Covalent Organic Frameworks as Electrode Materials for Alkali Metal-ion Batteries.

Covalent organic frameworks (COFs) are a class of porous crystalline polymeric materials constructed by linking organic small molecules through covalent bonds. COFs have the advantages of strong covalent bond network, adjustable pore structure, large specific surface area and excellent thermal stability, and have broad application prospects in various fields. Based on these advantages, rational COFs design strategies such as the introduction of active sites, construction of conjugated structures, and carbon material composite, etc. can effectively improve the conductivity and stability of the electrode materials in the field of batteries. This paper introduces the latest research results of high-performance COFs electrode materials in alkali metal-ion batteries (LIBs, SIBs, PIBs and LSBs) and other advanced batteries. The current challenges and future design directions of COFs-based electrode are discussed. It provides useful insights for the design of novel COFs structures and the development of high-performance alkali metal-ion batteries.

Covalent Organic Frameworks in Aqueous Zinc-Ion Batteries.

The development and utilization of green renewable energy are imperative with the aggravation of environmental pollution and energy crisis. In recent years, the exploration of electrochemical energy storage systems has gradually become a research hotspot in energy. Among them, aqueous zinc-ion batteries (ZIBs) have progressively developed into highly competitive and efficient energy storage devices owing to their inherent safety, natural abundance, and higher theoretical capacity. However, the practical application of ZIBs suffers from the limitation of challenges such as the absence of proper cathode materials and the unavoidable zinc dendrites and side reactions of Zn anode. Covalent organic frameworks (COFs) are an attractive class of electrode materials due to their inherent advantages, like structural designability, high stability, and ordered-open channels, bestowing them with great potential to overcome the problems of ZIBs. In this review, we concentrate on the discussion of designed strategies of COFs applied to ZIBs. Furthermore, the methods of using COFs to solve the challenging problems of cathode development, anode modification, and electrolyte optimization for ZIBs are summarized. Finally, the existing difficulties, solution measures, and prospects of COFs for ZIBs applications are discussed. Our commentary hopes to serve as a valuable reference for developing COFs-based ZIBs.

Antimony Oxides-Based Anode Materials for Alkali Metal-Ion Storage.

With the increasing demand for renewable energy, alkali metal-ion (lithium/sodium/potassium-ion) batteries play more and more important roles in the field of static storage and electrical vehicle industry. Novel anode materials with high reversible capacity, safety and long-term cycling stability are desiderated to meet the ever-growing demand for alkali metal-ion batteries with high electrochemical performance. Antimony oxides (Sbx Oy ) show electrochemical reaction activity with all of lithium, sodium and potassium, and are expected to be promising anode materials for alkali metal-ion storage due to their high theoretical capacities, appropriate operating potential and excellent safety properties. This review is devoted to overview the research progress on reaction mechanism and improvements in electrochemical performance of antimony oxides for alkali metal-ion storage, and look forward to their further prospects.

A Strong and Double-sided Self-Adhesive Hydrogel Sensor.

Flexible self-adhesive hydrogel sensors are attracting considerable concerns in recent years. However, creating a self-adhesive hydrogel sensor with excellent mechanical properties remains to be challenging. Herein, a double-sided self-adhesive hydrogel capable of strain sensor with high strength is demonstrated by penetration strategy. The middle poly(acrylic acid)-polyacrylamide/Fe3+ (PAA-PAM/Fe3+ ) tough layer endows the double-sided self-adhesive hydrogel with high mechanical properties, while the bilateral poly[2-(methacryloyloxy) ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide-polyacrylamide (PSBMA-PAM) adhesive layers are used to ensure excellent adhesiveness on diverse substrates. The tough layer of the double-sided self-adhesive hydrogel sensor shows a strong interface bonding force against the adhesive layer. The double-sided self-adhesive hydrogel sensor enables excellent adhesiveness on diverse substrates. More importantly, it can accurately detect different strains and human motions as a self-adhesive hydrogel strain sensor. This work manifests a new route of structural design to develop a self-adhesive hydrogel sensor with excellent mechanical properties that is suitable for a wide range of applications.

Green synthesis of glyco-CuInS2 QDs with visible/NIR dual emission for 3D multicellular tumor spheroid and in vivo imaging.

