Latest ArticlesLithium-sulfur batteries (LSBs) are among the most promising series of next-generation high density energy storage systems. However, the problem of "shuttle effect" caused by dissolution and migration of polysulfide intermediates has severely inhibited their practical applications. Herein, TiO2-carbon nanocomposites embedded hierarchical porous carbon (T-hPC) interlayers are fabricated via Ti3C2 MXene assisted phase separation and annealing method. The T-hPC processes micro- to macro-scale multi-pores along with highly adsorptive and catalytic carbon supported TiO2 nanoparticles, which significantly enhances the polysulfides immobilization and improves the redox reaction kinetics when applied as lithium-sulfur battery interlayers. An initial discharge specific capacity of 1551.1 mAh/g and a stable capacity of 893.8 mAh/g after 200 cycles at 0.5 C are obtained, corresponding to a capacity decay rate of only 0.04% per cycle. The investigations in this paper can provide a simple and effective strategy to enhance the electrochemical properties for lithium-sulfur batteries.
Bimetallic catalysts usually exhibit better performance than monometallic catalysts due to synergistic effect. However, there is a lack of exploring the synergistic effect on catalytic performance caused by the introduction of inactive metal ion. In this work, we design a molecular model system that can precisely regulate the metal site number and catalytic property. When these molecular metal compounds are used as homogeneous catalysts for photocatalytic CO2 reduction, the dinuclear heterometallic CuNi-L2 shows the highest CO2-to-CO conversion, which is 2.1 and 3.0 times higher than that of dinuclear homometallic Ni2-L2 and mononuclear Ni-L1. Density functional theory calculations demonstrate that, in CuNi-L2, the introduction of inactive CuII is easier to promote the photo-generated electrons transferring to the coupled active NiII site to achieve the highest activity. In addition, this work also provides insights to design and construct more efficient bimetallic catalysts in future.
Fe-N/C is a promising oxygen reduction reaction (ORR) catalyst to substitute the current widely used precious metal platinum. Cost-effectively fabricating the Fe-N/C material with high catalytic activity and getting in-depth insight into the responsible catalytic site are of great significance. In this work, we proposed to use biomass, tea leaves waste, as the precursor to prepare ORR catalyst. By adding 5% FeCl3 (wt%) into tea precursor, the pyrolysis product (i.e., 5%Fe-N/C) exhibited an excellent four-electron ORR activity, whose onset potential was only 10 mV lower than that of commercial Pt/C. The limiting current density of 5%Fe-N/C (5.75 mA/cm2) was even higher than Pt/C (5.44 mA/cm2). Compared with other biomass or metal organic frameworks derived catalysts, 5%Fe-N/C showed similar ORR activity. Also, both the methanol tolerance and material stability performances of as-prepared 5%Fe-N/C catalyst were superior to that of Pt/C. X-ray adsorption fine structure characterization revealed that the FeN4O2 might be the possible catalytic site. An appropriate amount of iron chloride addition not only facilitated catalytic site formation, but also enhanced material conductivity and reaction kinetics. The results of this work may be useful for the Fe based transition metal ORR catalyst design and application.
Separator is supposed to own outstanding thermal stability, superior wettability and electrolyte uptake, which is essential for developing high-rate and safe lithium metal batteries (LMBs). However, commercial polyolefin separators possess poor wettability and limited electrolyte uptake. For addressing this issue, we put forward a composite separator to implement above functions by doping layered-silicate (talcum) into polyvinylidene fluoride (PVDF). With significant improvement of electrolyte absorption benefiting from the strong adsorption energy values (-1.64 ~ -1.70 eV) between talcum and the electrolyte in lithium metal batteries, PVDF/Talcum (PVDF/TM) composite separator owns a small contact angle and superior electrolyte uptake. PVDF/TM composite separator with 10 wt% talcum (T-10) owns a tiny contact angle of 8°, while those of polypropylene (PP) and PVDF are 48° and 20° with commercial electrolyte. Moreover, the addition of thermotolerant talcum endows the T-10 composite separator with great thermostability, whose thermal shrinkage is only 5.39% at 150 ℃ for 0.5 h. The cell with LiFeO4 cathode and the T-10 composite separator reaches 91.7 mAh/g in discharge capacity at 4.8 mA/cm2 (10 C), far superior to that with pure PVDF separator (56.3 mAh/g) and PP (51.4 mAh/g).
