A comprehensive review of covalent organic frameworks (COFs) and their derivatives in environmental pollution control.

Covalent organic frameworks (COFs) have gained considerable attention due to their design possibilities as the molecular organic building blocks that can stack in an atomically precise spatial arrangement. Since the inception of COFs in 2005, there has been a continuous expansion in the product range of COFs and their derivatives. This expansion has led to the evolution of three-dimensional structures and various synthetic routes, propelling the field towards large-scale preparation of COFs and their derivatives. This review will offer a holistic analysis and comparison of the spatial structure and synthesis techniques of COFs and their derivatives. The conventional methods of COF synthesis (i.e., ultrasonic chemical, microwave, and solvothermal) are discussed alongside the synthesis strategies of new COFs and their derivatives. Furthermore, the applications of COFs and their derived materials are demonstrated in air, water, and soil pollution management such as gas capture, catalytic conversion, adsorption, and pollutant removal. Finally, this review highlights the current challenges and prospects for large-scale preparation and application of new COFs and the derived materials. In line with the United Nations Sustainable Development Goals (SDGs) and the needs of digital-enabled technologies (AI and machine learning), this review will encompass the future technical trends for COFs in environmental pollution control.

Microstructure-Reconfigured Graphene Oxide Aerogel Metamaterials for Ultrarobust Directional Sensing at Human-Machine Interfaces.

Graphene aerogels hold huge promise for the development of high-performance pressure sensors for future human-machine interfaces due to their ordered microstructure and conductive network. However, their application is hindered by the limited strain sensing range caused by the intrinsic stiffness of the porous microstructure. Herein, an anisotropic cross-linked chitosan and reduced graphene oxide (CCS-rGO) aerogel metamaterial is realized by reconfiguring the microstructure from a honeycomb to a buckling structure at the dedicated cross-section plane. The reconfigured CCS-rGO aerogel shows directional hyperelasticity with extraordinary durability (no obvious structural damage after 20 000 cycles at a directional compressive strain of ≤0.7). The CCS-rGO aerogel pressure sensor exhibits an ultrahigh sensitivity of 121.45 kPa-1, an unprecedented sensing range, and robust mechanical and electrical performance. The aerogel sensors are demonstrated to monitor human motions, control robotic hands, and even integrate into a flexible keyboard to play music, which opens a wide application potential in future human-machine interfaces.

Launching a Drop via Interplay of Buoyancy and Stick-Jump Dissolution.

According to Archimedes' principle, a submerged object with a density lower than that of aqueous acid solution is more buoyant than a smaller one. In this work, a remarkable phenomenon is reported wherein a dissolving drop on a substrate rises in the water only after it has diminished to a much smaller size, though the buoyancy is smaller. The drop consisting of a polymer solution reacts with the acid in the surrounding, yielding a water-soluble product. During drop dissolution, water-rich microdroplets form within the drop, merging with the external aqueous phase along the drop-substrate boundary. Two key elements determine the drop rise dynamics. The first is the stick-jump behavior during drop dissolution. The second is that buoyancy exerts a strong enough force on the drop at an Archimedean number greater than 1, while the stick-jump behavior is ongoing. The time of the drop rise is controlled by the initial size and the reaction rate of the drop. This novel mechanism for programmable drop rise may be beneficial for many future applications, such as microfluidics, microrobotics, and device engineering where the spontaneous drop detachment may be utilized to trigger a cascade of events in a dense medium.

Spontaneous Rise of Hydrogen Microbubbles in Interfacial Gas Evolution Reaction.

Liquid organic hydrogen carrier is a promising option for the transport and storage of hydrogen as a clean energy source. This study examines the stability and behavior of organic drops immobilized on a substrate during an interfacial hydrogen-evolution reaction (HER) at the drop surface and its surrounding aqueous solution. Hydrogen microbubbles form within the drop and rise to the drop apex. The growth rate of the hydrogen in-drop bubble increases with the concentration of the reactant in the surrounding medium. The drop remains stable till the buoyancy acting on the in-drop bubble is large enough to overcome the capillary force and the external viscous drag. The bubble spontaneously rises and carries a portion drop liquid to the solution surface. These spontaneous rising in-drop bubbles are detected in measurements using a high-precision sensor placed on the upper surface of the aqueous solution, reversing the settling phase from phase separation in the reactive emulsion. The finding from this work provides new insights into the behaviors of drops and bubbles in many interfacial gas evolution reactions in clean technologies.

