Structure-properties relationships of defined CNF single-networks crosslinked by telechelic PEGs.

The high structural anisotropy and colloidal stability of cellulose nanofibrils' enable the creation of self-standing fibrillar hydrogel networks at very low solid contents. Adding methacrylate moieties on the surface of TEMPO oxidized CNFs allows the formation of more robust covalently crosslinked networks by free radical polymerization of acrylic monomers, exploiting the mechanical properties of these networks more efficiently. This technique yields strong and elastic networks but with an undefined network structure. In this work, we use acrylate-capped telechelic polymers derived from the step-growth polymerization of PEG diacrylate and dithiothreitol to crosslink methacrylated TEMPO-oxidized cellulose nanofibrils (MATO CNF). This combination resulted in flexible and strong hydrogels, as observed through rheological studies, compression and tensile loading. The structure and mechanical properties of these hydrogel networks were found to depend on the dimensions of the CNFs and polymer crosslinkers. The structure of the networks and the role of individual components were evaluated with SAXS (Small-Angle X-ray Scattering) and photo-rheology. A thorough understanding of hybrid CNF/polymer networks and how to best exploit the capacity of these networks enable further advancement of cellulose-based materials for applications in packaging, soft robotics, and biomedical engineering.

Metallic Wood through Deep-Cell-Wall Metallization: Synthesis and Applications.

Metallic wood combines the unique structural benefits of wood and the properties of metals and is thus promising for applications ranging from heat transfer to electromagnetic shielding to energy conversion. However, achieving metallic wood with full use of wood structural benefits such as anisotropy and multiscale porosity is challenging. A key reason is the limited mass transfer in bulk wood where fibers have closed ends. In this work, programmed removal of cell-wall components (delignification and hemicellulose extraction) was introduced to improve the accessibility of cell walls and mass diffusion in wood. Subsequent low-temperature electroless Cu plating resulted in a uniform continuous Cu coating on the cell wall, and, furthermore, Cu nanoparticles (NPs) insertion into the wood cell wall. A novel Cu NPs-embedded multilayered cell-wall structure was created. The unique structure benefits compressible metal-composite foam, appealing for stress sensors, where the multilayered cell wall contributes to the compressibility and stability. The technology developed for wood metallization here could be transferred to other functionalizations aimed at reaching fine structure in bulk wood.

Gradience Free Nanoinsertion of Fe3O4 into Wood for Enhanced Hydrovoltaic Energy Harvesting.

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.

Strong, Shape-Memory Lignocellulosic Aerogel via Wood Cell Wall Nanoscale Reassembly.

Polymer shape-memory aerogels (PSMAs) are prospects in various fields of application ranging from aerospace to biomedicine, as advanced thermal insulators, actuators, or sensors. However, the fabrication of PSMAs with good mechanical performance is challenging and is currently dominated by fossil-based polymers. In this work, strong, shape-memory bio-aerogels with high specific surface areas (up to 220 m2/g) and low radial thermal conductivity (0.042 W/mK) were prepared through a one-step treatment of native wood using an ionic liquid mixture of [MTBD]+[MMP]-/DMSO. The aerogel showed similar chemical composition similar to native wood. Nanoscale spatial rearrangement of wood biopolymers in the cell wall and lumen was achieved, resulting in flexible hydrogels, offering design freedom for subsequent aerogels with intricate geometries. Shape-memory function under stimuli of water was reported. The chemical composition and distribution, morphology, and mechanical performance of the aerogel were carefully studied using confocal Raman spectroscopy, AFM, SAXS/WAXS, NMR, digital image correlation, etc. With its simplicity, sustainability, and the broad range of applicability, the methodology developed for nanoscale reassembly of wood is an advancement for the design of biobased shape-memory aerogels.

Functionalized Wood Veneers as Vibration Sensors: Exploring Wood Piezoelectricity and Hierarchical Structure Effects.

