Distributed electrified heating for efficient hydrogen production.

This study introduces a distributed electrified heating approach that is able to innovate chemical engineering involving endothermic reactions. It enables rapid and uniform heating of gaseous reactants, facilitating efficient conversion and high product selectivity at specific equilibrium. Demonstrated in catalyst-free CH4 pyrolysis, this approach achieves stable production of H2 (530 g h-1 L reactor -1) and carbon nanotube/fibers through 100% conversion of high-throughput CH4 at 1150 °C, surpassing the results obtained from many complex metal catalysts and high-temperature technologies. Additionally, in catalytic CH4 dry reforming, the distributed electrified heating using metallic monolith with unmodified Ni/MgO catalyst washcoat showcased excellent CH4 and CO2 conversion rates, and syngas production capacity. This innovative heating approach eliminates the need for elongated reactor tubes and external furnaces, promising an energy-concentrated and ultra-compact reactor design significantly smaller than traditional industrial systems, marking a significant advance towards more sustainable and efficient chemical engineering society.

Residual Strain and Nanostructural Effects during Drying of Nanocellulose/Clay Nanosheet Hybrids: Synchrotron X-ray Scattering Results.

Cellulose nanofibrils (CNF) with 2D silicate nanoplatelet reinforcement readily form multifunctional composites by vacuum-assisted self-assembly from hydrocolloidal mixtures. The final nanostructure is formed during drying. The crystalline nature of CNF and montmorillonite (MTM) made it possible to use synchrotron X-ray scattering (WAXS, SAXS) to monitor structural development during drying from water and from ethanol. Nanostructural changes in the CNF and MTM crystals were investigated. Changes in the out-of-plane orientation of CNF and MTM were determined. Residual drying strains previously predicted from theory were confirmed in both cellulose and MTM platelets due to capillary forces. The formation of tactoid platelet stacks could be followed. We propose that after filtration, the constituent nanoparticles in the swollen, solid gel already have a "fixed" location, although self-assembly and ordering processes take place during drying.

Ultrastrong Ionotronic Films Showing Electrochemical Osmotic Actuation.

A multifunctional soft material with high ionic and electrical conductivity, combined with high mechanical properties and the ability to change shape can enable bioinspired responsive devices and systems. The incorporation of all these characteristics in a single material is very challenging, as the improvement of one property tends to reduce other properties. Here, a nanocomposite film based on charged, high-aspect-ratio 1D flexible nanocellulose fibrils, and 2D Ti3 C2 Tx MXene is presented. The self-assembly process results in a stratified structure with the nanoparticles aligned in-plane, providing high ionotronic conductivity and mechanical strength, as well as large water uptake. In hydrogel form with 20 wt% liquid, the electrical conductivity is over 200 S cm-1 and the in-plane tensile strength is close to 100 MPa. This multifunctional performance results from the uniquely layered composite structure at nano- and mesoscales. A new type of electrical soft actuator is assembled where voltage as low as ±1 V resulted in osmotic effects and giant reversible out-of-plane swelling, reaching 85% strain.

Formation and stability of studtite in bicarbonate-containing waters.

Studtite and meta-studtite are the only two uranyl peroxides found in nature. Sparsely soluble studtite has been found in natural uranium deposits, on the surface of spent nuclear fuel in contact with water and on core material from major nuclear accidents such as Chernobyl. The formation of studtite on the surface of nuclear fuel can have an impact on the release of radionuclides to the biosphere. In this work, we have experimentally studied the formation of studtite as function of HCO3- concentration and pH. The results show that studtite can form at pH ≤ 10 in solutions without added HCO3-. At pH ≤ 7, the precipitate was found to be mainly studtite, while at 8 ≤ pH ≤ 9.8, a mixture of studtite and meta-schoepite was found. Studtite formation from UO22+ and H2O2 was observed at [HCO3-] ≤ 2 mM and studtite was only found to dissolve at [HCO3-] > 2 mM.