Transient Zwitterions Dynamics Empowered Adaptive Interface for Ultra-Stable Zn Plating/Stripping.

A highly reversible zinc anode is crucial for the commercialization of zinc-ion batteries. However, the change in the microstructure of the electric double layer originated from the dynamic change in charge density on the electrode greatly impacts anode reversibility during charge/discharge, which is rarely considered in previous research. Herein, the zwitterion additive is employed to create an adaptive interface by coupling the transient zwitterion dynamics upon the change of interfacial charge density. Ab initio molecular dynamics simulations suggest the molecular orientation and adsorption groups of zwitterions will be determined by the charging state of the electrode. ZnSO4 electrolyte with zwitterion fulfills a highly reversible Zn anode with an average Coulombic efficiency of up to 99.85%. Zn/Zn symmetric cells achieve greatly enhanced cycling stability for 700 h with extremely small voltage hysteresis of 29 mV under 5 mA cm-2 with 5 mAh cm-2 . This study validates the adaptive interface based on transient dynamics of zwitterions, which sheds new light on developing highly reversible metal anodes with a high utilization rate.

MXene/Nitrogen-Doped Carbon Nanosheet Scaffold Electrode toward High-Performance Solid-State Zinc Ion Supercapacitor.

While MXene is widely used as an electrode material for supercapacitor, the intrinsic limitation of stacking caused by the interlayer van der Waals forces has yet to be overcome. In this work, a strategy is proposed to fabricate a composite scaffold electrode (MCN) by intercalating MXene with highly nitrogen-doped carbon nanosheets (CN). The 2D structured CN, thermally converted and pickling from Zn-hexamine (Zn-HMT), serves as a spacer that effectively prevents the stacking of MXene and contributes to a hierarchically scaffolded structure, which is conducive to ion movement; meanwhile, the high nitrogen-doping of CN tunes the electronic structure of MCN to facilitate charge transfer and providing additional pseudocapacitance. As a result, the MCN50 composite electrode achieves a high specific capacitance of 418.4 F g-1 at 1 A g-1. The assembled symmetric supercapacitor delivers a corresponding power density of 1658.9 W kg-1 and an energy density of 30.8 Wh kg-1. The all-solid-state zinc ion supercapacitor demonstrates a superior energy density of 68.4 Wh kg-1 and a power density of 403.5 W kg-1 and shows a high capacitance retention of 93% after 8000 charge-discharge cycles. This study sheds a new light on the design and development of novel MXene-based composite electrodes for high performance all-solid-state zinc ion supercapacitor.

Hydrophobic Multilayered PEG@PAN/MXene/PVDF@SiO2 Composite Film with Excellent Thermal Management and Electromagnetic Interference Shielding for Electronic Devices.

With the rapid development of electronic industry, it's pressing to develop multifunctional electromagnetic interference (EMI) shielding materials to ensure the stable operation of electronic devices. Herein, multilayered flexible PEG@PAN/MXene (Ti3C2Tx)/PVDF@SiO2 (PMF) composite film has been constructed from the level of microstructure design via coaxial electrospinning, coating spraying, and uniaxial electrospinning strategies. Benefiting from the effective encapsulation for PEG and high conductivity of MXene coating, PEG@PAN/MXene composite film with MXene coating loading density of 0.70 mg cm-2 exhibits high thermal energy storage density of 120.77 J g-1 and great EMI shielding performance (EMI SE of 34.409 dB and SSE of 49.086 dB cm3 g-1) in X-band (8-12 GHz). Therefore, this advanced composite film can not only help electronic devices prevent the influence of electromagnetic pollution in the X-band but also play an important role in electronic device thermal management. Additionally, the deposition of nano PVDF@SiO2 fibers (289 ± 128 nm) endowed the PMF composite film with great hydrophobic properties (water contact angle of 126.5°) to ensure the stable working of hydrophilic MXene coating, thereby breaks the limitation of humid application environments. The finding paves a new way for the development of novel multifunctional EMI shielding composite films for electronic devices.

Overview of Inorganic Electrolytes for All-Solid-State Sodium Batteries.

