Controllable and Reversible Assembly of Nanofiber from Natural Macromolecules via Protonation and Deprotonation.

Nanofiber is the critical building block for many biological systems to perform various functions. Artificial assembly of molecules into nanofibers in a controllable and reversible manner will create "smart" functions to mimic those of their natural analogues and fabricate new functional materials, but remains an open challenge especially for nature macromolecules. Herein, the controllable and reversible assembly of nanofiber (CSNF) from natural macromolecules with oppositely charged groups are successfully realized by protonation and deprotonation of charged groups. By controlling the electrostatic interaction via protonation and deprotonation, the size and morphology of the assembled nanostructures can be precisely controlled. A strong electrostatic interaction contributes to large nanofiber with high strength, while poor electrostatic interaction produces finer nanofiber or nanoparticle. And especially, the assembly, disassembly, and reassembly of the nanofiber occurs reversibly through protonation and deprotonation, thereby paving a new way for precisely controlling the assembly process and structure of nanofiber. The reversible assembly allows the nanostructure to dynamically reorganize in response to subtle perturbation of environment. The as-prepared CSNF is mechanical strong and can be used as a nano building block to fabricate high-strength film, wire, and straw. This study offers many opportunities for the biomimetic synthesis of new functional materials.

Carbon Fiber Film with Multi-Hollow Channels to Expedite Oxygen Electrocatalytic Reaction Kinetics for Flexible Zn-Air Battery.

The high oxygen electrocatalytic overpotential of flexible cathodes due to sluggish reaction kinetics result in low energy conversion efficiency of wearable zinc-air batteries (ZABs). Herein, lignin, as a 3D flexible carbon-rich macromolecule, is employed for partial replacement of polyacrylonitrile and constructing flexible freestanding air electrodes (FFAEs) with large amount of mesopores and multi-hollow channels via electrospinning combined with annealing strategy. The presence of lignin with disordered structure decreases the graphitization of carbon fibers, increases the structural defects, and optimizes the pore structure, facilitating the enhancement of electron-transfer kinetics. This unique structure effectively improves the accessibility of graphitic-N/pyridinic-N with oxygen reduction reaction (ORR) activity and pyridinic-N with oxygen evolution reaction (OER) activity for FFAEs, accelerating the mass transfer process of oxygen-active species. The resulting N-doped hollow carbon fiber films (NHCFs) exhibit superior bifunctional ORR/OER performance with a low potential difference of only 0.60 V. The rechargeable ZABs with NHCFs as metal-free cathodes possess a long-term cycling stability. Furthermore, the NHCFs can be used as FFAEs for flexible ZABs which have a high specific capacity and good cycling stability under different bending states. This work paves the way to design and produce highly active metal-free bifunctional FFAEs for electrochemical energy devices.

Tight Binding and Dual Encapsulation Enabled Stable Thick Silicon/Carbon Anode with Ultrahigh Volumetric Capacity for Lithium Storage.

Silicon (Si) is regarded as one of the most promising anode materials for high-performance lithium-ion batteries (LIBs). However, how to mitigate its poor intrinsic conductivity and the lithiation/delithiation-induced large volume change and thus structural degradation of Si electrodes without compromising their energy density is critical for the practical application of Si in LIBs. Herein, an integration strategy is proposed for preparing a compact micron-sized Si@G/CNF@NC composite with a tight binding and dual-encapsulated architecture that can endow it with superior electrical conductivity and deformation resistance, contributing to excellent cycling stability and good rate performance in thick electrode. At an ultrahigh mass loading of 10.8 mg cm-2 , the Si@G/CNF@NC electrode also presents a large initial areal capacity of 16.7 mA h cm-2 (volumetric capacity of 2197.7 mA h cm-3 ). When paired with LiNi0.95 Co0.02 Mn0.03 O2 , the pouch-type full battery displays a highly competitive gravimetric (volumetric) energy density of ≈459.1 Wh kg-1 (≈1235.4 Wh L-1 ).

Shape-Memory and Anisotropic Carbon Aerogel from Biomass and Graphene Oxide.

Biomass, as the most abundant and sustainable resource on the earth, has been regarded as an ideal carbon source to prepare various carbon materials. However, manufacturing shape-memory carbon aerogels with excellent compressibility and elasticity from biomass remains an open challenge. Herein, a cellulose-derived carbon aerogel with an anisotropic architecture is fabricated with the assistance of graphene oxide (GO) through a directional freeze-drying process and carbonization. The carbon aerogel displays excellent shape-memory performances, with high stress and height retentions of 93.6% and 95.5% after 1000 compression cycles, respectively. Moreover, the carbon aerogel can identify large ranges of compression strain (10-80%), and demonstrates excellent current stability during cyclic compression. The carbon aerogel can precisely capture a variety of biological signals in the human body, and thus can be used in wearable electronic devices.