Wood xerogel for fabrication of high-performance transparent wood.

Optically transparent wood has been fabricated by structure-retaining delignification of wood and subsequent infiltration of thermo- or photocurable polymer resins but still limited by the intrinsic low mesopore volume of the delignified wood. Here we report a facile approach to fabricate strong transparent wood composites using the wood xerogel which allows solvent-free infiltration of resin monomers into the wood cell wall under ambient conditions. The wood xerogel with high specific surface area (260 m2 g-1) and high mesopore volume (0.37 cm3 g-1) is prepared by evaporative drying of delignified wood comprising fibrillated cell walls at ambient pressure. The mesoporous wood xerogel is compressible in the transverse direction and provides precise control of the microstructure, wood volume fraction, and mechanical properties for the transparent wood composites without compromising the optical transmittance. Transparent wood composites of large size and high wood volume fraction (50%) are successfully prepared, demonstrating potential scalability of the method.

Processing strategy for reduced energy demand of nanostructured CNF/clay composites with tailored interfaces.

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.

Electrical current modulation in wood electrochemical transistor.

The nature of mass transport in plants has recently inspired the development of low-cost and sustainable wood-based electronics. Herein, we report a wood electrochemical transistor (WECT) where all three electrodes are fully made of conductive wood (CW). The CW is prepared using a two-step strategy of wood delignification followed by wood amalgamation with a mixed electron-ion conducting polymer, poly(3,4-ethylenedioxythiophene)-polystyrene sulfonate (PEDOT:PSS). The modified wood has an electrical conductivity of up to 69 Sm-1 induced by the formation of PEDOT:PSS microstructures inside the wood 3D scaffold. CW is then used to fabricate the WECT, which is capable of modulating an electrical current in a porous and thick transistor channel (1 mm) with an on/off ratio of 50. The device shows a good response to gate voltage modulation and exhibits dynamic switching properties similar to those of an organic electrochemical transistor. This wood-based device and the proposed working principle demonstrate the possibility to incorporate active electronic functionality into the wood, suggesting different types of bio-based electronic devices.

An Oxidative Enzyme Boosting Mechanical and Optical Performance of Densified Wood Films.

Nature has evolved elegant ways to alter the wood cell wall structure through carbohydrate-active enzymes, offering environmentally friendly solutions to tailor the microstructure of wood for high-performance materials. In this work, the cell wall structure of delignified wood is modified under mild reaction conditions using an oxidative enzyme, lytic polysaccharide monooxygenase (LPMO). LPMO oxidation results in nanofibrillation of cellulose microfibril bundles inside the wood cell wall, allowing densification of delignified wood under ambient conditions and low pressure into transparent anisotropic films. The enzymatic nanofibrillation facilitates microfibril fusion and enhances the adhesion between the adjacent wood fiber cells during densification process, thereby significantly improving the mechanical performance of the films in both longitudinal and transverse directions. These results improve the understanding of LPMO-induced microstructural changes in wood and offer an environmentally friendly alternative for harsh chemical treatments and energy-intensive densification processes thus representing a significant advance in sustainable production of high-performance wood-derived materials.

Recyclable nanocomposites of well-dispersed 2D layered silicates in cellulose nanofibril (CNF) matrix.

Nanocomposites based on components from nature, which can be recycled are of great interest in new materials for sustainable development. The range of properties of nacre-inspired hybrids of 1D cellulose and 2D clay platelets are investigated in nanocomposites with improved nanoparticle dispersion in the starting hydrocolloid mixture. Films with a wide range of compositions are prepared by capillary force assisted physical assembly (vacuum-assisted filtration) of TEMPO-oxidized cellulose nanofibers (TOCN) reinforced by exfoliated nanoclays of three different aspect ratios: saponite, montmorillonite and mica. X-ray diffraction and transmission electron micrographs show almost monolayer dispersion of saponite and montmorillonite and high orientation parallel to the film surface. Films exhibit ultimate strength up to 573 MPa. Young's modulus exceeds 38 GPa even at high MTM contents (40-80 vol%). Optical transmittance, UV-shielding, thermal shielding and fire-retardant properties are measured, found to be very good and are sensitive to the 2D nanoplatelet dispersion.