All-solid-state sodium batteries (AS3B) emerged as a strong contender in the global electrochemical energy storage market as a replacement for current lithium-ion batteries (LIB) owing to their high abundance, low cost, high safety, high energy density, and long calendar life. Inorganic electrolytes (IEs) are highly preferred over the conventional liquid and solid polymer electrolytes for sodium-ion batteries (SIBs) due to their high ionic conductivity (∼10-2-10-4 S cm-1), wide potential window (∼5 V), and overall better battery performances. This review discusses the bird's eye view of the recent progress in inorganic electrolytes such as Na-ß"-alumina, NASICON, sulfides, antipervoskites, borohydride-type electrolytes, etc. for AS3Bs. Current state-of-the-art inorganic electrolytes in correlation with their ionic conduction mechanism present challenges and interfacial characteristics that have been critically reviewed in this review. The current challenges associated with the present battery configuration are overlooked, and also the chemical and electrochemical stabilities are emphasized. The substantial solution based on ongoing electrolyte development and promising modification strategies are also suggested.

A Simple and Effective Physical Ball-Milling Strategy to Prepare Super-Tough and Stretchable PVA@MXene@PPy Hydrogel for Flexible Capacitive Electronics.

Biomimetic flexible electronics for E-skin have received increasing attention, due to their ability to sense various movements. However, the development of smart skin-mimic material remains a challenge. Here, a simple and effective approach is reported to fabricate super-tough, stretchable, and self-healing conductive hydrogel consisting of polyvinyl alcohol (PVA), Ti3 C2 Tx MXene nanosheets, and polypyrrole (PPy) (PMP hydrogel). The MXene nanosheets and Fe3+ serve as multifunctional cross-linkers and effective stress transfer centers, to facilitate a considerable high conductivity, super toughness, and ultra-high stretchability (elongation up to 4300%) for the PMP hydrogel with. The hydrogels also exhibit rapid self-healing and repeatable self-adhesive capacity because of the presence of dynamic borate ester bond. The flexible capacitive strain sensor made by PMP hydrogel shows a relatively broad range of strain sensing (up to 400%), with a self-healing feature. The sensor can precisely monitor various human physiological signals, including joint movements, facial expressions, and pulse waves. The PMP hydrogel-based supercapacitor is demonstrated with a high capacitance retention of ≈92.83% and a coulombic efficiency of ≈100%.

An Overview of Metal-Organic Framework Based Electrocatalysts: Design and Synthesis for Electrochemical Hydrogen Evolution, Oxygen Evolution, and Carbon Dioxide Reduction Reactions.

Due to the increasing global energy demands, scarce fossil fuel supplies, and environmental issues, the pursued goals of energy technologies are being sustainable, more efficient, accessible, and produce near zero greenhouse gas emissions. Electrochemical water splitting is considered as a highly viable and eco-friendly energy technology. Further, electrochemical carbon dioxide (CO2 ) reduction reaction (CO2 RR) is a cleaner strategy for CO2 utilization and conversion to stable energy (fuels). One of the critical issues in these cleaner technologies is the development of efficient and economical electrocatalyst. Among various materials, metal-organic frameworks (MOFs) are becoming increasingly popular because of their structural tunability, such as pre- and post- synthetic modifications, flexibility in ligand design and its functional groups, and incorporation of different metal nodes, that allows for the design of suitable MOFs with desired quality required for each process. In this review, the design of MOF was discussed for specific process together with different synthetic methods and their effects on the MOF properties. The MOFs as electrocatalysts were highlighted with their performances from the aspects of hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and electrochemical CO2 RR. Finally, the challenges and opportunities in this field are discussed.

Mechanically-robust electrospun nanocomposite fiber membranes for oil and water separation.

Mechanically-robust nanocomposite membranes have been developed via crosslinking chemistry and electrospinning technique based on the rational selection of dispersed phase materials with high Young's modulus (i.e., graphene and multiwalled carbon nanotubes) and Cassie-Baxter design and used for oil and water separation. Proper selection of dispersed phase materials can enhance the stiffness of nanocomposite fiber membranes while their length has to be larger than their critical length. Chemical modification of the dispersed phase materials with fluorochemcials and their induced roughness were critical to achieve superhydrophobocity. Surface analytic tools including goniometer, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, atomic force microscopy (AFM) and scanning electron microscope (SEM) were applied to characterize the superhydrophobic nanocomposite membranes. An AFM-based nanoindentation technique was used to measure quantitativly the stiffness of the nanocomposite membranes for local region and whole composites, compared with the results by a tensile test technique. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques were used to confirm composition and formation of nanocomposite membranes. These membranes demonstrated excellent oil/water separation. This work has potential application in the field of water purification and remediation.