Assembling nanocelluloses into fibrous materials and their emerging applications.

Nanocelluloses, derived from various plants or specific bacteria, represent the renewable and sophisticated nano building blocks for emerging functional materials. Especially, the assembly of nanocelluloses as fibrous materials can mimic the structural organization of their natural counterparts to integrate various functions, thus holding great promise for potential applications in various fields, such as electrical device, fire retardance, sensing, medical antibiosis, and drug release. Due to the advantages of nanocelluloses, a variety of fibrous materials have been fabricated with the assistance of advanced techniques, and their applications have attracted great interest in the past decade. This review begins with an overview of nanocellulose properties followed by the historical development of assembling processes. There will be a focus on assembling techniques, including traditional methods (wet spinning, dry spinning, and electrostatic spinning) and advanced methods (self-assembly, microfluidic, and 3D printing). In particular, the design rules and various influencing factors of assembling processes related to the structure and function of fibrous materials are introduced and discussed in detail. Then, the emerging applications of these nanocellulose-based fibrous materials are highlighted. Finally, some perspectives, key opportunities, and critical challenges on future research trends within this field are proposed.

Mass Production of Sulfur-Tuned Single-Atom Catalysts for Zn-Air Batteries.

Single-atom catalysts (SACs) show great potential for rechargeable Zn-air batteries (ZABs); however, scalable production of SACs from sustainable resources is difficult owing to poor control of the local coordination environment. Herein, lignosulfonate, a by-product of the papermaking industry, is utilized as a multifunctional bioligand for the mass production of SACs with highly active MN4 S sites (M represents Fe, Cu, and Co) via strong metalnitrogen/sulfur coordination. This effectively adjusts the charge distribution and promotes the catalytic performance, leading to highly durable and excellent performance in oxygen reduction and evolution reactions for ZABs. This study paves the way for the industrial production of cost-effective SACs in a sustainable manner.

A Liquid Metal Microdroplets Initialized Hemicellulose Composite for 3D Printing Anode Host in Zn-Ion Battery.

Maintaining a steady affinity between gallium-based liquid metals (LM) and polymer binders, particularly under continuous mechanical deformation, such as extrusion-based 3D printing or plating/stripping of Zinc ion (Zn2+ ), is very challenging. Here, an LM-initialized polyacrylamide-hemicellulose/EGaIn microdroplets hydrogel is used as a multifunctional ink to 3D-print self-standing scaffolds and anode hosts for Zn-ion batteries. The LM microdroplets initiate acrylamide polymerization without additional initiators and cross-linkers, forming a double-covalent hydrogen-bonded network. The hydrogel acts as a framework for stress dissipation, enabling recovery from structural damage due to the cyclic plating/stripping of Zn2+ . The LM-microdroplet-initialized polymerization with hemicelluloses can facilitate the production of 3D printable inks for energy storage devices.

Colloidal stability of negatively charged cellulose nanocrystalline in aqueous systems.

Colloidal stability of negatively charged cellulose nanocrystalline (CNC) in the presence of inorganic and organic electrolytes was investigated by means of dynamic light scattering and atomic force microscopy. CNC could be well dispersed in distilled water due to the electrostatic repulsion among negatively charged sulfate ester groups. Increasing the concentration of inorganic cation ions (Na(+) and Ca(2+)) resulted in CNC aggregation. CNC in divalent cation ion Ca(2+) solution exhibited less stability than that in monovalent cation ion Na(+) solution. Organic low-molecular-weight electrolyte sodium dodecyl sulfate (SDS) favored the stability of CNC suspension, whereas organic high-molecular-weight electrolyte sodium carboxymethyl cellulose (CMC) induced CNC particle aggregation due to intermolecular bridging interaction or entanglement. Cationic polyacrylamide (CPAM) caused a serious aggregation of CNC particles even at low concentration of CPAM. At low ionic strength (Na(+), 1 mM), CNC were stable in aqueous solution at the pH range of 2-11.

Cytomembrane-Inspired MXene Ink with Amphiphilic Surfactant for 3D Printed Microsupercapacitors.