Functional wood materials often rely on active additives due to the weak piezoelectric response of wood itself. Here, we chemically modify wood to form functionalized, eco-friendly wood veneer for self-powered vibration sensors. Only the piezoelectricity of the cellulose microfibrils is used, where the drastic improvement comes only from molecular and nanoscale wood structure tuning. Sequential wood modifications (delignification, oxidation, and model fluorination) are performed, and effects on vibration sensing abilities are investigated. Wood veneer piezoelectricity is characterized by the piezoresponse force microscopy mode in atomic force microscopy. Delignification, oxidation, and model fluorination of wood-based sensors provide output voltages of 11.4, 23.2, and 60 mV by facilitating cellulose microfibril deformation. The vibration sensing ability correlates with improved piezoelectricity and increased cellulose deformation, most likely by large, local cell wall bending. This shows that nanostructural wood materials design can tailor the functional properties of wood devices with potential in sustainable nanotechnology.

Nanostructurally Controllable Strong Wood Aerogel toward Efficient Thermal Insulation.

Eco-friendly materials with superior thermal insulation and mechanical properties are desirable for improved energy- and space-efficiency in buildings. Cellulose aerogels with structural anisotropy could fulfill these requirements, but complex processing and high energy demand are challenges for scaling up. Here we propose a scalable, nonadditive, top-down fabrication of strong anisotropic aerogels directly from wood with excellent, near isotropic thermal insulation functions. The aerogel was obtained through cell wall dissolution and controlled precipitation in lumen, using an ionic liquid (IL) mixture comprising DMSO and a guanidinium phosphorus-based IL [MTBD][MMP]. The wood aerogel shows a unique structure with lumen filled with nanofibrils network. In situ formation of a cellulosic nanofibril network in the lumen results in specific surface areas up to 280 m2/g and high yield strengths >1.2 MPa. The highly mesoporous structure (average pore diameter ∼20 nm) of freeze-dried wood aerogels leads to low thermal conductivities in both the radial (0.037 W/mK) and axial (0.057 W/mK) directions, showing great potential as scalable thermal insulators. This synthesis route is energy efficient with high nanostructural controllability. The unique nanostructure and rare combination of strength and thermal properties set the material apart from comparable bottom-up aerogels. This nonadditive synthesis approach is believed to contribute significantly toward large-scale design and structure control of biobased aerogels.

Facile Processing of Transparent Wood Nanocomposites with Structural Color from Plasmonic Nanoparticles.

Wood is an eco-friendly and abundant substrate and a candidate for functionalization by large-scale nanotechnologies. Infiltration of nanoparticles into wood, however, is hampered by the hierarchically structured and interconnected fibers in wood. In this work, delignified wood is impregnated with gold and silver salts, which are reduced in situ to plasmonic nanoparticles via microwave-assisted synthesis. Transparent biocomposites are produced from nanoparticle-containing wood in the form of load-bearing materials with structural color. The coloration stems from nanoparticle surface plasmons, which require low size dispersity and particle separation. Delignified wood functions as a green reducing agent and a reinforcing scaffold to which the nanoparticles attach, predesigning their distribution on the surface of fibrous "tubes". The nanoscale structure is investigated using scanning transmission electron microscopy (STEM), energy-dispersive spectroscopy (EDS), and Raman microscopy to determine particle size, particle distribution, and structure-property relationships. Optical properties, including response to polarized light, are of particular interest.

Top-Down Approach Making Anisotropic Cellulose Aerogels as Universal Substrates for Multifunctionalization.

Highly porous, strong aerogels with anisotropic structural properties are of great interest for multifunctional materials for applications including insulators in buildings, filters for oil cleanup, electrical storage devices, etc. Contemporary aerogels are mostly extracted from fossil resources and synthesized from bottom-up techniques, often requiring additional strategies to obtain high anisotropy. In this work, a universal approach to prepare porous, strong, anisotropic aerogels is presented through exploiting the natural hierarchical and anisotropic structure of wood. The preparation comprises nanoscale removal of lignin, followed by dissolution-regeneration of nanofibers, leading to enhanced cell wall porosity with nanofibrillated networks occupying the pore space in the cellular 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 even higher than most cellulose-based aerogels for its assigned strength. The aerogel can serve as a platform for multifunctional composites including scaffolds for catalysis, gas separation, or liquid purification due to its porous matrix or as binder-free electrodes in electronics. To demonstrate the multifunctionality, the aerogels are successfully decorated with metal nanoparticles (Ag) and metal oxide nanoparticles (TiO2) by in situ synthesis, coated by the conductive polymer (PEDOT:PSS), and carbonized to yield conductive aerogels. This approach is found to be a universal way to prepare highly porous anisotropic aerogels.