There is an urgent demand for tuning the selectivity and activity of the photocatalysts to remove co-existent pollutants simultaneously. Herein, we introduced the surficial activity sites into the bismuth oxybromide (BiOBr), including the Bi/Bi-O defects and hetero Cu atoms, and then the higher photocatalytic activity and selectivity of BiOBr were realized for degradation phenol and ciprofloxacin (CIP). It can be found that the Bi/Bi-O defects played more important role in enhancing the photocatalytic activity for degradation of phenol, while the Cu atoms significantly improved the photocatalytic activity for removing CIP. Moreover, the heterogeneous Cu atoms as the activity sites excited the reaction between phenol and CIP even under dark condition and were beneficial for synchronously removing phenol and CIP. This work provides a feasible way for BiOX photocatalyst to remove co-existent pollutants and may have a practical application.
2-Phenylethylamine (2-PEA) is one of the main ingredients for stimulants. Therefore, it is necessary to limit its use and illegal trade by conveniently detecting 2-PEA vapour. Here, a QCM based 2-PEA gas sensor was constructed by using aldehyde functionalized mesoporous carbon (FDU-15-CHO) as sensing materials designed according to Schiff base adsorption role. The 2D hexagonal mesoporous structures of the sensing material have been confirmed by small-angle X-ray diffraction (SXRD), transmission electron microscopy (TEM), and N2 adsorption-desorption isotherms. The covalent grafting of aldehyde group onto the FDU-15 was confirmed by Fourier transform infrared spectroscopy (FT-IR). FDU-15-CHO based Quartz Crystal Microbalance (QCM) sensor shows better sensitivity to 2-PEA than its parent FDU-15. Besides, the detection limit of FDU-15-CHO based sensor can reach down to 1 ppm, and its selectivity and reproducibility are satisfactory. The high concentrations of active sites in the mesopores of FDU-15 are believed to facilitate 2-PEA adsorption, and thus the presence of the -CHO group leading to sensitive and selective response, which is verified by Gaussian simulation
Taking advantage of the Warburg effect in cancer cells, glucose conjugation has emerged as a useful strategy for targeted delivery of anticancer agents. Pristimerin is a naturally occurring triterpenoid that displays potent but non-selective cytotoxicity. We developed a convergent and modular approach to construction of glucose−payload conjugates featuring copper-mediated azide−alkyne cycloaddition and prepared a glucose conjugate of pristimerin through this approach. The anticancer activity of this conjugate was evaluated in cancer cells and normal cells; however, the selectivity toward cancer cells was not significantly improved. We then examined the extracellular stability of the conjugate and found that its ester linkage was cleaved rapidly in Dulbecco's Modified Eagle's Medium at 37 ℃, which resulted in the release of pristimerin. In fact, the inorganic components in this medium were sufficient to induce the cleavage. Given that the subtle difference between intrinsic stability and extracellular stability of the conjugate linker is often underappreciated, this work highlights the importance of the latter in the development of target-selective conjugates.
