Latest ArticlesThis work investigates the impact of vertex modification on the host-guest chemistry of a hexahedral Zn(Ⅱ)-based metal-organic cage (MOC) 1 containing fluorinated components. Structural characterization via single-crystal X-ray diffraction (SCXRD), 1H NMR, and electrospray ionization time-of-flight mass spectra (ESI-TOF MS) confirmed the low-symmetry hexahedral architectures of 1·NTf2 and 1·OTf, with fluorine atoms positioned at cage windows. 1H/19F NMR spectra of 1·NTf2 and 1·OTf showed slow-exchange binding behavior with external anions. 1·NTf2 had a single set of peaks in the imine signal area, while 1·OTf had two distinct groups of signals. Combined with competitive anion titration results, it can be inferred that NTf2- has a stronger binding affinity with the cage structure. Host-guest studies with pyrene (Py) and its hydrogenated analogs revealed complete displacement of OTf- but not NTf2-, highlighting the superior binding strength of NTf2-. Comparative isothermal titration calorimetry (ITC) data showed reduced association constants for 1·OTf with pyrene (Py) and its analogs 4,5,9,10-tetrahydropyrene (4H-Py) and hexadecahydropyrene (16H-Py) compared to 2·OTf, attributed to electron-withdrawing fluorine substituents altering charge distribution, which was confirmed by the electrostatic potential analysis of the cage skeleton. These findings underscore how vertex functionalization modulates anion selectivity and guest-binding thermodynamics in MOCs, offering insights for designing tailored supramolecular hosts.
Poly(ethylene oxide) (PEO) electrolytes present a promising option for next-generation solid-state high-energy-density batteries. However, the poor ionic conductivity and inefficiency transference number pose significant barriers to its broader application. Herein, an in-built synthesis of poly(ethylene oxide) with zwitterionic poly(ionic liquid) composite electrolyte (PEO/Zwit PIL) is employed by a thio-lene click reaction. The introduction of Zwit PIL can help the composite electrolyte fully dissociation lithium salts and optimize the solvation structure. Molecular dynamics simulations elucidate fast Li+ transport through a structural diffusion mechanism upon the addition of Zwit PIL to the composite electrolyte, simultaneously facilitating a high ionic conductivity and transference number. The composite electrolyte also demonstrates a high self-adhesive to construct a robust and tough electrode-electrolyte interface. The assembled full cell (LiFePO4PEO-Zwit PILLi) exhibits a discharge capacity of 153 mAh/g at 60 ℃ and highly stable cyclic performance up to 200 cycles at 0.2 C. The employment of Zwit PIL within PEO for novel solid-state electrolytes furnishes an alternative approach to the design of high-performance, next-generation, sustainable batteries.
The conversion of carbon dioxide (CO2) into valuable fuels or chemicals through photothermal catalysis is an efficient way to alleviate the global energy crisis and climate change. Regulating active sites and modifying photothermal conversion characteristics are conducive to photothermal catalytic reactions. In this study, the defect-rich tantalum oxide on tantalum foil decorated with Ru nanoparticles (Ru/Ta2O5-x/Ta) was synthesized using pulsed laser under thermal ablation effects. The presence of oxygen defects enhanced the photothermal conversion efficiency. Meanwhile, the interface between Ru and Ta2O5-x facilitated the adsorption of CO2, and Ru nanoparticles served as efficient active sites for the hydrogenation of CO2 to methane (CH4). The Ru/Ta2O5-x/Ta catalyst exhibited excellent photothermal conversion efficiency (reaching 343.4 ℃ at 1.76 W/cm2) and excellent catalytic activity with a CH4 yield of 50.6 mol g(Ru)-1 h-1 (CH4 selectivity of 98%). The experimental and theoretical results demonstrated that the catalytic sites of Ru/Ta2O5-x/Ta in combination with light irradiation promoted CO2 activation, intermediate formation and CO* transformation, thereby accelerating the production of CH4. Moreover, the application of the pulsed laser was extended to construct the photothermal catalyst with high photothermal temperature and efficient catalytic sites.
In this work, the aggregation-enhanced antenna effect of chiral mononuclear Eu(Ⅲ) complexes containing dynamic modules in aqueous solution was used for the first time to significantly improve the optical imaging performance of various types of cells and zebrafish. Specifically, the chiral mononuclear Eu(Ⅲ) complexes (R/S-1 and R/S-2) containing molecular rotors or vibration unit modules have almost negligible emission in the molecule state, but after aggregation in aqueous solution, they form nanoparticles with a sharp increase in emission peaks. It is worth noting that the above photophysical properties lead to R/S-1 and R/S-2 having high-resolution cell imaging effects on various cells, and localizing in lysosomal organelles. In addition, R/S-1 and R/S-2 also show high-resolution optical imaging effects on zebrafish. This work not only opens a door to expand the bioimaging performance of lanthanide complex emitters but also opens a new perspective for the construction of new dynamic lanthanide complexes with bright emissions.