Ion Hopping: Design Principles for Strategies to Improve Ionic Conductivity for Inorganic Solid Electrolytes.

Solid electrolytes are considered as an ideal substitution of liquid electrolytes, avoiding the potential hazards of volatilization, flammability, and explosion for liquid electrolyte-based rechargeable batteries. However, there are significant performance gaps to be bridged between solid electrolytes and liquid electrolytes; one with a particular importance is the ionic conductivity which is highly dependent on the material types and structures. In this review, the general physical image of ion hopping in the crystalline structure is revisited, by highlighting two main kernels that impact ion migration: ion hopping pathways and skeletons interaction. The universal strategies to effectively improve ionic conductivity of inorganic solid electrolytes are then systematically summarized: constructing rapid diffusion pathways for mobile ions; and reducing resistance of the surrounding potential field. The scoped strategies offer an exclusive view on the working principle of ion movement regardless of the ion species, thus providing a comprehensive guidance for the future exploitation of solid electrolytes.

Supramolecular Network Structured Gel Polymer Electrolyte with High Ionic Conductivity for Lithium Metal Batteries.

Polymer-based solid electrolytes (PSEs) offer great promise in developing lithium metal batteries due to their attractive features such as safety, light weight, low cost, and high processability. However, a PSE-based lithium battery usually requires a relatively high temperature (60 °C or above) to complete charge and discharge due to the poor ionic conductivity of PSEs. Herein, a gel polymer electrolytes (GPEs) film with a supramolecular network structure through a facile one-step photopolymerization is designed and developed. The crosslinked structure and quadruple hydrogen bonding fulfil the GPEs with high thermal stability and good mechanical property with a maximum tensile strain of 48%. The obtained GPEs possess a high ionic conductivity of 3.8 × 10-3 S cm-1 at 25 °C and a decomposition voltage ≥ 4.6 V (vs Li/Li+ ). The cells assembled with LiFePO4 cathode and Li anode, present an initial discharge specific capacity of 155.6 mAh g-1 and a good cycling efficiency with a capacity retention rate of 81.1% after 100 charges/discharge cycles at 0.1 C at ambient temperature. This work encompasses a route to develop high performance PSEs that can be operated at room temperature for future lithium metal batteries.

Electrolyte Salts and Additives Regulation Enables High Performance Aqueous Zinc Ion Batteries: A Mini Review.

Aqueous zinc ion batteries (ZIBs) are regarded as one of the most ideally suited candidates for large-scale energy storage applications owning to their obvious advantages, that is, low cost, high safety, high ionic conductivity, abundant raw material resources, and eco-friendliness. Much effort has been devoted to the exploration of cathode materials design, cathode storage mechanisms, anode protection as well as failure mechanisms, while inadequate attentions are paid on the performance enhancement through modifying the electrolyte salts and additives. Herein, to fulfill a comprehensive aqueous ZIBs research database, a range of recently published electrolyte salts and additives research is reviewed and discussed. Furthermore, the remaining challenges and future directions of electrolytes in aqueous ZIBs are also suggested, which can provide insights to push ZIBs' commercialization.

A Strand Entangled Supramolecular PANI/PAA Hydrogel Enabled Ultra-Stretchable Strain Sensor.

Hydrogel electronics have attracted growing interest for emerging applications in personal healthcare management, human-machine interaction, etc. Herein, a "doping then gelling" strategy to synthesize supramolecular PANI/PAA hydrogel with a specific strand entangled network is proposed, by doping the PANI with acrylic acid (AA) monomers to avoid PANI aggregation. The high-density electrostatic interaction between PAA and PANI chains serves as a dynamic bond to initiate the strand entanglement, enabling PAA/PANI hydrogel with ultra-stretchability (2830%), high breaking strength (120 kPa), and rapid self-healing properties. Moreover, the PAA/PANI hydrogel-based sensor with a high strain sensitivity (gauge factor = 12.63), a rapid responding time (222 ms), and a robust conductivity-based sensing behavior under cyclic stretching is developed. A set of strain sensing applications to precisely monitor human movements is also demonstrated, indicating a promising application prospect as wearable devices.

Latticed-Confined Conversion Chemistry of Battery Electrode.