Millions of microplastics released from a biodegradable polymer during biodegradation/enzymatic hydrolysis.

In this article, we show that enzymatic hydrolysis of a biodegradable polyester (poly(ε-caprolactone)) by Amano Lipase PS in an aqueous (buffer) environment yielded rapidly an excessive number of microplastic particles; merely 0.1 g of poly(ε-caprolactone) film was demonstrated to yield millions of particles. There were also indications of non-enzymatic hydrolysis at the same conditions, but this did not yield any particles within the time frame of the experiment (up to 6 days). Microplastic particles formed had irregular shapes with an average size of around 10 µm, with only a few reaching 60 µm. The formation of microplastic particles resulted from the uneven hydrolysis/erosion rate across the polymer film surface, which led to a rough and undulating surface with ridge, branch, and rod-shaped micro-protruding structures. The consequent detachment and fragmentation of these micro-sized protruding structures resulted in the release of microplastics to the surroundings. Together with microplastics, hydrolysis products such as acidic monomers and oligomers were also released during the enzymatic hydrolysis process, causing a pH decrease in the surrounding liquid. The results suggest that the risk of microplastic pollution from biodegradable plastics is notable despite their biodegradation. Special attention needs to be paid when using and disposing of biodegradable plastics, considering the enormous impact of the paradigm shift towards more biodegradable products on the environment.

Eco-Friendly Bioinspired Interface Design for High-Performance Cellulose Nanofibril/Carbon Nanotube Nanocomposites.

Inspired by a wood-like multicomponent structure, an interface-reinforced method was developed to fabricate high-performance cellulose nanofibril (CNF)/carbon nanotube (CNT) nanocomposites. Holocellulose nanofibrils (HCNFs) with core-shell structure were first obtained from bagasse via mild delignification and mechanical defibration process. The well-preserved native hemicellulose as the amphiphilic shell of HCNFs could act as a binding agent, sizing agent, and even dispersing agent between HCNFs and CNTs. Remarkably, both the tensile strength at high relative humidity (83% RH) and electrical conductivity of the HCNF/CNT nanocomposites were significantly improved up to 121 MPa and 321 S/m, respectively, demonstrating great superiority compared to normal CNF/CNT composite films. Furthermore, these HCNF/CNT composites with outstanding integrated performances exhibited great potential in the field of flexible liquid sensing.

The Microscopic Structure-Property Relationship of Metal-Organic Polyhedron Nanocomposites.

Monodispersed hairy nanocomposites with typical 2 nm (isophthalic acid)24 Cu24 metal-organic polyhedra (MOP) as a core protected by 24 polymer chains with controlled narrow molecular weight distribution has been probed by imaging and scattering studies for the heterogeneity of polymers in the nanocomposites and the confinement effect the MOPs imposing on anchored polymers. Typical confined-extending surrounded by one entanglement area is proposed to describe the physical states of the polymer chains. This model dictates the counterintuitive thermal and rheological properties and prohibited solvent exchange properties of the nanocomposites, whilst those polymer chain states are tunable and deterministic based on their component inputs. From the relationship between the structure and behavior of the MOP nanocomposites, a MOP-composited thermoplastic elastomer was obtained, providing practical solutions to improve mechanical/rheological performances and processabilities of inorganic MOPs.

Highly Durable Superhydrophobic Polymer Foams Fabricated by Extrusion and Supercritical CO2 Foaming for Selective Oil Absorption.