Glyco-quantum dots (glyco-QDs) have attracted significant interest in bioimaging applications, notably in cancer imaging, because they effectively combine the glycocluster effect with the exceptional optical properties of QDs. The key challenge now lies in how to eliminate the high heavy metal toxicity originating from traditional toxic Cd-based QDs for in vivo bioimaging. Herein, we report an eco-friendly pathway to prepare nontoxic Cd-free glyco-QDs in water by the "direct" reaction of thiol-ending monosaccharides with metal salts precursors. The formation of glyco-CuInS2 QDs could be explained by a nucleation-growth mechanism following the LaMer model. As-prepared four glyco-CuInS2 QDs were water-soluble, monodispersed, spherical in shape and exhibited size range of 3.0-4.0 nm. They exhibited well-separated dual emission in the visible region (500-590 nm) and near-infrared range (~ 827 nm), which may be attributable to visible excitonic emission and near-infrared surface defect emission. Meanwhile, the cell imaging displayed the reversibly distinct dual-color (green and red) fluorescence in tumor cells (HeLa, A549, MKN-45) and excellent membrane-targeting properties of glyco-CuInS2 QDs based on their good biorecognition ability. Importantly, these QDs succeed in penetrating uniformly into the interior (the necrotic zone) of 3D multicellular tumor spheroids (MCTS) due to their high negative charge (zeta potential values ranging from - 23.9 to - 30.1 mV), which overcame the problem of poor penetration depth of existing QDs in in vitro spheroid models. So, confocal analysis confirmed their excellent ability to penetrate and label tumors. Thus, the successful application in in vivo bioimaging of these glyco-QDs verified that this design strategy is an effective, low cost and simple procedure for developing green nanoparticles as cheap and promising fluorescent bioprobes.

Water contaminant: Use it but do not shield it to synthesize co-polymers with multiple emission colours.

Due to the high affinity with water molecules, amide compounds are easily contaminated by moisture; therefore, the water interference effect cannot be totally excluded from the amide-involved reactions. Thus, the perfect solution is to use the interference effect but not shield it in a real application. In this work, we introduced different contents of sodium acrylate (AAS) to scavenge water from the monomers of N-isopropylacrylamide (NIPAm) when copolymerized with TPA-Vinyl-4CN. Herein, water molecules play a role as nucleophilic reagents to attack highly active functional groups as -C=C-CN from TPA-Vinyl-4CN, leading to a blue emissive TPA-Vinyl-2CHO. From this study, we made a deep awareness of the interactions between three reaction partners of AAS and NIPAm as well as TPA-Vinyl-4CN. Our results clearly demonstrated the fact that water can be perfectly used and controlled by the water absorbent of AAS, developing a new approach to synthesizing multiple emission-coloured polymers by using only one luminogen of TPA-Vinyl-4CN.

Waste Cabbage-Integrated Nutritional Superabsorbent Polymers for Water Retention and Absorption Applications.

To alleviate soil impoverishment and water shortage in desert areas, as well as to reduce the impact of waste cabbage on the environment and human health, we used waste cabbage as a substrate, 2-acrylamide-2-methyl-1-propane sulfonic acid (AMPS) and acrylic acid (AA) as polymerization units, and NH4Cl and KNO3 as nutriment to obtain two waste cabbage-superabsorbent polymers (CB-SAPNH4Cl and CB-SAPKNO3) by the one-pot method. The chemical structure, thermal stability, and morphology of the polymers were investigated by Fourier-transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), and scanning electron microscope (SEM). Meanwhile, the water retention, water absorption, and salt resistance were compared with the purchased polymers. The results showed that the nutriment was successfully encapsulated inside the polymer, and CB-SAPNH4Cl and CB-SAPKNO3 at 1% nutrient concentration showed excellent water retention properties, salt resistance, and water absorption performance of 1546 and 1131 g/g (distilled water), 306 and 277 g/g (tap water), and 116 and 91 g/g (0.9% NaCl solution). Therefore, they are highly promising materials for the application.

Facile Polymerization Strategy for the Construction of Eu3+-Based Fluorescent Materials with the Capability of Distinguishing D2O from H2O.