The electrochemical conversion reaction, usually featured by multiple redox processes and high specific capacity, holds great promise in developing high-energy rechargeable battery technologies. However, the complete structural change accompanied by spontaneous atomic migration and volume variation during the charge/discharge cycle leads to electrode disintegration and performance degradation, therefore severely restricting the application of conventional conversion-type electrodes. Herein, latticed-confined conversion chemistry is proposed, where the "intercalation-like" redox behavior is realized on the electrode with a "conversion-like" high capacity. By delicately formulating the high-entropy compounds, the pristine crystal structure can be preserved by the inert lattice framework, thus enabling an ultra-high initial Coulombic efficiency of 92.5% and a long cycling lifespan over a thousand cycles after the quasistatic charge-discharge cycle. This lattice-confined conversion chemistry unfolds a ubiquitous insight into the localized redox reaction and sheds light on developing high-performance electrodes toward next-generation high-energy rechargeable batteries.

Fiber Surface/Interfacial Engineering on Wearable Electronics.

Surface/interfacial engineering is an essential technique to explore the fiber materials properties and fulfil new functionalities. An extensive scope of current physical and chemical treating methods is reviewed here together with a variety of real-world applications. Moreover, a new surface/interface engineering approach is also introduced: self-assembly via π-π stacking, which has great potential for the surface modification of fiber materials due to its nondestructive working principle. A new fiber family member, metal-oxide framework (MOF) fiber shows promising candidacy for fiber based wearable electronics. The understanding of surface/interfacial engineering techniques on fiber materials is advanced here and it is expected to guide the rational design of future fiber based wearable electronics.

Conversion-Alloying Anode Materials for Sodium Ion Batteries.

The past decade has witnessed a rapidly growing interest toward sodium ion battery (SIB) for large-scale energy storage in view of the abundance and easy accessibility of sodium resources. Key to addressing the remaining challenges and setbacks and to translate lab science into commercializable products is the development of high-performance anode materials. Anode materials featuring combined conversion and alloying mechanisms are one of the most attractive candidates, due to their high theoretical capacities and relatively low working voltages. The current understanding of sodium-storage mechanisms in conversion-alloying anode materials is presented here. The challenges faced by these materials in SIBs, and the corresponding improvement strategies, are comprehensively discussed in correlation with the resulting electrochemical behavior. Finally, with the guidance and perspectives, a roadmap toward the development of advanced conversion-alloying materials for commercializable SIBs is created.

A stimuli-responsive gel impregnated surface with switchable lipophilic/oleophobic properties.

In this paper, we developed a novel morphing surface technique consisting of a 3D printed miniature groove structure and injected stimuli-responsive hydrogel pattern, which is capable of switching between lipophilicity and oleophobicity under certain stimuli. Under swelling, the geometrical change of the hydrogel will buckle the surface due to the structural confinement and create a continuous transition of surface topology. Thus, it will yield a change in the surface wetting property from oleophilic to super-oleophobic with a contact angle of oil of 85° to 165°. We quantitatively investigate this structure-property relationship using finite element analysis and analytical modeling, and the simulation results and the modeling are in good agreement with the experimental ones. This morphing surface also holds potential to be developed into an autonomous system for future sub-sea/off-shore engineering applications to separate oil and water.

A Nature-Inspired, Flexible Substrate Strategy for Future Wearable Electronics.

Flexibility plays a vital role in wearable electronics. Repeated bending often leads to the dramatic decrease of conductivity because of the numerous microcracks formed in the metal coating layer, which is undesirable for flexible conductors. Herein, conductive textile-based tactile sensors and metal-coated polyurethane sponge-based bending sensors with superior flexibility for monitoring human touch and arm motions are proposed, respectively. Tannic acid, a traditional mordant, is introduced to attach to various flexible substrates, providing a perfect platform for catalyst absorbing and subsequent electroless deposition (ELD). By understanding the nucleation, growth, and structure of electroless metal deposits, the surface morphology of metal nanoparticles can be controlled in nanoscale with simple variation of the plating time. When the electroless plating time is 20 min, the normalized resistance (R/R0 ) of as-made conductive fibers is only 1.6, which is much lower than a 60 min ELD sample at the same conditions (R/R0 ≈ 5). This is because a large number of unfilled gaps between nanoparticles prevent metal films from cracking under bending. Importantly, the Kelvin problem is relevant to deposited conductive coatings because metallic cells have a honeycomb-like structure, which is a rationale to explain the relationships of conductivity and flexibility.