Respiratory antibiotics have been proven clinically beneficial for the treatment of severe lung infections such as Pseudomonas aeruginosa. Maintaining a high local concentration of inhaled antibiotics for an extended time in the lung is crucial to ensure an adequate antimicrobial efficiency. In this study, we aim to investigate whether an extended exposure of ciprofloxacin (CIP), a model fluoroquinolone drug, in the lung epithelial lining fluid (ELF) could be achieved via a controlled-release formulation strategy. CIP solutions were intratracheally instilled to the rat lungs at 3 different rates, i.e., T0h (fast), T2h (medium), and T4h (slow), to mimic different release profiles of inhaled CIP formulations in the lung. Subsequently, the concentration-time profiles of CIP in the plasma and the lung ELF were obtained, respectively, to determine topical exposure index (ELF-Plasma AUC Ratio, EPR). The in silico PBPK model, validated based on the in vivo data, was used to identify the key factors that influence the disposition of CIP in the plasma and lungs. The medium and slow rates groups exhibited much higher EPR than that fast instillation group. The ELF AUC of the medium and slow instillation groups were about 200 times higher than their plasma AUC. In contrast, the ELF AUC of the fast instillation group was only about 20 times higher than the plasma AUC. The generated whole-body PBPK rat model, validated by comparison with the in vivo data, revealed that drug pulmonary absorption rate was the key factor that determined pulmonary absorption of CIP. This study suggests that controlled CIP release from inhaled formulations may extend the exposure of CIP in the ELF post pulmonary administration. It also demonstrates that combining the proposed intratracheal installation model and in silico PBPK model is a useful approach to identify the key factors that influence the absorption and disposition of inhaled medicine.
Developing convenient, fast-response and high-performance formaldehyde detection sensor is significant but challenging. Herein, two CeO2 phases (Fm3m and P42/mnm), three facets (CeO2(100), CeO2(110) and CeO2(111)) and three adsorption sites (top, bridge and hollow) are selected as substrate to interact with formaldehyde. Twenty-eight candidated transition metals (TM) are doped on CeO2 surfaces to investigate the performance of detecting formaldehyde by density functional theory. It shows that (ⅰ) CeO2 in a cubic fluorite structure with the space group Fm3m is suitable for formaldehyde adsorption compared with P42/mnm; (ⅱ) TM-CeO2(100) (TM = Au, Hf, Nb, Ta, Zr) are considered as candidated materials to absorb formaldehyde ascribed to lower adsorption energies. The d-band center, partial density of states, charge density difference and electron localization function are employed to clarify the mechanism of TM-doped CeO2 improving the performance of formaldehyde adsorption. It obviously displays that TM doped CeO2(100) changes the d orbit and rearranges electrons resulting in the superior ability to the adsorbed formaldehyde. This work provides theoretical guidance and experimental motivation for the development of novel formaldehyde sensor based on metal oxide semiconductor materials.
The biodegradable substitution materials for bone tissue engineering have been a research hotspot. As is known to all, the biodegradability, biocompatibility, mechanical properties and plasticity of the substitution materials are the important indicators for the application of implantation materials. In this article, we reported a novel binary substitution material by blending the poly(lactic-acid)-co-(trimethylene-carbonate) and poly(glycolic-acid)-co-(trimethylene-carbonate), which are both biodegradable polymers with the same segment of flexible trimethylene-carbonate in order to accelerate the degradation rate of poly(lactic-acid)-co-(trimethylene carbonate) substrate and improve its mechanical properties. Besides, we further fabricate the porous poly(lactic-acid)-co-(trimethylene-carbonate)/poly(glycolic-acid)-co-(trimethylene-carbonate) scaffolds with uniform microstructure by the 3D extrusion printing technology in a mild printing condition. The physicochemical properties of the poly(lactic-acid)-co-(trimethylene-carbonate)/poly(glycolic-acid)-co-(trimethylene-carbonate) and the 3D printing scaffolds were investigated by universal tensile dynamometer, fourier transform infrared reflection (FTIR), scanning electron microscope (SEM) and differential scanning calorimeter (DSC). Meanwhile, the degradability of the PLLA-TMC/GA-TMC was performed in vitro degradation assays. Compared with PLLA-TMC group, PLLA-TMC/GA-TMC groups maintained the decreasing Tg, higher degradation rate and initial mechanical performance. Furthermore, the PLLA-TMC/GA-TMC 3D printing scaffolds provided shape-memory ability at 37 ℃. In summary, the PLLA-TMC/GA-TMC can be regarded as an alternative substitution material for bone tissue engineering.