Two-dimensional (2D) material-based hydrogels have been widely utilized as the ink for extrusion-based 3D printing in various electronics. However, the viscosity of the hydrogel ink is not high enough to maintain the self-supported structure without architectural deformation. It is also difficult to tune the microstructure of the printed devices using a low-viscosity hydrogel ink. Herein, by mimicking a phospholipid bilayer in a cytomembrane, the amphiphilic surfactant nonaethylene glycol monododecyl ether (C12E9) was incorporated into MXene hydrogel. The incorporation of C12E9 offers amphiphilicity to the MXene flakes and produces a 3D interlinked network of the MXene flakes. The 3D interlinked network offers a high-viscosity, homogenized flake distribution and enhanced printability to the ink. This ink facilitates the alignment of the MXene flakes during extrusion as well as the formation of the aligned micro- and sub-microsized porous structures, leading to the improved electrochemical performance of the printed microsupercapacitor. This study provides an example for the preparation of microelectronics with tunable microstructures.

Nanocomposite films based on xylan-rich hemicelluloses and cellulose nanofibers with enhanced mechanical properties.

Interest in xylan-rich hemicelluloses (XH) film is growing, and efforts have been made to prepare XH films with improved mechanical properties. This work described an effective approach to produce nanocomposite films with enhanced mechanical properties by incorporation of cellulose nanofibers (CNFs) into XH. Aqueous dispersions of XH (64-75 wt %), sorbitol (16-25 wt %), and CNF (0-20 wt %) were cast at a temperature of 23 °C and 50% relative humidity. The surface morphology of the films was revealed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The thermal properties and crystal structure of the films were evaluated by thermal analysis (TG) and X-ray diffraction (XRD). The surface of XH films with and without CNF was composed primarily of nanonodules, and CNFs were embedded in the XH matrix. Freeze-dried XH powder was amorphous, whereas the films with and without CNF showed a distinct peak at around 2θ = 18°, which suggested that XH molecules aggregated or reordered in the casting solution or during water evaporation. Furthermore, the nanocomposite films had improved thermal stability. XH film with 25 wt % plasticizer (sorbitol, based on dry XH weight) showed poor mechanical properties, whereas incorporation of CNF (5-20 wt %, based on the total dry mixture) into the film resulted in enhanced mechanical properties due to the high aspect ratio and mechanical strength of CNF and strong interactions between CNF and XH matrix. This effective method makes it possible to produce hemicellulose-based biomaterials of high quality.

Iron Single Atom Catalyzed Quinoline Synthesis.

The production of high-value chemicals by single-atom catalysis is an attractive proposition for industry owing to its remarkable selectivity. Successful demonstrations to date are mostly based on gas-phase reactions, and reports on liquid-phase catalysis are relatively sparse owing to the insufficient activation of reactants by single-atom catalysts (SACs), as well as, their instability in solution. Here, mechanically strong, hierarchically porous carbon plates are developed for the immobilization of SACs to enhance catalytic activity and stability. The carbon-based SACs exhibit excellent activity and selectivity (≈68%) for the synthesis of substituted quinolines by a three-component oxidative cyclization, affording a wide assortment of quinolines (23 examples) from anilines and acetophenones feedstock in an efficient, atom-economical manner. Particularly, a Cavosonstat derivative can be synthesized through a one-step, Fe1 -catalyzed cyclization instead of traditional Suzuki coupling. The strategy is also applicable to the deuteration of quinolines at the fourth position, which is challenging by conventional methods. The synthetic utility of the carbon-based SAC, together with its reusability and scalability, renders it promising for industrial scale catalysis.

Xylan-Derived Light Conversion Nanocomposite Film.

A new type of sustainable light conversion nanocomposite film was fabricated by using carboxymethyl xylan as matrix and xylan-derived carbon dots (CDs) as both light conversion regents and nano reinforcements. The results demonstrate that CDs can not only significantly enhance the mechanical strength of the nanocomposite film because of chemical reaction between CDs and carboxymethyl xylan, but also impart the film with excellent optical properties. With 1.92 wt% CDs, the tensile strength and elastic modulus of the film are increased by 114.3% and 90.7%, respectively. Moreover, the film has typical excitation and emission spectra, enabling the efficient absorption of UV and the conversion of UV to blue light. This xylan-derived light conversion nanocomposite film is expected to be used in agricultural planting and food packaging.

Functional Chitosan-based Materials for Biological Applications.

