Most ReadCovalent organic frameworks (COFs) are crystalline porous polymeric materials composed of organic monomers connected by strong covalent bonds and offer high stability, good crystallinity, a large specific surface area, and controllable structures. COFs are widely used in the fields of adsorption and separation, catalysis, photovoltaics, and drug-delivery. The structural regulation and performance optimization of COFs can be realized through the modification of ligands and the selection of linkage methods. In which, the types of linkage are closely related to the stability and performance of COFs. In this review, nitrogen-containing linkage-bonds (NCLBs) in COFs are divided into N-containing double bonds, N-containing conjugated rings and N-containing unconjugated rings. The association between structure and performance of COFs is elaborated and the synthesis methods of COFs are systematically summarized. Moreover, the structural design, theoretical prediction and machinable application of COFs are prospected
Achieving high energy densities for all-solid-state lithium batteries is restricted by the poor high voltage stability of solid electrolytes. Herein, F-doping strategy is successfully employed on Li3InCl6 to obtain enhanced voltage stability and electrode compatability towards bare LiNi0.7Mn0.2Co0.1O2 at high voltages. The optimized Li3InCl5.5F0.5 electrolyte exhibits a decreased conductivity of 1.00 mS/cm, a wider voltage window, and improved electrochemical performance in solid-state batteries when cycled at upper cut-off voltages of 4.5 and 4.8 V (vs. Li+/Li0). The generation of more stable LiInF4 phase in the cathode mixture of Li3InCl5.5F0.5-based battery ensures superior electrochemical performances compared to the Li3InCl6-based battery. The former battery exhibits a higher discharge capacity of 218.9 mAh/g and coulombic efficiency of 86.7% for the first cycle, and retains 80.0% of its original value after 100 cycles when cycled in the range of 3.0–4.5 V (vs. Li+/Li0). In contrast, the Li3InCl6-based battery exhibits lower capacities and faster degradation under the same conditions due to the formation of InCl3 phase with poor electrochemical stability. This work facilitates the advancement of high energy density solid-state battery technologies by utilizing high-voltage cathodes.
Conventional hydrometallurgy recycling process for treating wasted lithium-ion batteries (LIBs) typically results in the consumption of large amounts of corrosive leachates. Recent research on reusable leachate is expected to significantly improve the economic and environmental benefits, but is usually limited to specific and unique chemical reactions which could only apply to one type of metal elements. Herein, we report the co-extraction of multiple metal elements can be extracted without adding precipitates by mixed crystal co-precipitation, which enables the reusability of the leachate. We show that an oxalic acid (OA): choline chloride (ChCl): ethylene glycol (EG) type DES leachate system can leach transition metals from wasted LiNixCoyMn1-x-yO2 (NCM) cathode materials with satisfactory efficiency (The time required for complete leaching at 120 ℃ is 1.5 h). The transition metals were then efficiently extracted (with a recovery efficiency of over 96% for all elements) by directly adding water without precipitants. Noteworthy, the leachate can be efficiently recovered by directly evaporating the added water. The successful realization of reusability of leachate for the synergistic extraction of multiple elements relies on the regulation of the mixed crystal co-precipitation coefficient, which is realized by rationally design the reaction condition (composition of leachate, temperature and time) and induces the extraction of originally soluble manganese element. Our strategy is expected to be generally applicable and highly competent for industrial applications.
Urea-assisted water electrolysis offers a promising route to reduce energy consumption for hydrogen production and meanwhile treat urea-rich wastewater. Herein, we devised a shear force-involved polyoxometalate-organic supramolecular self-assembly strategy to fabricate 3D hierarchical porous nanoribbon assembly Mn-VN cardoons. A bimetallic polyoxovanadate (POV) with the inherent structural feature of Mn surrounded by [VO6] octahedrons was introduced to trigger precise Mn incorporation in VN lattice, thereby achieving simultaneous morphology engineering and electronic structure modulation. The lattice contraction of VN caused by Mn incorporation drives electron redistribution. The unique hierarchical architecture with modulated electronic structure that provides more exposed active sites, facilitates mass and charge transfer, and optimizes the associated adsorption behavior. Mn-VN exhibits excellent activity with low overpotentials of 86 mV and 1.346 V at 10 mA/cm2 for hydrogen evolution reaction (HER) and urea oxidation reaction (UOR), respectively. Accordingly, in the two-electrode urea-assisted water electrolyzer utilizing Mn-VN as a bifunctional catalyst, hydrogen production can occur at low voltage (1.456 V@10 mA/cm2), which has the advantages of energy saving and competitive durability over traditional water electrolysis. This work provides a simple and mild route to construct nanostructures and modulate electronic structure for designing high-efficiency electrocatalysts.
Bacterial infection, insufficient angiogenesis, and oxidative damage are generally regarded as key issues that impede wound healing, making it necessary to prepare new biomaterials to simultaneously address these problems. In this work, monodispersed CeO2@CuS nanocomposites (NCs) were successfully prepared with tannin (TA) as the reductant and linker. Due to abundant oxygen vacancies in CeO2 and the polyphenolic structure of TA, the TA-CeO2@CuS NCs exhibited a remarkable antioxidant ability to scavenge excessive reactive oxygen species (ROS), which would likely induce serious inflammation. In addition, the TA-CeO2@CuS NCs demonstrated excellent antibacterial capability with near-infrared ray (NIR) irradiation, and the released copper ions could promote the regeneration of blood vessels. These synergistic effects indicated that the synthesized TA-CeO2@CuS NCs could serve as a promising biomaterial for multimodal wound therapy.