The severe water contamination caused by oil leakage is calling for low-cost and high-performance absorbent materials for selective oil removal. In this study, a scalable green method was proposed to produce polypropylene (PP)/poly(tetrafluoroethylene) (PTFE) composite foams via conventional processing techniques including twin-screw extrusion and supercritical carbon dioxide foaming. To produce the superhydrophobic foam, micro- and nanosized PTFE particles were melt blended with PP and subsequently foamed. Ascribed to the nanofibrillation of microsized PTFE during processing, the fabricated foam exhibited a special highly porous structure with PTFE nanofibrils and nanoparticles uniformly distributed on the pore surfaces within the PP matrix, which resulted in a remarkably high water contact angle of 156.8° and a low contact angle hysteresis of 1.9°. Unlike traditional surface-modified superhydrophobic absorbers, the foams prepared are entirely superhydrophobic, which means that they remain superhydrophobic when being fractured or cut. Moreover, they are highly durable and maintained the superhydrophobicity when subjected to ultrasonication and mechanical sanding. When used in selective oil absorption, the durable foams exhibited excellent absorption efficiency and high stability in repetitive and long-term use. These advantages make the PP/PTFE foam a promising superabsorbent material for water remediation.

Porous liquid zeolites: hydrogen bonding-stabilized H-ZSM-5 in branched ionic liquids.

Porous liquids, as a newly emerging type of porous material, have great potential in gas separation and storage. However, the examples and synthetic strategies reported so far likely represent only the tip of the iceberg due to the great difficulty and challenge in engineering permanent porosity in liquid matrices. Here, by taking advantage of the hydrogen bonding interaction between the alkane chains of branched ionic liquids and the Brønsted sites in H-form zeolites, as well as the mechanical bond of the long alkyl chain of the cation penetrated into the zeolite channel at the interface, the H-form zeolites can be uniformly stabilized in branched ionic liquids to form porous liquid zeolites, which not only significantly improve their gas sorption performance, but also change the gas sorption-desorption behavior because of the preserved permanent porosity. Furthermore, such a facile synthetic strategy can be extended to fabricate other types of H-form zeolite-based porous liquids by taking advantage of the tunability of the counter-anion (e.g., NTf2-, BF4-, EtSO4-, etc.) in branched ionic liquids, thus opening up new opportunities for porous liquids for specific applications in energy and environment.

Spatial-Temporal Characteristics of Confined Polymer Motion Determine Proton Conduction of Polyoxometalate-Poly(ethylene glycol) Hybrid Nanocomposites.

Highly efficient proton conductors, polyoxometalate-poly(ethylene glycol) (POM-PEG) hybrid nanocomposites, have been synthesized by encapsulating a single PEG chain inside the 1D nanochannel defined by the frameworks of POMs. By employing two types of neutron scattering techniques complemented by thermal analysis, we prove that in a nanochannel a single PEG chain stays as a distorted helix. More importantly, we reveal that the PEG segments perform a localized longitudinal random walk and quantitatively show the strong correlation between the local motion of PEG and the macroscopic proton conduction of the material. On the basis of these spatial-temporal characteristics, a microscopic picture for the proton conduction process of POM-PEG hybrid materials is proposed.

Superior Impact Toughness and Excellent Storage Modulus of Poly(lactic acid) Foams Reinforced by Shish-Kebab Nanoporous Structure.

Poly(lactic acid) (PLA) foams, with the combination of shish-kebab and spherulite nanoporous structure in skin and core layer respectively, was prepared using a novel technique comprising loop oscillating push-pull molding (LOPPM) and supercritical carbon dioxide low-temperature foaming process (SC-CO2LTFP). The foams present superior impact toughness which is 6-fold higher than that of neat PLA, and no significant decrease was observed for the storage modulus. Moreover, SC-CO2LTFP at soaking temperature ranging from 110 to 150 °C were performed to determine the evolution of pore morphology. The ultratough and supermoduli are unprecedented for PLA, and are in great need for broader applications.