Aggregation-induced emission (AIE) and antenna effect (AE) are two important luminescence behaviors. Connecting them into polymers is a promising but challenging work, which can supply opportunities for luminescence materials with extensive applications. In this work, AIE-active Eu3+-coordinated polymers (Poly-Eu-1, -2, -3, and -4) have been synthesized, and the efficient AE was verified. This finding presents a facile approach to obtain the Ln3+-based solid luminescence materials due to the synergistic effect from AIE and AE. Also, benefiting from the film-processing ability and water solubility, Poly-Eu-1, -2, -3, and -4 could be employed with different application purposes. In the solution phase, they can be used as sensitive optical probes to detect trace amounts of H2O and D2O, and the limit of detection (LOD) of Poly-Eu-2 toward D2O in H2O is determined to be 7.8 ppm. This discovery is a novel strategy for the construction of D2O optical sensors with a totally intervention-free style.

Two aggregation-induced emission (AIE)-active reaction-type probes: for real-time detecting and imaging of superoxide anions.

Fluorescent probes are powerful tools for investigating reactive oxygen species (ROS) in living organisms. The overproduced "primary" ROS of superoxide anions (O2˙-) cause a chain of oxidative damage. In order to monitor O2˙- level fluctuations in living cells, we synthesized two reaction-type probes of TPA-DHP-1,2,3 and TPA-PPA-1,2,3, which were composed of an electron-rich triphenylamine (TPA) and the very active functional groups of dihydropyridine (DHP) and pyridinium (PPA). Intriguingly, DHP and PPA were able to carry out easy proton abstractions and nucleophilic reactions in the presence of O2˙-, resulting in the corresponding products with sharp wavelength shifts, and elevated fluorescence intensities. Therefore, undesirable background fluorescence interference can be reduced during the monitoring and imaging process. Meanwhile, the developed dual-channel monitoring strategy not only provides observations of the O2˙- level fluctuations, but could also be employed to image the dynamic accumulation process of probes in the different cell organelles. Therefore, the design could provide a simple, accurate and universal platform for biological applications in future research work.

One-step spray-coating process for the fabrication of colorful superhydrophobic coatings with excellent corrosion resistance.

A simple method was used to generate colorful hydrophobic stearate particles via chemical reactions between inorganic salts and sodium stearate. Colored self-cleaning superhydrophobic coatings were prepared through a facile one-step spray-coating process by spraying the stearate particle suspensions onto stainless steel substrates. Furthermore, the colorful superhydrophobic coating maintains excellent chemical stability under both harsh acidic and alkaline circumstances. After being immersed in a 3.5 wt % NaCl aqueous solution for 1 month, the as-prepared coatings remained superhydrophobic; however, they lost their self-cleaning property with a sliding angle of about 46 ± 3°. The corrosion behavior of the superhydrophobic coatings on the Al substrate was characterized by the polarization curve and electrochemical impedance spectroscopy (EIS). The electrochemical corrosion test results indicated that the superhydrophobic coatings possessed excellent corrosion resistance, which could supply efficient and long-term preservation for the bare Al substrate.

Methyl Cinnamate-Derived Fluorescent Rigid Organogels Based on Cooperative π-π Stacking and C═O···π Interactions Instead of H-Bonding and Alkyl Chains.

A new class of rigid low-molecular-mass organic gelators (LMOGs) was synthesized by McMurry and Heck reactions, and their gels and photophysical properties were investigated. The LMOGs lacked alkyl chain and H-bonding units and produced good gelation ability in selected mixed organic solvents facilitated by cooperative π-π stacking and C═O···π interactions. Sensitive gel-sol transformation by molecular aggregation and disaggregation was easily achieved upon heating and cooling. H-H 2D NOESY and X-ray diffraction (XRD) patterns showed the π-π stacking and C═O···π interactions between tiny methyl acrylate groups as "tails". Importantly, this soft interaction model offers a useful tool for the future design and construction of supramolecular structures. At present, the LMOGs reported herein offer a sensitive gel-formation ability and aggregation-induced emission (AIE) property and thus have promising application potentials as functional soft matter in amorphous materials, photoelectric materials, and so on.

One-step fabrication of robust fabrics with both-faced superhydrophobicity for the separation and capture of oil from water.