BACKGROUND: Bio-based materials, as the plentiful and renewable resources for natural constituents which are essential for biomedical and pharmaceutical applications, have not been exploited adequately yet. Chitosan is a naturally occurring polysaccharide obtained from chitin, which has recently attracted widespread attention owing to its excellent activity. This review shows the methods of extraction and modification of chitosan and provides recent progress of synthesis and use of chitosan-based materials in biological applications. METHODS: By consulting the research literature of the last decade, the recent progresses of functional chitosan-based materials for biological applications were summarized and divided into the methods of extraction chitosan, the chemical modification of chitosan, chitosan-based materials for biological applications were described and discussed. RESULTS: Chemical modification of chitosan broadens its applications, leading to developing numerous forms of chitosan-based materials with excellent properties. The excellent bioactivity of chitosan-based material enables it serves potential applications in biomedical fields. CONCLUSION: Chitosan-based materials not only exhibit the excellent activities of chitosan but also show other appealing performance of combined materials, even give the good synergistic properties of chitosan and its composite materials. Further studies are needed to define the ideal physicochemical properties of chitosan for each type of biomedical applications. The development of various functional chitosan-based materials for biological applications will be an important field of research, and this kind of material has important commercial value.

An Iron-Decorated Carbon Aerogel for Rechargeable Flow and Flexible Zn-Air Batteries.

Mechanically stable and foldable air cathodes with exceptional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities are key components of wearable metal-air batteries. Herein, a directional freeze-casting and annealing approach is reported for the construction of a 3D honeycomb nanostructured, N,P-doped carbon aerogel incorporating in situ grown FeP/Fe2 O3 nanoparticles as the cathode in a flexible Zn-air battery (ZAB). The aqueous rechargeable Zn-air batteries assembled with this carbon aerogel exhibit a remarkable specific capacity of 648 mAh g-1 at a current density of 20 mA cm-2 with a good long-term durability, outperforming those assembled with commercial Pt/C+RuO2 catalyst. Furthermore, such a foldable carbon aerogel with directional channels can serve as a freestanding air cathode for flexible solid-state Zn-air batteries without the use of carbon paper/cloth and additives, giving a specific capacity of 676 mAh g-1 and an energy density of 517 Wh kg-1 at 5 mA cm-2 together with good cycling stability. This work offers a new strategy to design and synthesize highly effective bifunctional air cathodes to be applied in electrochemical energy devices.

Cobalt Single-Atom-Intercalated Molybdenum Disulfide for Sulfide Oxidation with Exceptional Chemoselectivity.

The identification of chemoselective oxidation process en route to fine chemicals and specialty chemicals is a long-standing pursuit in chemical synthesis. A vertically structured, cobalt single atom-intercalated molybdenum disulfide catalyst (Co1 -in-MoS2 ) is developed for the chemoselective transformation of sulfides to sulfone derivatives. The single-atom encapsulation alters the electron structure of catalyst owing to confinement effect and strong metal-substrate interaction, thus enhancing adsorption of sulfides and chemoselective oxidation at the edge sites of MoS2 to achieve excellent yields of up to 99% for 34 examples. The synthetic scopes can be extended to sulfide-bearing alkenes, alkynes, aldehydes, ketones, boronic esters, and amines derivatives as a toolbox for the synthesis of high-value, multifunctional sulfones and late-stage functionalization of pharmaceuticals, e.g., Tamiflu. The synthetic utility of cobalt single atom-intercalated MoS2 , together with its reusability, scalability, and simplified purification process, renders it promising for industrial productions.

Cellulose carbon aerogel/PPy composites for high-performance supercapacitor.

Energy storage and conversion systems have recently attracted great interest in application of various electronic devices. Conductive polymers are promising pseudocapacitive materials for supercapacitors due to their low cost, low environmental impact, high pseudo capacitance, and ease of fabrication. However, the poor cycling stability limits their application. Here, we use cellulose as a carbon precursor to prepare a hierarchical porous carbon aerogel as a support for conductive polymer polypyrrole (PPy). The hierarchical porous architecture not only enables the efficient penetration and uniform loading of PPy throughout the carbon network, but also ensures a rapid transfer of electrolytes and the high accessibility of PPy. The as-prepared hybrid shows a high specific capacitance of 387.6 F g-1 (0.5 A g-1 in 1.0 M H2SO4) and excellent cycling stability (92.6% capacitance retention after 10,000 cycles). This work provides an effective method to sustainably fabricate porous composite electrodes from renewable cellulose for supercapacitor.

Lignocellulosic Biomass Derived Functional Materials: Synthesis and Applications in Biomedical Engineering.

