by the elastocapillary forces upon water evaporation. The self‐densified film also shows high optical transmittance (80%) and high optical haze (70%) with interesting biaxial light scattering behavior owing to the natural alignment of cellulose microfibrils.

Highly porous, strong aerogels with anisotropicstructural properties are of great interest for multifunctionalmaterials for applications including insulators in buildings,filters for oil cleanup, electrical storage devices,etc. Contem-porary aerogels are mostly extracted from fossil resources andsynthesized from bottom-up techniques, often requiring addi-tional strategies to obtain high anisotropy. In this work, auniversal approach to prepare porous, strong, anisotropicaerogels is presented through exploiting the natural hierarchicaland anisotropic structure of wood. The preparation comprisesnanoscale removal of lignin, followed by dissolution−regener-ation of nanofibers, leading to enhanced cell wall porosity with nanofibrillated networks occupying the pore space in thecellular wood structure. The aerogels retain structural anisotropy of natural wood, exhibit specific surface areas up to 247 m2/g, and show high compression strength at 95% porosity. This is a record specific area value for wood aerogels/foams and evenhigher than most cellulose-based aerogels for its assigned strength. The aerogel can serve as a platform for multifunctionalcomposites including scaffolds for catalysis, gas separation, or liquid purification due to its porous matrix or as binder-freeelectrodes in electronics. To demonstrate the multifunctionality, the aerogels are successfully decorated with metalnanoparticles (Ag) and metal oxide nanoparticles (TiO2)byin situsynthesis, coated by the conductive polymer(PEDOT:PSS), and carbonized to yield conductive aerogels. This approach is found to be a universal way to prepare highlyporous anisotropic aerogels.