In this work, a facile and inexpensive one-step sonochemistry irradiation method was developed for the fabrication of SiO2 nanoparticles functionalized with octadecyltrimethoxysilane and their in situ incorporation into cotton fabrics. The double sides of as-prepared fabrics show both superhydrophobic and superoleophilic properties simultaneously with a high water contact angle of 159 ± 1° and an oil contact angle of 0°. Thus, it can be used to separate and capture a series of oils from water, like kerosene, toluene and chloroform, etc. In addition, the as-prepared fabrics still have superhydrophobicity with a water contact angle of above 150° after 40 separation cycles with the separation efficiency for the kerosene-water mixture always above 94.6%. More importantly, the as-prepared fabrics showed robust and stable superhydrophobic properties towards hot water, many corrosive solutions (acidic, basic, salt liquids) and mechanical abrasion. Therefore, this reported fabric has the advantages of scalable fabrication, high separation efficiency, stable recyclability, and excellent durability, exhibiting the strong potential for industrial production.

N,N'-[(2E,3E)-Butane-2,3-diylidene]bis[4-fluoro-2-(1-phenyl-eth-yl)aniline].

The title mol-ecule, C32H30F2N2, a product of the condensation reaction of butane-2,3-dione and 4-fluoro-2-(1-phenyl-eth-yl)aniline, is located about an inversion centre. In the asymmetric unit, the dihedral angle between the planes of the benzene and phenyl rings is 84.27 (5)°. Neither hydrogen bonding nor aromatic stacking is observed in the crystal structure.

Construction of Bimetallic-Anchored Two-Dimensional Nanosheets on COF for Rechargeable Zinc-Air Batteries.

The preparation of carbon materials by doping bimetallic oxides into triazine frameworks (COFs) is a promising electrocatalyst with the potential to replace precious metals in energy storage systems. In this experiment, a covalent triazine framework (COF) was synthesized by 1,4-dicyanobenzene (DCB) and zinc chloride, in which the COF and transition metals were used as carbon, nitrogen, cobalt, and iron sources. According to the properties of this COF, the destruction of the catalyst during pyrolysis can be prevented. The enhanced catalytic performance of the catalysts can be seen by testing all of the samples of catalysts in an alkaline medium. The high half-wave potential (E1/2) of 0.86 V is comparable to Pt/C and also shows excellent durability by testing. Zinc-air batteries were assembled using the prepared catalysts, and the batteries were tested for specific capacity (548 mAh g-1) and power density (189 mW cm-2). This work provides a new direction for COF-derived catalysts for carbon materials.

Bimetallic iron complex constructed clusters and single atoms neighboring structure to enhance oxygen reduction reaction performance.

Electrocatalysts are useful in lowering the energy barrier in oxygen reduction reaction (ORR). In this study, a catalyst with neighboring Fe single-atom and cluster is created by adsorbing a bimetallic Fe complex onto N-doped carbon and then pyrolyzing it. The resulting catalyst has good performance and a half-wave potential of 0.89 V. When used in Zn-air batteries, the voltage drops by only 8.13 % after 145 h of cycling. Theoretical studies show that electrons transfer from neighboring clusters to single atoms and the catalyst has a lower d-band center. These reduce intermediate desorption energy, hence improving ORR performance. This work demonstrates the capacity to adjust the catalytic properties through the interaction of diverse metal structures, which helps to design more efficient catalysts.

Tailoring the covalent organic frameworks based polymer materials for solar-driven atmospheric water harvesting.

Atmospheric water harvesting through reticular materials is an innovation that has the potential to change the world. Here, this study offers a technique for creating a solar-powered hygroscopic polymer material for atmospheric water harvesting with the reticular materials. The results show that the porous hygroscopic polymer materials can achieve high performance with high vapor capture (up to ac. 28.8-49.7 mg/g at 28-38 %RH and 25  â„ƒ), rapid photothermal conversion efficiency (up to 32.2 â„ƒ within 15 min under 1000 W/m-2 light at 25 â„ƒ), a low desorption temperature (lower than 40 â„ƒ), and an effective water release rate. Besides, the material also has excellent water-retention properties, which can effectively store desorbed liquid water in polymer networks for use by vegetation during water demand periods. The strategy opens new avenues for atmospheric water-harvesting materials, which will hopefully solve the global crisis of freshwater shortages.

Synthesis of soybean soluble polysaccharide-based eco-friendly emulsions for soil erosion prevention and control.