Aqueous zinc-ion batteries are promising candidates for large-scale energy storage, but their practical application is hindered by the issues of Zn dendrite growth and side reactions. To address these challenges, a mesoporous carbon anchored with zincophilic nitrogen and oxygen sites (NOPC) is prepared by pyrolyzing NH4Cl-incorporated ZIF-8 and constructed as a protective layer on Zn anode. In the NOPC layer, the zincophilic nitrogen and oxygen sites facilitate uniform Zn2+ nucleation, while the abundant mesopores homogenize Zn2+ flux, effectively enabling dendrite-free deposition. Moreover, the NOPC layer suppresses interfacial side reactions by isolating the Zn surface from active H2O. Remarkably, the Zn anode protected by the NOPC layer achieves an ultralong cycle life exceeding 6000 h at 1 mA/cm2 and 1 mAh/cm2, and maintains a high Coulombic efficiency of 99.8% for 4600 cycles, indicating superior stability and reversibility. When paired with NaV3O8·1·5H2O cathode, the full cell displays a capacity retention of 85.1% after 3000 cycles at 5 A/g. This study demonstrates that the engineering of zincophilic sites and meso-porosity in carbon-based protective layers represents an effective strategy for enhancing the performance of aqueous zinc-ion batteries.
Tin-oxo clusters (TOCs) have attracted considerable attention owing to their various structures and wide potential applications. However, there is still a lack of effective methods to assemble high-nuclearity TOCs. Moreover, the periphery of reported TOCs is rarely N-rich ligands, limiting the comprehensive investigation of the structure-property relationship. In this work, we used the strategy of pyrazole-thermal-assisted organotin aggregation to construct a series of the largest N-rich Sn18 clusters with S4 axial symmetry. These Sn18 clusters have inorganic electron-withdrawing halogen atoms and organic electron-rich pyrazole derivatives, differing from the reported high-nuclearity TOCs only with carboxylate ligands. Owing to the high symmetry and multiple electron-withdrawing/-donating ligands, the Sn18 clusters served as the platform to investigate the relationship between structure and third-order nonlinear optical (NLO) property by Z-scan measurement. Different from the single organic ligand in the previous study, the multiple kinds of ligands in the Sn18 clusters have an important effect on the NLO property. Enhancing the push-pull electronic effect and introducing C–Cl···π interactions between different ligands can promote the NLO properties. Thus, CTGU-SnC-16 exhibits the best broadband NLO properties at 532 and 1064 nm, differing from the reported metal-oxo clusters only at 532 nm. This work not only affords an effective synthetic strategy for constructing high-nuclearity TOCs but also deepens the understanding of the structure-property relationship of clusters.
Solid-state zinc-air batteries (SZABs) and solid-state zinc-ion batteries (SZIBs) exhibit significant potential for applications in flexible electronic devices, due to zinc's abundance, enhanced safety, high theoretical energy density, and eco-friendliness. Recently, various SZABs and SZIBs utilizing advanced solid-state electrolytes (SEs) and cathodes have been developed. However, the conductivity of the cathode, as well as the construction of active sites and ion transport pathways during charging and discharging, require further investigation. Additionally, the electrolyte plays a critical role in solid-state batteries, directly impacting the output performance of the battery, cycling stability, and operational lifespan. Thus, the development of high-quality electrolytes alongside efficient and stable electrodes is essential for the large-scale application of solid-state batteries. This review examines the working principles and assembly processes of SZABs and SZIBs and summarizes the superior properties of various cathodes and electrolytes, thereby offering new perspectives for advancing high-performance SZABs and SZIBs.
The instability of the Zn metal anode in aqueous zinc-ion batteries is the main culprit limiting promotion and practicability. Solid-liquid hybrid electrolytes, as an emerging system containing electrochemically inert fillers, have been proposed and shown significant progress in recent years. The electrolyte regulation for suppressing side reactions mainly depends on the state of bound water molecules, so exploring the influence of intrinsic properties of fillers on electrolyte structure is of great significance. This work compared the effects of kaolin and its derived mullite on the state of bound water molecules and electrochemical behaviors in hybrid electrolytes. Relying solely on the high specific surface area of mullite is not sufficient to provide enough ion diffusion paths and limit water molecule activity, resulting in severe polarization and side reactions. The layered structure of kaolin can accommodate a large number of water molecules, which constructs hydrogen bonding networks for H+ transport as the charge carrier with lower energy barrier. Hence, the kaolin-based electrolytes can inherit both low polarization of conventional liquid electrolytes and the durability to side reactions of hybrid electrolytes simultaneously. As a result, the aqueous Zn-MnO2 battery with kaolin-based electrolyte can provide high specific capacity of ~300 mAh/g at 100 mA/g, and maintain at least 164 and 85.2 mAh/g at 300 and 500 mA/g for > 500 cycles.
Piezoelectric materials can efficiently convert widely available mechanical energy to usable electrical energy or chemical energy, which represent a type of promising sustainable materials and is worth being extensively explored. Covalent organic frameworks (COFs), with their finely tunable structures and properties, have emerged as exciting materials for piezoelectric applications. This review aims to discuss the strategy for enhanced piezoelectric properties of COFs and the applications of COFs in the piezoelectric field, including piezocatalysis and piezoelectric nanogenerators. Then, the effect of pressure on the structure of COFs is introduced, which may provide new perspectives for the design of COFs in piezoelectricity. The review concludes that COFs offer a versatile platform for developing advanced piezoelectric materials, with potential in wide range of applications. The insights provided in this review are hoped to guide the direction of future research in the field of COF-based piezoelectric materials.
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