The pertinent issue of resources shortage arising from global climate change in the recent years has accentuated the importance of materials that are environmentally friendly. Despite the merits of current material like cellulose as the most abundant natural polysaccharide on earth, the incorporation of lignocellulosic biomass has the potential to value-add the recent development of cellulose-derivatives in drug delivery systems. Lignocellulosic biomass, with a hierarchical structure is comprised of cellulose, hemicellulose and lignin. As an excellent substrate that is renewable, biodegradable, biocompatible and chemically accessible for modified materials, lignocellulosic biomass sets forth a myriad of applications. To date, materials derived from lignocellulosic biomass have been extensively explored for new technological development and applications, such as biomedical, green electronics and energy products. In this review, chemical constituents of lignocellulosic biomass are first discussed before we critically examine the potential alternatives in the field of biomedical application. In addition, the pretreatment methods for extracting cellulose, hemicellulose and lignin from lignocellulosic biomass as well as their biological applications including drug delivery, biosensor, tissue engineering etc. are reviewed. It is anticipated there will be an increasing interest and research findings in cellulose, hemicellulose and lignin from natural resources, which help provide important directions for the development in biomedical applications.

Tailoring the physicochemical properties of chitosan-derived N-doped carbon by controlling hydrothermal carbonization time for high-performance supercapacitor application.

Although a few methods have been employed to fabricate N-doped porous carbons from various N-containing biomass resources, it is still a big challenge to obtain porous carbons with high supercapacitance performances. Herein, we demonstrate that aN-doped porous carbon with superior supercapacitance can be prepared from chitosan by properly controlling hydrothermal carbonization (HC). The physicochemical and supercapacitance properties of the HC-derived carbon are highly time-dependent and can be readily tailored. As compared with traditional direct pyrolysis, the proper control of HC time plays a very important role in promoting the supercapacitance performances of the N-doped carbon by increasing turbostratic structure, doped N content and active N species, specific surface area, and especially balancing micro- and mesoporosity. These synergistic effects produce a N-doped carbon with an ultrahigh specific capacitance of 406 ± 36 F g-1 in a three-electrode system, outstanding rate capability, and ultrahigh energy density (23.6 ± 3.1 W h kg-1).

Hierarchically Porous Carbon Plates Derived from Wood as Bifunctional ORR/OER Electrodes.

Porous carbon electrodes have emerged as important cathode materials for metal-air battery systems. However, most approaches for fabricating porous carbon electrodes from biomass are highly energy inefficient as they require the breaking down of the biomass and its subsequent reconstitution into powder-like carbon. Here, enzymes are explored to effectively hydrolyze the partial cellulose in bulk raw wood to form a large number of nanopores, which helps to maximally expose the inner parts of the raw wood to sufficiently dope nitrogen onto the carbon skeletons during the subsequent pyrolysis process. The resulting carbons exhibit excellent catalytic activity with respect to the oxygen reduction and oxygen evolution reactions. As-fabricated cellulose-digested, carbonized wood plates are mechanically strong, have high conductivity, and contain a crosslinked network and natural ion-transport channels and can be employed directly as metal-free electrodes without carbon paper, polymer binders, or carbon black. When used as metal-free cathodes in zinc-air batteries, they result in a specific capacity of 801 mA h g-1 and an energy density of 955 W h kg-1 with the long-term stability of the batteries being as high as 110 h. This work paves the way for the ready conversion of abundant biomass into high-value engineering products for energy-related applications.

Lignin Nanosphere-Supported Cuprous Oxide as an Efficient Catalyst for Huisgen [3+2] Cycloadditions under Relatively Mild Conditions.

In this work, low-cost lignin nanospheres were fabricated and further applied as an efficient and sustainable support for preparing cuprous oxide (Cu2O) "green" catalyst by using electrospraying technology. The unalloyed lignin, a special three-dimensional molecular structure, was successfully processed into uniform nanospheres under an electrospraying condition. The synthesized lignin-supported Cu2O catalyst had a well-defined nanosphere structure, and Cu2O nanoparticles with sizes less than 30 nm were supported by exposed layers of lignin nanospheres. There were C⁻O⁻Cu bonds formed between the lignin nanospheres and the metallic nanoparticles. The lignin nanospheres and the lignin nanosphere-supported catalyst werfe characterized by utilizing XRD, SEM, TEM, XPS, EDS, and TGA. The immobilization of Cu2O nanoparticles on the lignin nanospheres was beneficial for dispersion of the Cu2O nanoparticles and preventing their aggregation, which could cause catalyst deactivation, which favored the Huisgen [3+2] cycloaddition reaction. The triazole synthesis results indicated that the lignin nanosphere-supported Cu2O catalyst had a high catalytic performance with 99% yield under solvent-free conditions. Furthermore, the as-synthesized catalyst could be recycled for four times without significantly losing its catalytic activity.