This paper introduces the synthesis of an environmentally friendly emulsion that can be used as a soil anti-water erosion material. SSPS-g-P(BA-co-MMA-co-AA) emulsions were prepared using free radical copolymerization with soybean soluble polysaccharide (SSPS), acrylic acid (AA), butyl acrylate (BA), and methyl methacrylate (MMA). The structure, thermal stability, and morphology were characterized using FT-IR,TG,SEM, and particle diameter analysis. The resistance to water erosion, compressive strength and water retention of emulsion-treated loess/laterite was studied and germination tests were conducted. The results demonstrated that the duration of washout resistance of loess with 0.50 wt% emulsion exceeded 99 h, and the water erosion rate was 56.0 % after 72 h, while the water erosion rate of pure loess is 100.0 % after 4 min;the duration of washout resistance of laterite with 0.50 wt% emulsion exceeded 2 h, which was 8 times longer than pure laterite;The compressive strengths of 0.5 wt% emulsion-treated loess/laterite were 3.5 Mpa and 5.8 MPa, respectively, which were 7 and 9 times higher than that of pure soil. The plant seeds germinated normally half a month after planting. These findings suggest that emulsions can be used to control soil erosion without affecting the germination of plant seeds.

Fine nanostructure design of metal chalcogenide conversion-based cathode materials for rechargeable magnesium batteries.

Magnesium-ion batteries (MIBs) a strong candidate to set off the second-generation energy storage boom due to their double charge transfer and dendrite-free advantages. However, the strong coulombic force and the huge diffusion energy barrier between Mg2+ and the electrode material have led to need for a cathode material that can enable the rapid and reversible de-insertion of Mg2+. So far, researchers have found that the sulfur-converted cathode materials have a greater application prospect due to the advantages of low price and high specific capacity, etc. Based on these advantages, it is possible to achieve the goal of increasing the magnesium storage capacity and cycling stability by reasonable modification of crystal or morphology. In this review, we focus on the application of a variety of sulfur-converted cathode materials in MIBs in recent years from the perspective of microstructural design, and provide an outlook on current challenges and future development.

Preparation and properties of a metal-organic frameworks polymer material based on Sa-son seed gum capable of simultaneously absorbing liquid water and water vapor.

Atmospheric water harvesting (AWH) technology has attracted significant attention as an effective strategy to tackle the global shortage of freshwater resources. Work has focused on the use of hydrogel-based composite adsorbents in water harvesting and water conservation. The approaches adopted to make use of hygroscopic inorganic salts which subject to a "salting out" effect. In this study, we report the first use of modified UIO-66-NH2 as a functional steric cross-linker and Sa-son seed gum was used as polymeric substrate to construct super hygroscopic hydrogels by free radical copolymerization. The maximum water uptake on SMAGs (572 cm3·g-1) outperforms pure UIO-66-NH2 (317 cm3·g-1). Simultaneously, our first attempt to use it for anti-evaporation applications in an arid environment (Lanzhou, China) simulating sandy areas. The evaporation rate of the anti-evaporation material treated with 0.20 % super moisture-absorbent gels (SMAGs) decreased by 6.1 % over 64 h period under natural condition in Lanzhou, China. The prepared material can not only absorb liquid water but also water vapor, which can provide a new way for water collection and conservation technology. The design strategy of this material has wide applications ranging from atmospheric water harvesting materials to anti-evaporation technology.

Activating graphite with defects and oxygenic functional groups to boost sodium-ion storage.

Sodium-ion batteries have been one of the most promising alternatives for lithium-ion batteries (LIBs) for large-scale energy storage systems due to cost-efficiency and rich resources of sodium. However, graphite, a commercial anode material of LIBs, shows a very low reversible capacity for sodium-ion storage because of the weak binding between sodium and graphite. Herein, an activated graphite (AG) material with abundant defects including edges and vacancies with oxygenic functional groups is well-designed and fabricated by a facile and eco-friendly ball-milling method. The structural evolutions during the ball-milling process and their effects on electrochemical sodium-ion storage performance are investigated. A stable reversible capacity of 139.1 mA h g-1 can be achieved at 1.0 A g-1 even after 4500 cycles for the AG-50 electrode with the 50-hour ball-milling treatment, amounting to a very low decay ratio of 0.0034% per cycle. Based on physical characterizations and density functional theory calculations, the greatly improved specific capacity and cycling stability of the AG anode for sodium-ion storage can be attributed to the enlarged interlayer space, increased specific surface area, and introduced defects caused by ball-milling treatment, which provide vast active sites for reversible sodium-ion storage based on a adsorption/desorption mechanism, thus leading to great improvement in the specific capacity of the AG electrode. These results can provide a meaningful reference for the application of modified graphite for high-performance sodium storage.