Excessive Fe3+ ion concentrations in wastewater pose a long-standing threat to human health. Achieving low-cost, high-efficiency quantification of Fe3+ ion concentration in unknown solutions can guide environmental management decisions and optimize water treatment processes. In this study, by leveraging the rapid, real-time detection capabilities of nanopores and the specific chemical binding affinity of tannic acid to Fe3+, a linear relationship between the ion current and Fe3+ ion concentration was established. Utilizing this linear relationship, quantification of Fe3+ ion concentration in unknown solutions was achieved. Furthermore, ethylenediaminetetraacetic acid disodium salt was employed to displace Fe3+ from the nanopores, allowing them to be restored to their initial conditions and reused for Fe3+ ion quantification. The reusable bioinspired nanopores remain functional over 330 days of storage. This recycling capability and the long-term stability of the nanopores contribute to a significant reduction in costs. This study provides a strategy for the quantification of unknown Fe3+ concentration using nanopores, with potential applications in environmental assessment, health monitoring, and so forth.
Sulfide solid electrolytes with an ultrahigh ionic conductivity are considered to be extremely promising alternatives to liquid electrolytes for next-generation lithium batteries. However, it is difficult to obtain a thin solid electrolyte layer with good mechanical properties due to the weak binding ability between their powder particles, which seriously limits the actual energy density of sulfide all-solid-state lithium batteries (ASSLBs). Fortunately, the preparation of sulfide-polymer composite solid electrolyte (SPCSE) membranes by introducing polymer effectively reduces the thickness of solid electrolytes and guarantees high mechanical properties. In this review, recent progress of SPCSE membranes for ASSLBs is summarized. The classification of components in SPCSE membranes is first introduced briefly. Then, the preparation methods of SPCSE membranes are categorized according to process characteristics, in which the challenges of different methods and their corresponding solutions are carefully reviewed. The energy densities of the full battery composed of SPCSE membranes are further given whenever available to help understanding the device-level performance. Finally, we discuss the potential challenges and research opportunities for SPCSE membranes to guide the future development of high-performance sulfide ASSLBs.
Aqueous zinc ion batteries (AZIBs) are promising energy storage devices. However, the formation of dendrites, hydrogen evolution, and corrosion reaction seriously affect their electrochemical performance. Herein, the synergistic effect of ion-migration regulation and interfacial engineering has been confirmed as the potential strategy by kaolin functionalized glass fiber separator (KL-GF) to alleviate these problems. The rapid and orderly Zn2+ migration was achieved to improve the transfer kinetics and induced uniform zinc deposition by more zinc-philic sites of KL-GF. Based on the interfacial engineering, the side reactions were effectively mitigated and crystal planes were regulated through KL-GF. The hydrophilicity of KL alleviated the corrosion and hydrogen evolution. Importantly, a preferential orientation of Zn (002) crystal plane by KL-GF was induced to further realize dendrite-free deposition by density functional theory (DFT) and X-ray diffraction (XRD) characterization. Hence, the Zn|KL-GF|MnO2 cell maintained a high discharge capacity of 96.8 mAh/g at 2 A/g after 1000 cycles. This work can provide guidance enabling high-performance zinc anode for AZIBs.
This article reviews the latest research advances of tetrahedral framework nucleic acid (tFNA)-based systems in their fabrication, modification, and the potential applications in biomedicine. TFNA arises from the synthesis of four single-stranded DNA chains. Each chain contains brief sequences that complement those found in the other three, culminating in the creation of a pyramid-shaped nanostructure of approximately 10 nanometers in size. The first generation of tFNA demonstrates inherent compatibility with biological systems and the ability to permeate cell membrane effectively. These attributes translate into remarkable capabilities for regulating various cellular biological processes, fostering tissue regeneration, and modulating immune responses. The subsequent evolution of tFNA introduces enhanced adaptability and a relatively higher degree of biological stability. This advancement encompasses structural modifications, such as the addition of functional domains at the vertices or side arms, integration of low molecular weight pharmaceuticals, and the implementation of diverse strategies aimed at reversing multi-drug resistance in tumor cells or microorganisms. These augmentations empower tFNA-based systems to be utilized in different scenarios, thus broadening their potential applications in various biomedical fields.
In view of widespread existence and toxicity, removal and detection of bisphenols is imperative to assess environmental risks and reduce harm to human health. Although many techniques have been reported, constructing fast and sensitive method remains a challenge. Herein, porous poly(divinylbenzene) polymer was synthesized in-situ on the Fe3O4 particles by means of distillation-precipitation polymerization and functioned as sorbents to extract bisphenols. Employing Fe3O4@poly(divinylbenzene) as sorbent, a magnetic solid-phase extraction coupling with liquid chromatography was developed to detect trace bisphenols in water. This method presented low detection limits (0.01–0.03 ng/mL), high enrichment ability (enrichment factor, 327–343), and good reproducibility. Moreover, the method showed satisfactory recoveries in the detection of lake water (80.60%-116.2%) and egg sample (75.17%-120.0%). Impressively, Fe3O4@PDVB has excellent adsorption capacity, which can realize rapid kinetic adsorption of bisphenols with equilibrium time all less than 10 s. The maximum adsorption capacities reached 1074.8, 1049.7, 1299.1 and 1329.5 mg/g for bisphenol F, bisphenol A, bisphenol B and bisphenol AF with Langmuir isotherm model. The adsorption mechanism of Fe3O4@PDVB to bisphenols was investigated and demonstrated that hydrophobic interactions played a key role, together with assistance of stacking interactions and hydrogen interactions. Overall, this work provides a promising sorbent material with ultra-fast and large adsorption capacities for extraction of bisphenols from water.